JP2001142182A - Color image forming method using silver halide color photographic sensitive material for photographing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method in which the effect of enhancing color reproducibility and sharpness produced by a DIR coupler is maintained even when a silver halide color photographic sensitive material used in photographing is subjected to a combination of image processing and development and a color print is obtained without subsidiary distortion of color balance and gradation in ordinary image processing and to provide an image forming method suitable also for rapid processing and simple processing. SOLUTION: A silver halide color photographic sensitive material for photographing containing a coupler which forms no color and releases a photographically useful group or its precursor while forming a ring by intramolecular nucleophilic substitution reaction by a nitrogen atom derived from a developing agent and combined directly to the coupling position in the product of coupling reaction with the developing agent is developed, the image information of the resulting image is photo-electrically read and image processing, retouch and output to a printer are carried out to obtain a color print.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material for photography. Specifically, the present invention relates to a color image forming method which is versatile in the color photographic market, has simplicity and quickness, and can obtain a color print with sufficient image quality.

[0002]

2. Description of the Related Art In the current color photographic market, it is desired that the time between a photograph shop receiving a photographed color film from a customer and passing a color print to the customer be short. There is a demand for rapid development of color photographic paper for producing color prints from developed films. On the other hand, in the color photography industry, along with the diversification of image forming means such as color ink jet and color thermal transfer, there is a demand for further improvement of image quality of color prints in order to respond to the user's photographic quality orientation.

As a means for meeting the demands of the market on both sides, there has been proposed a method of speeding up or simplifying a developing process and performing image processing on an obtained image to maintain or improve image quality. Specifically, Japanese Patent Application Laid-Open No. 11-52
Nos. 526, 11-52527 and 11-5252
No. 8 performs simple and quick processing, omitting the fixing step and the bleaching step or both in color negative film development processing, and reads the obtained image photoelectrically to produce time-series electrical image information. A method is disclosed in which the image information is subjected to image quality correction by image processing to obtain an image equivalent to or superior to that obtained when standard development is performed without omitting steps.

On the other hand, in response to the latter demand for improving the image quality of color prints and responding to the photographic quality orientation of users, the development of photosensitive materials for photography having high sensitivity and excellent in sharpness and color reproducibility has been strongly promoted. Requested. As a means for improving sharpness, it is known that the use of a DIR coupler which reacts with an oxidized form of a developing agent and releases a development inhibitor is effective. DIR couplers are broadly classified into those which release a development inhibitor or a precursor thereof by a coupling reaction with an oxidized form of a developing agent at the time of development and simultaneously form a dye, and those of a type which form a dye with an oxidized form of a developing agent. There is a type that releases a development inhibitor or a precursor thereof, but the reaction product is a compound that is not substantially a dye or a compound that flows out into a developer,
The latter two types of compounds are known by the terms colorless couplers and outflow couplers, respectively.

The latter type of DIR couplers, ie, colorless couplers and outflow couplers, do not substantially contribute to the formation of a color image and are therefore used in a photosensitive layer which develops any color without causing color turbidity. This is an advantage over the former. No-color couplers include U.S. Pat. No. 4,482,629 and JP-A-63-37350.
Those described in specifications such as U.S. Pat. No. 5,026,628 and European Patent Publication Nos. 0443530 and 0514869 are known. On the other hand, as an outflow coupler, Japanese Patent Publication No. 1-52742, JP-A-4-356
No. 042 and No. 8-44011.

When a photosensitive material containing these colorless couplers or outflow couplers is used in combination with the above-described image processing to form an image, a reading load upon photoelectrically reading an image obtained by development by a scanner is increased. This is advantageous in that the reading accuracy is improved and the reading accuracy is improved, which is effective for improving the color reproducibility and sharpness. However, on the other hand, color prints obtained from these non-colorless or effluent coupler-containing materials have gradation distortions that cannot be sufficiently corrected by image processing, and as a result, color prints obtained by image processing Has a shortage of low concentration parts,
Distortion of the color balance in the intermediate density portion, insufficient gradation reproduction, and the like are observed. Therefore, it was found that if the distortion of the gradation can be corrected, the image quality can be further improved.
This distortion is considered to be complicatedly related to the exposure dependence of these colorless or outflow couplers, the coupling competition relationship with the main coupler, each color tone of the image area, and the exposure level relationship of each density region. , Has not been resolved. Therefore, there is a need for a means for responding to the needs of the market at a higher level to speed up the development processing and improve the photographic image quality.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned defects associated with the processing of a color photographic light-sensitive material so as to speed up the development process and improve the image quality of a color print. Specifically, from a silver halide color photographic light-sensitive material for photography, an effect of improving color reproducibility and sharpness is exhibited by a DIR coupler, and there is no secondary color balance or gradation distortion caused by the DIR coupler. An object of the present invention is to provide a color image forming method for obtaining a color print. A further object of the present invention is to provide a color image forming method which does not impair the image quality improvement effect of the DIR coupler even when simple processing or rapid processing is performed.

[0008]

In order to solve the above-mentioned problems, the present inventor has proposed a type of DIR coupler, a positive effect of improving color reproducibility and sharpness brought by the coupler, and a gradation which cannot be corrected by image processing. Focusing on the relationship with the negative effect of image distortion, we searched for a DIR coupler that has a large effect of improving color reproducibility and sharpness, and that has small gradation distortion that cannot be corrected by image processing. The inventors have found that specific DIR couplers having characteristics suitable for the purpose of the present invention have reached the present invention described below.

1. In a color image forming method using a silver halide color photographic light-sensitive material for photography containing at least one coupler which releases a photographically useful group or a precursor thereof by a coupling reaction with an oxidized developing agent, the coupler comprises a coupling agent. A coupler which releases a photographically useful group or its precursor with ring formation by an intramolecular nucleophilic substitution reaction by a nitrogen atom derived from a developing agent in a reaction product and directly bonded to a coupling position, and said color image formation A step of: (1) subjecting the photosensitive material to a development process;
(2) a series of steps of photoelectrically reading image information of an image obtained by the development process, converting the image information into electrical image information, and (3) performing image processing on the electrical image information. Color image forming method.

[0010] 2. In a color image forming method using a silver halide color photographic light-sensitive material for photography containing at least one coupler which releases a photographically useful group or a precursor thereof by a coupling reaction with an oxidized developing agent, the coupler comprises a coupling agent. A coupler which releases a photographically useful group or its precursor with ring formation by an intramolecular nucleophilic substitution reaction by a nitrogen atom derived from a developing agent in a reaction product and directly bonded to a coupling position, and said color image formation A step of: (1) subjecting the photosensitive material to a development process;
(2) image information of an image obtained by the development process is photoelectrically read and converted into electrical image information; (3) image processing is performed on the electrical image information; and (4) image-processed electrical information is obtained. 2. The color image forming method according to the above item 1, comprising a series of steps of outputting image information to a printer to obtain a color print.

3. 3. The color image forming method as described in 1 or 2, wherein the coupler is represented by the following general formula (I). General formula (I) COUP-AEB (wherein COUP represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents
In the coupling product of COUP and oxidized developing agent, a 4- to 8-membered ring is formed by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and the electrophilic site E. It represents a divalent linking group or a single bond capable of releasing B, and may be bonded to COUP at the coupling position of COUP, or may be bonded to COUP at a position other than the coupling position of COUP.
B represents a photographically useful group or a precursor thereof).

4. The development processing is a development processing that does not include at least one of (1) a bleaching step comprising at least one of bleaching and bleach-fixing processing, and (2) a fixing step comprising at least one of fixing and bleach-fixing processing. 4. The color image forming method according to any one of the above items 1 to 3, wherein

5. The above-mentioned development processing is carried out at a color development of 45 °.
C. The color image forming method as described in any one of 1 to 4 above, wherein the development is performed at a temperature of at least C or within 1 minute.

By the above-mentioned coupling reaction with the oxidized developing agent, the nucleophilic substitution reaction in the molecule by the nitrogen atom derived from the developing agent and directly bonded to the coupling position in the product of the coupling reaction, accompanied by ring formation. A coupler that releases a photographically useful group or a precursor thereof is a colorless coupler or an outflow coupler (hereinafter, when referring to both the colorless and outflow couplers of the present invention, they are referred to as "colorless couplers" to represent both). The light-sensitive material contained not only exerts the original effects of the DIR coupler on the image quality such as improvement in sharpness and color reproducibility, but also has little gradation distortion that cannot be sufficiently corrected by image processing. By developing the material, applying image processing to the obtained image information and outputting it to a color print, there is no gradation distortion, and sharpness and color reproducibility are improved. , Images of excellent quality can be obtained.

In the colorless coupler, the step of releasing a photographically useful group or a precursor thereof during the color development step is as follows:
Although it is a two-step process of the intramolecular nucleophilic substitution reaction following the coupling reaction, it has the advantage of high coupling activity and excellent stability, but it is difficult to correct in image processing. It is presumed that this is related to the fact that the gradation distortion is small.

The colorless couplers described above, particularly the couplers represented by the general formula (I), have a small gradation distortion that is difficult to correct by image processing, so that the effect of improving image quality by image processing can be sufficiently exhibited. . Therefore, even if the development processing is simplified or the processing time is shortened, the image can be corrected by image processing to have an image quality equal to or higher than that obtained when standard development is performed. That is, the development process of the color light-sensitive material for photography generally comprises color development, bleaching, fixing, washing and / or stabilization,
Further, an image stabilizing bath may be added between each partial process as an intermediate washing process or a final immersion process.However, an image obtained when the bleaching process is omitted from this normal developing process is a mixture of developed silver and a dye image. The image obtained when the fixing step was omitted was an image in which silver halide and a dye image were mixed, and the desilvering step was omitted, such as bleach-fixing or omission of both bleaching and fixing. An image sometimes obtained is an image in which developed silver, undeveloped silver halide, and a dye image are mixed. In the method of the present invention, even if such an image is obtained, the image is substantially eliminated from the image obtained by performing a standard development process by removing or reducing the influence of the dye image and the inclusion by image processing. It is possible to correct the image quality and output it. Therefore, both shortening of the development processing time and improvement of image quality such as color reproducibility and sharpness without gradation distortion can be achieved.

In the case where the development time of the photosensitive material is to be reduced at a high temperature or the development time is shortened by using a highly active developer, the image forming method of the present invention can be applied to such rapid processing. This is advantageous because the distortion of the gradation associated with is reduced. Therefore, the present invention is particularly effective in short-time processing in which a color negative film is developed at a temperature of 38 ° C. over a period of 3 minutes and 15 seconds at 45 ° C. or more or within 1 minute. Can be demonstrated. Hereinafter, the details of the present invention will be further described by embodiments.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a colorless coupler having a structure in which a silver halide color photographic material (hereinafter also referred to as a color photographic material or simply a photographic material) undergoes a process of releasing a specific photographically useful group. By using, on the image quality,
Since low replenishment development and / or rapid development or both can be performed without causing adverse effects on the development work, first, the colorless coupler used in the present invention, and then the image processing of the present invention The details of the photosensitive material containing the non-color coupler and the development process will be described below.

The photographically useful group-releasing coupler used in the present invention is coupled with an oxidized developing agent, and the intramolecular nucleophilic reaction with a nitrogen atom derived from the developing agent in the coupling product and directly bonded to the coupling position. It releases a photographically useful group or a precursor thereof with ring formation by a substitution reaction, and is preferably represented by the following general formula (I). Formula (I) COUP-A-E -B In the formula, COUP represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents COUP and an oxidized developing agent. In the product of coupling with the compound, the nitrogen atom directly attached to the coupling position derived from the developing agent and the intramolecular nucleophilic substitution reaction between the electrophilic site E can release B with a 4- to 8-membered ring formation. It represents a possible divalent linking group or single bond, and may be bonded to COUP at the coupling position of COUP, or may be bonded to COUP at a position other than the coupling position of COUP. B represents a photographically useful group or a precursor thereof.

Examples of the developing agent which can be used in the present invention include US Pat. Nos. 2,919,015, 2,592,364 and 5,240,821.
No., JP-A-48-64933, JP-A-4-121739, page 9, upper right column 1
Phenylenediamine and aminophenol-based developing agents described in line 11 to the lower left column, line 11, EP Patent No. 545491A1,
Sulfonylhydrazine-based developing agents described in 565165A1 and the like, JP-A-8-286340, 9-152702, and carbamoylhydrazine-based developing agents described in 9-211818 and the like, preferably 4- Amino-N, N-diethylaniline, 3
-Methyl-4-amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-
P-phenylenediamine based developing agents such as methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline .

The coupler residue represented by COUP includes yellow coupler residues generally known as photographic couplers (for example, open-chain ketomethine type coupler residues such as acylacetanilide and malondianilide), and magenta coupler residues. (E.g., coupler residues such as 5-pyrazolone type or pyrazolotriazole type), cyan coupler residues (e.g., phenol type, naphthol type or pyrrolotriazole type coupler residues), US Pat. -128824, 7-128823, 6-222526, 9-25
No. 8400, No. 9-258401, No. 9-269573, Yellow having a new skeleton described in No. 6-27612, a magenta or cyan dye-forming coupler residue or other Coupler residues (see, for example, US Pat.
No. 345, coupler residues that form a colorless substance by reacting with an oxidized aromatic amine-based developing agent described in No. 3,982,041 and the like, and aromatic amine-based compounds described in U.S. Pat. (A coupler residue that reacts with an oxidized developing agent to form a black or neutral color substance).

The coupler residue represented by COUP may be a monomer or a part of a dimer coupler, oligomer or polymer coupler, in which case the coupler contains more than one PUG. May be. Preferred examples of the COUP of the general formula (I) are shown below, but the COUP of the general formula (I) is not limited thereto.

[0023]

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[0024]

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In the formula, * represents a bonding position to A. X is hydrogen
Atom, halogen atom (for example, fluorine atom, chlorine atom,
Bromine atom, iodine atom), R₃₁-, R₃₁O-, R₃₁S-, R₃₁OC
OO-, R₃₂COO-, R₃₂(R₃₃) NCOO-, R₃₂CON (R₃₃)-
Y is an oxygen atom, a sulfur atom, R ₃₂N = or R₃₂Indicates ON =. This
Where R₃₁Is an alkyl group, alkenyl group, alkynyl
Group, an aryl group or a heterocyclic group.

The alkyl group represented by R ₃₁ is preferably a substituted or unsubstituted alkyl group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms, and specific examples include methyl, ethyl, propyl, and isopropyl. , Butyl, isobutyl,
t-butyl, t-amyl, hexyl, cyclohexyl, 2-
Ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, and octadecyl. The alkenyl group and alkynyl group represented by R ₃₁ are preferably a substituted or unsubstituted alkenyl group or alkynyl group having 2 to 32 carbon atoms, more preferably 2 to 22 carbon atoms, and include cyclic ones. Specific examples include vinyl, 2-propenyl, ethynyl, and 2-propynyl. Here, when the alkyl group, the alkenyl group, and the alkynyl group have a substituent, the “carbon number” means the total carbon number including the carbon number of the substituent. Similarly, the group other than the alkyl group, the alkenyl group and the alkynyl group means the total carbon number including the carbon number of the substituent.

The aryl group represented by R ₃₁ is preferably a substituted or unsubstituted aryl group having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms.
Tolyl and naphthyl. The heterocyclic group represented by R ₃₁ preferably has 1 to 32 carbon atoms, more preferably 1 to 32 carbon atoms.
~ 22 substituted or unsubstituted 3 to 8 members (preferably 5 or 6
Member), and specific examples thereof include 2-furyl and 2-furyl.
Pyrrolyl, 2-thienyl, 3-tetrahydrofuranyl, 4-pyridyl, 2-pyrimidinyl, 2- (1,3,4-thiadiazolyl),
2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselenazolyl, 2-quinolyl, 2-
Oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl, 2- (1,3,4 oxadiazolyl), 2-imidazolyl and the like.

R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₃₂ and R ₃₃ have the same meaning as R ₃₁ . Preferably, X represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, or R ₃₂ CON (R ₃₃ )-, Y represents an oxygen atom, R ₃₁ represents an alkyl group or an aryl group, R ₃₂ and R ₃₃ each independently represents a hydrogen atom, an alkyl group or an aryl group.

Suitable substituents for the groups described above and below and "substituents" described below include, for example, halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, alkyl group, fluoroalkyl Group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acyl group, alkyl or arylsulfonyl group, acylamino group, alkyl or arylsulfonylamino group, carbamoyl group, sulfamoyl group, Alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an aminocarbonyloxy group, and an aminocarbonylamino group.

R ₁₁ and R ₁₂ are each independently R ₃₂ CO—, R ₃₁ O
_{CO-, R 32 (R 33)} NCO-, R 31 SOn-, R 3 2 (R 33) NSO 2 -, a group represented by a cyano group or the following formula. Where R ₃₁ , R ₃₂
And R ₃₃ are as defined above, and n represents 1 or 2.

[0031]

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Y ₁ is an oxygen atom, a sulfur atom, or -N (R ₃₂ )-
And Z represents a 5- or 6-membered nitrogen-containing heterocycle together with N and Y ₁ (a non-metal atom group necessary for forming a condensed ring which may be condensed with a benzene ring, a naphthalene ring, or a heterocycle (preferably R ₁₃ represents a group having the same meaning as R ₃₁ described above, and R ₁₄ represents R ₃₂ —, R ₃₂ CON (R ₃₃ ) —, R ₃₂ (R ₃₃ ) N—, and R ₃₁ SO ₂ N. (R
₃₂ )-, R ₃₁ S-, R ₃₁ O-, R ₃₁ OCON (R ₃₂ )-, R ₃₂ (R ₃₃ ) NCON (R
₃₄₎ - represents _{R 31 OCO-, R 32 (R} 33) NCO- or a cyano group. Here, R ₃₁ , R ₃₂ and R ₃₃ are as defined above, and R ₃₄ is R
Represents the same group as ₃₂ .

[0033] represents each R ₁₅ and R ₁₆ independently represents a hydrogen atom or a substituent, preferably _{R 31 -, R 32 CON (} R 33) -, R 31 SO 2 N
(R ₃₂ )-, R ₃₁ S-, R ₃₁ O-, R ₃₁ OCON (R ₃₂ )-, R ₃₂ (R ₃₃ ) NCON
_{(R 34) -, R 31} OCO-, R 32 (R 33) NCO-, a halogen atom or a cyano group, more preferably a group represented by R _31. Here, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are as defined above.

R₁₇Represents a substituent, and p represents an integer of 0 to 4.
And q represents an integer of 0 to 3. R₁₇Of the substituent represented by
A good example is R₃₁-, R₃₂CON (R₃₃)-, R₃₁OCON (R₃₂)
-, R ₃₁SO_TwoN (R₃₂)-, R₃₂(R₃₃) NCON (R₃₄)-, R₃₁S-, R₃₁O
-, A halogen atom. Where R₃₁, R₃₂, R₃₃
And R₃₄Is as defined above. Also, p and q are 2 or more
For each R₁₇Are the same but different
Or an adjacent R₁₇Even if they combine to form a ring
Good. Preferred embodiments of the general formulas (I-1E) and (I-2E) are water
At least one of the ortho positions of the acid group is R₃₂CONH-, R₃₁OCONH
-Or R₃₂(R₃₃) NCONH- substituted.

R₁₈Represents a substituent, and r represents an integer of 0 to 6.
And s represents an integer of 0 to 5. R₁₈Of the substituent represented by
A good example is R₃₂CON (R₃₃)-, R₃₁OCON (R₃₂)-, R₃₁
SO_TwoN (R₃₂)-, R₃₂(R₃₃) NCON (R₃₄)-, R₃₁S-, R₃₁O-, R
₃₂(R₃₃) NCO-, R₃₂(R₃₃) NSO_Two-, R ₃₁OCO-, cyano group or
A halogen atom. Where R₃₁, R₃₂, R₃₃You
And R₃₄Is as defined above. If r and s are 2 or more,
Each R₁₈May be the same or different
Then the adjacent R₁₈They may combine with each other to form a ring.
Preferred embodiments of general formulas (I-1F), (I-2F) and (I-3F)
Means that the ortho position of the hydroxyl group is R₃₂CONH-, R₃₂HNCONH-, R₃₂(R
₃₃) NSO_Two-Or R₃₂It has been substituted with NHCO-.

R₁₉Represents a hydrogen atom or a substituent, and is preferably
H, R₃₂-, R₃₂CON (R₃₃)-, R₃₁SO_TwoN (R₅₃)-, R₃₁S-, R
₃₁O-, R₃₁OCON (R₃₂)-, R₃₂(R₃₃) NCON (R₃₄)-, R₃₁OCO-,
R₃₂(R_{Three Three}) NSO_Two-, R₃₂(R₃₃) NCO-, halogen atom or shear
And more preferably R ₃₁Is a group represented by
You. Where R₃₁, R₃₂, R₃₃And R₃₄Is synonymous with the above
You.

R₂₀And R_{twenty one}Are each independently a hydrogen atom or
Represents a substituent, preferably R₃₂-, R₃₂CON (R₃₃)-, R₃₁SO_TwoN
(R₃₂)-, R₃₁S-, R₃₁O-, R₃₁OCON (R₃₂)-, R₃₂(R₃₃) NCON
(R₃₄)-, R₃₂(R₃₃) NCO-, R₃₂(R₃₃) NSO_Two-, R₃₁OCO-, halo
Gen atom and cyano group, more preferably R
₃₂(R₃₃) NCO-, R₃₂(R₃₃) NSO_Two-, Trifluoromethyl group,
R ₃₁Represents OCO- and cyano groups. Where R₃₁, R₃₂, R₃₃
And R₃₄Is as defined above.

E is -CO-, -CS-, -COCO-, -SO-, -SO _2- , -P
(= O) (R ₅₁ )-, -P (= S) (R ₅₁ )-, ｛R ₅₁ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group,
Represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkylthio group, an alkenylthio group, an alkynylthio group, or an arylthio group. An electrophilic group such as 又 は or
-C (R ₅₂ ) (R ₅₃ )-, (R ₅₂ and R ₅₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; each alkyl group, alkenyl group, alkynyl group, an aryl group, a heterocyclic group represents the same meaning.) as described in R _31, is preferably -CO-.

A is obtained by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E in the coupling product of COUP and the oxidized developing agent (preferably 4 To 8 members, more preferably 5
With a ring formation of from 7 to 7 members, more preferably 6 members
Represents a divalent linking group or a single bond capable of releasing B. Examples of the linking group represented by A include the following. *-(CO) _n1- (Y) _n2- [C (R ₄₁ ) (R ₄₂ )] _n4 -** *-(CO) _n1- [N (R ₄₃ )] _n3- [C (R ₄₁ ) ( R ₄₂ )] _n4 -** *-(Y) _n2- (CO) _n1- [C (R ₄₁ ) (R ₄₂ )] _n4 -** *-[N (R ₄₃ )] _n3- (CO) _n1 -[C (R ₄₁ ) (R ₄₂ )] _n4 -***-(CO) _n1- [C (R ₄₁ ) (R ₄₂ )] _n4- (Y) _n2 -** *-(CO) _n1- [C (R ₄₁ ) (R ₄₂ )] _n4- [N (R ₄₃ )] _n3 -** *-(Y) _n2 -**, *-[N (R ₄₃ )] _n3 -**

In the formula, * represents a site that binds to COUP;
* Represents a site bonded to E, Y represents an oxygen atom or a sulfur atom, and R ₄₁ , R ₄₂ and R ₄₃ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
A Hajime Tamaki (these alkyl groups, alkenyl group, alkynyl group, aryl group, heterocyclic group has the same meaning as described in R _31.) Represent, each of R _41, R ₄₂ and R ₄₃
May combine with each other or with COUP to form a ring.

R ₄₁ and R ₄₂ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ₄₃
Is preferably a hydrogen atom or an alkyl group. n1 and
n3 represents an integer of 0 to 2, n2 represents 0 or 1, n4 represents an integer of 1 to 5 (when n3 and n4 represent an integer of 2 or more, N (R ₄₃ ) and C ( R ₄₁ ) and (R ₄₂ ) may be the same or different.) And a nitrogen atom directly derived from the developing agent in the coupling product of COUP and the oxidized developing agent and directly bonded to the coupling position. The values of n1 + n2 + n4, n1 + n3 + n4, n2 and n3 are selected so that a 4- to 8-membered ring is formed by an intramolecular nucleophilic substitution reaction with the electrophilic site E. However, when —N (R ₄₃ ) — is directly bonded to E, R ₄₃ is preferably not a hydrogen atom. Further, when the linking group A is linked at the coupling position of COUP, the portion directly linked to COUP is not -Y-.

The bonding position between COUP and the linking group A is determined by the intramolecular nucleophilic reaction between the nitrogen atom derived from the developing agent and the electrophilic site E in the coupling product after the coupling reaction between the coupler and the oxidized developing agent. By substitution reaction (preferably 4 to
8 members, more preferably 5 to 7 members, even more preferably 6 members
Any member capable of releasing B with ring formation can be used, but is preferably at or near the coupling position of COUP (the atom next to the coupling position or the atom next to it). . The coupler of the present invention wherein the linking group A is bonded to 1) the coupling position, 2) the atom adjacent to the coupling position and 3) the adjacent atom adjacent to the coupling position of the coupler residue represented by COUP; With the coupler of the present invention
Oxidized aromatic amine developing agent represented by ArNH ₂ (Ar =
The reaction with NH) can be represented by the following formula.

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B represents a photographically useful group or a precursor thereof. B
Is preferably represented by the following general formula. #-(T) _k -PUG In the formula, # represents a site linked to E, T represents a timing group capable of releasing PUG after release from E, and k
Represents an integer of 0 to 2, preferably 0 or 1, and PUG represents a photographically useful group.

As a timing group represented by T, for example, a group capable of releasing PUG by utilizing a hemiacetal cleavage reaction described in US Pat. Nos. 4,146,396, 4,625,516 or 4,986,297; U.S. Pat.No. 4,424,962,
No. 5719017 or a group releasing PUG by using an intramolecular ring closure reaction described in No. 57,099,87, etc., JP-B-54-39727, JP-A-57-136640, JP-A-57-154234, JP-A-4-1992 No. 261530, same
No. 4-211246, No. 6-324439, No. 9-114058, U.S. Pat.
Group releasing PUG by electron transfer via π electrons described in 4409323 or 4421845, JP-A-57-179842,
JP-A-4-261530, a group that releases PUG by generating carbon dioxide as described in JP-A-5-313322, a group that releases PUG by a hydrolysis reaction of imino ketal described in U.S. Pat. No. 2,626,317, a group which releases PUG by an ester hydrolysis reaction, or a group which releases PUG by utilizing a reaction with a sulfite ion described in European Patent No. 5,720,84. Preferred examples of the timing group represented by T include, for example, the following timing groups, but are not limited thereto.

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In the formula, * binds to the electrophilic site E or **
** indicates a site that binds to PUG or *
You. Y_TwoRepresents an oxygen atom or a sulfur atom, preferably oxygen
Represents an atom. R₆₁Represents a substituent, preferably R₃₁-, R
₃₂CON (R₃₃)-, R₃₁SO_TwoN (R₃₂)-, R ₃₁S-, R₃₁O-, R₃₁O
CON (R₃₂)-, R₃₂(R₃₃) NCON (R₃₄)-, R₃₂(R₃₃) NCO-, R
₃₂(R ₃₃) NSO_Two-, R₃₁OCO-, halogen atom, nitro group and
And a cyano group. Where R₃₁, R₃₂, R₃₃And R₃₄Is
Is synonymous with the above. R₆₁Is R₆₂, R₆₃, R₆₄Conclude with any of
They may combine to form a ring. n₁Represents an integer of 0 to 4.
 n₁Each represents an integer of 2 or more,₆₁Are the same
Or different, R₆₁Join together to form a ring
May be implemented.

R ₆₂ , R ₆₃ and R ₆₄ represent the same groups as R _32, and n ₂ represents 0 or 1. R ₆₂ and R ₆₃ may combine to form a spiro ring. R ₆₂ and R ₆₃ are preferably a hydrogen atom or a (1 to 20 carbon atoms, preferably 1 to 10) alkyl group, (carbon number 2 to 32, preferably 2 to 10) alkenyl, (2 carbon atoms 32, preferably 2-10) alkynyl groups, more preferably a hydrogen atom. R ₆₄ is preferably an alkyl group (having 1 to 20, preferably 1 to 10 carbon atoms), an alkenyl group (having 2 to 20, preferably 2 to 10 carbon atoms), an alkenyl group (having 2 to 20, preferably 2 to 10 carbon atoms) 10) alkynyl group or aryl group (of 6 to 20, preferably 6 to 10 carbon atoms). R ₆₅ is R _32- , R ₃₂ (R ₃₃ ) NCO-, R ₃₂ (R ₃₃ ) NSO _2- ,
R ₃₁ OCO- and R ₃₂ CO- are represented. Here, R ₃₁ , R ₃₂ and R ₃₃ are as defined above. R ₆₅ preferably represents R ₃₂ and more preferably represents an aryl group having 6 to 20 carbon atoms.

The photographically useful group represented by PUG may be any PUG known in the art. Examples thereof include development inhibitors, bleach accelerators, development accelerators, dyes, bleach inhibitors, couplers, developing agents, development aids, reducing agents,
Silver halide solvent, silver complexing agent, fixing agent, image toner,
Includes stabilizers, hardeners, tanning agents, fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers, desensitizers, and fluorescent brighteners, It is not limited to these. Preferably, the PUG is a development inhibitor (e.g., U.S. Pat.
No. 384657, No. 3615506, No. 3617
No. 291, No. 3733201, No. 5200306
No., British Patent No. 1450479, European Patent No. 8677
Nos. 63, 892306 and 892307), bleaching accelerators (for example, Research Discl)
osure 1973, Item No. 11449, European Patent 193
No. 389, U.S. Pat. Nos. 4,959,299 and 4,912.
No. 024, No. 5,318,879), dyes (for example, U.S. Pat. Nos. 3,880,658, 3,931,144, 3,932,380, and 39).
Dyes described in Nos. 32381 and 39429987), couplers (for example, US Pat. No. 2,998,314)
No. 2,808,329, No. 2,689,793, No. 2,742,832, No. 5,348,847, etc.), development aids (for example, US Pat. No. 4,895,595)
No. 78, development aids described in JP-A-10-48787 and the like, development accelerators (for example, US Pat. No. 4,390,618)
No., development accelerators described in JP-A-2-56543),
Reducing agents (for example, JP-A-63-109439 and JP-A-63-1);
No. 28342) and optical brighteners (for example, the optical brighteners described in US Pat. Nos. 4,774,181 and 5,236,804). The pKa of the conjugate acid of PUG is 1
It is preferably 3 or less, more preferably 11 or less.

PUG is more preferably a development inhibitor,
Preferred development inhibitors are mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptothiadiazole derivatives, mercaptooxadiazole derivatives, mercaptoimidazole derivatives, mercaptobenzimidazole derivatives, mercaptobenzthiazole derivatives, mercaptobenzoxazole derivatives, tetrazole derivatives, 1,2, Examples thereof include a 3-triazole derivative, a 1,2,4-triazole derivative, a purine derivative, and a benzotriazole derivative. In the present invention, at least the following groups are not PUG.

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In the formula, *** represents a site linked to the electrophilic site represented by E or the timing group represented by T, and R ₇₁ represents a substituted or unsubstituted alkyl group, alkenyl group, or alkynyl group. And R ₇₂ represents an unsubstituted alkyl group, alkenyl group, or alkynyl group.

Preferred embodiments of the colorless coupler used in the present invention are those represented by the above formula (I-2) or (I-3), and more preferably (I-3) (formula (I) -2), (I-
In 3), A, E, B and preferred ranges thereof are the same as those described above. ). A more preferred embodiment of the general formula (I-3) is represented by the following general formula (I-3a), more preferably the following general formula (I-3b), and particularly preferably the general formula (I-3c) expressed. In addition, general formula (I-3c) and Ar
Oxidized form of aromatic amine developing agent represented by NH ₂ (Ar = N
The structure of the cyclized product obtained by the reaction with H) can be represented by the general formula (II).

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In the formula, Q ₁ and Q ₂ are each a non-metallic atomic group necessary to form a 5- or 6-membered ring and to cause a coupling reaction with an oxidized developing agent at an atom at the base of X. Yes, X, T, k, PUG, R ₁₈ and R ₃₂ are as defined above. s
Represents an integer of 0 to 4. R ₄₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and more preferably represents an alkyl group. It represents (these alkyl groups, alkenyl group, alkynyl group, aryl group, heterocyclic group has the same meaning as described in R _31.). Hereinafter, specific examples of the coupler contained in the light-sensitive material used in the present invention will be described, but the present invention is not limited thereto.

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Specific examples of the synthesis of the coupler used in the present invention are shown below. Synthesis of coupler of compound example (3) A coupler of compound example (3) was synthesized according to the following scheme.

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Synthesis of Compound 3b Compound 3a (50 g) and o-tetradecyloxyaniline (51.1 g)
N, N-dimethylacetamide (250 ml (hereinafter,
)) N, N-dimethylacetamide of dicyclohexylcarbodiimide (41.3 g) was added to the solution at 30 ° C.
(60 mL) solution was added dropwise. After the reaction solution was stirred at 50 ° C. for 1 hour, ethyl acetate (250 mL) was added and cooled to 20 ° C. After suction filtration of the reaction solution, 1N hydrochloric acid aqueous solution (250 mL) was added to the filtrate, followed by separation. Hexane (100 mL) was added to the organic layer, and the precipitated crystals were collected by filtration, washed with acetonitrile, and dried to obtain Compound 3b (71 g).

Synthesis of Compound 3c An aqueous solution (150 ml) of sodium hydroxide (30 g) was added dropwise to a solution of compound 3b (71 g) in methanol (350 mL) / tetrahydrofuran (70 mL), and the mixture was stirred at 60 ° C. for 1 hour under a nitrogen atmosphere. . After cooling the reaction solution to 20 ° C., concentrated hydrochloric acid was added dropwise until the system became acidic. The precipitated crystals were filtered, washed with water, washed with acetonitrile, and then dried to obtain compound 3c (63 g).

Synthesis of Compound 3d A solution of Compound 3c (20 g), succinimide (5.25 g) and a 37% formalin aqueous solution (4.3 mL) in ethanol (150 mL) was stirred and refluxed for 5 hours. After cooling to 20 ° C, the precipitated crystals were filtered,
Drying yielded compound 3d (16 g).

Synthesis of Compound 3e A solution of Compound 3d (7 g) in dimethyl sulfoxide (70 mL) was added at 60 ° C.
Then, sodium borohydride (1.32 g) was added slowly so as not to exceed 70 ° C., and the mixture was stirred at that temperature for 15 minutes. The reaction solution was slowly added to 1N aqueous hydrochloric acid (100 mL), and then extracted with ethyl acetate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The origin component was removed with a short path column (developing solvent: ethyl acetate / hexane = 2/1), and then recrystallized from an ethyl acetate / hexane system to obtain compound 3e (3.3 g).

Synthesis of Compound (3) In a solution of bis (trichloromethyl) carbonate (1.98 g) in dichloromethane (80 mL) was added phenoxycarbonylbenzotriazole (4.78 g) and N, N-dimethylaniline (2.42 g) in dichloromethane (100 mL). / Ethyl acetate (200 mL) solution was added dropwise,
Stirred at C for 2 hours. (Solution S) Compound 3e (2.0 g) and a solution of N, N-dimethylaniline (0.60 g) in tetrahydrofuran (20 mL) / ethyl acetate (20 mL) were added.
After 120 mL of the above solution S was added dropwise at 20 ° C, the mixture was stirred at 20 ° C for 2 hours. . After slowly adding the reaction solution to 1N aqueous hydrochloric acid (200 mL),
Extracted with ethyl acetate (200 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. After purifying the column (developing solvent: ethyl acetate / hexane = 1/5),
1.3 g (mp = 138-14) by recrystallization from hexane
0 ° C.). (The compound was identified by elemental analysis, NMR and Mass spectrum.)

Synthesis of coupler of compound example (31) The coupler of compound example (31) was synthesized according to the following scheme.

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Synthesis of Compound 31b A solution of compound 31a (50 g) and bromotetradecane (78.6 g) in 1-methylpyrrolidone (150 mL) synthesized in the same manner as for compound 3c was stirred at 120 ° C. for 5 hours, and then cooled to 25 ° C. Then, the mixture was poured into ethyl acetate (600 mL) / water (600 mL). The organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was recrystallized from an ethyl acetate / hexane system to obtain compound 31b (48 g).

Synthesis of Compound 31c A solution of compound 31b (6.5 g) and dimethylaniline (3.1 g) in tetrahydrofuran (20 ml) was added dropwise to a solution of bis (trichloromethyl) carbonate (1.9 g) in tetrahydrofuran (5 mL) at 10 ° C. . After the reaction solution was stirred at 25 ° C. for 1 hour, it was poured into ethyl acetate (100 mL) / 1N aqueous hydrochloric acid (100 mL). The organic layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure.
The concentrated residue was recrystallized from an ethyl acetate / hexane system to obtain compound 31c (5.4 g).

Synthesis of Compound 31 Compound 31c (3.0 g), mercaptotetrazole derivative A (2.1
g) and a solution of N, N-diisopropyl-N-ethylamine (1.2 g) in toluene (50 mL) were stirred at 80 ° C. for 5 hours. Reaction solution 3
After cooling to 0 ° C., the mixture was poured into ethyl acetate (100 mL) / aqueous sodium bicarbonate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Concentrate the residue to a column (developing solvent:
Ethyl acetate / hexane = 1/2) was purified to obtain 2.5 g of the exemplary compound (31). (Compound identification is elemental analysis,
Performed by NMR and Mass spectra. )

Synthesis of Coupler of Compound Example (32) The coupler of Compound Example (32) was synthesized according to the following scheme.

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Synthesis of Compound 32a Compound 31c (4.5 g), p-hydroxybenzaldehyde (5.0
g) and a solution of N, N-diisopropyl-N-ethylamine (4.8 g) in toluene (100 mL) were refluxed for 5 hours with stirring. After cooling the reaction solution to 30 ° C., ethyl acetate (500 mL) / aqueous sodium bicarbonate solution (500
mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by a column (developing solvent: ethyl acetate / hexane = 1/3) to obtain Compound 32a (3.8 g).

Synthesis of Compound 32b Sodium borohydride was added to a solution of Compound 32a (3.8 g) in methanol (100 mL) and tetrahydrofuran (20 mL) at 25 ° C.
(0.48 g) was added and stirred for 1 hour. The reaction solution was poured into ethyl acetate (100 mL) / 1N aqueous hydrochloric acid (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by a column (developing solvent: ethyl acetate / hexane = 1/2) to obtain Compound 32b (3.7 g).

Synthesis of Compound 32c A solution of compound 32b (3.5 g) in dichloromethane (20 mL) was added at 10 ° C.
Then, phosphorus tribromide (0.7 g) was added thereto, followed by stirring for 1 hour. The reaction solution was poured into ethyl acetate (100 mL) / 1N aqueous hydrochloric acid (100 mL).
The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by column (developing solvent: ethyl acetate / hexane = 1/4) to give Compound 32c (2.8%).
g) was obtained.

Synthesis of Compound 32 Compound 32c (2.5 g), mercaptotetrazole derivative A (1.7
g) and N, N-diisopropyl-N-ethylamine (1.0 g)
The N, N-dimethylacetamide (10 mL) solution was stirred at 25 ° C. for 2 hours. The reaction solution was poured into ethyl acetate (100 mL) / aqueous sodium bicarbonate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by column (developing solvent: ethyl acetate / hexane = 1/1) to obtain 1.7
g of Exemplified Compound (32) was obtained. (The compound was identified by elemental analysis, NMR and Mass spectrum.)

Synthesis of Coupler of Compound Example (35) The coupler of Compound Example (35) was synthesized according to the following scheme.

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Synthesis of Compound 35a Compound 3c (10 g) and benzaldehyde (2.8 g) were stirred at 120 ° C. for 1 hour under a nitrogen stream, and then cooled to room temperature. The reaction residue was recrystallized from ethyl acetate / hexane to give compound 35a (10.1 g).

Synthesis of Compound 35b Compound 35a (10.1 g) was added to 10% -Pd / C (1 g) and ethyl acetate (150 g).
mL), and the mixture was stirred at room temperature under a hydrogen atmosphere of 20 kg / cm ² for 3 hours. After the catalyst was filtered off, it was concentrated under reduced pressure. Compound 35b was obtained by recrystallizing the concentrated residue from an ethyl acetate / hexane system.
(7.2 g) was obtained.

Synthesis of Compound 35c A solution of compound 35b (7.2 g) and N, N-dimethylaniline (3.1 g) in tetrahydrofuran (20 mL) was added to a solution of bis (trichloromethyl) carbonate (1.9 g) in tetrahydrofuran (5 mL) at 10 ° C. Was dropped. After the reaction solution was stirred at 25 ° C. for 1 hour, it was poured into ethyl acetate (100 mL) / 1N aqueous hydrochloric acid (100 mL). The organic layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The concentrated residue was purified by a column (developing solvent: ethyl acetate / hexane = 1/4) to obtain Compound 35c (5.5 g).

Synthesis of Compound 35 A solution of Compound 35c (3.0 g), 1,8-diazabicyclo [5.4.0] -7-undecene (8.8 g) and 3-mercaptopropionic acid (2.0 g) in toluene (100 mL) was added to 50 Stirred at C for 2 hours. Reaction solution
After cooling to 30 ° C., the mixture was poured into ethyl acetate (500 mL) / aqueous sodium bicarbonate (500 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by column (developing solvent: ethyl acetate / hexane = 1/1) to obtain 1.6
g of Exemplified Compound (35) was obtained. (The compound was identified by elemental analysis, NMR and Mass spectrum.)

Synthesis of coupler of compound example (37) The coupler of compound example (37) was synthesized according to the following scheme.

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Synthesis of Compound (37) A solution of bis (trichloromethyl) carbonate (9.5 g) in toluene (1
Phenoxycarbonylbenzotriazole (19.1 mL).
g) in tetrahydrofuran (75 mL) was added dropwise at 10 ° C.
The mixture was stirred at 40 ° C for 3 hours. After the solvent was distilled off under reduced pressure, 200 ml of hexane was added to the concentrated residue, and the mixture was stirred for 1 hour. The crystals were filtered and dried to obtain carbamoyl chloride of phenoxycarbonylbenzotriazole (22.3 g). The phenoxycarbonylbenzotriazole carbamoyl chloride (6.6 g) was added to a solution of the compound 37a (10.0 g) and N, N-dimethylaniline (2.9 g) synthesized in the same manner as the compound 31b in tetrahydrofuran (100 mL) at 10 ° C. Add slowly, 2
Stirred at 0 ° C. for 2 hours. Ethyl acetate (300 mL) / 1
The solution was slowly added to N aqueous hydrochloric acid (300 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Column of concentrated residue (developing solvent: ethyl acetate / hexane = 1/4)
After purification, the residue was recrystallized from an ethyl acetate / hexane system to obtain 7.9 g (mp 99 to 103 ° C.) of the exemplary compound (37).
(The compound was identified by elemental analysis, NMR and Mass spectrum.)

In the present invention, the photographically useful group-releasing coupler can be used in any layer in the light-sensitive material. That is, a photosensitive layer (a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer, a donor layer having a multilayer effect having a spectral sensitivity distribution different from those of the main photosensitive layer), a non-photosensitive layer (for example, a protective layer, a yellow layer) Any of a filter layer, an intermediate layer, and an antihalation layer can be used. When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any one of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer. It can also be added. It is preferably used for a photosensitive layer and / or a non-photosensitive layer adjacent to the photosensitive layer.

In the present invention, the amount of the photographically useful group-releasing coupler used in the light-sensitive material is in the range of 5.times.10@-4 to 2 g / m @ 2. It is preferably in the range of 1.times.10@-3 to 1 g / m @ 2, more preferably 5.times.10@-3 to 5.times.10@-1 g / m @ 2.
Range.

In the present invention, for the use of the photographically useful group-releasing coupler in a light-sensitive material, any known dispersion method can be employed depending on the compound. For example, when the compound is alkali-soluble, it may be added as an aqueous alkaline solution or as a solution dissolved in an organic solvent miscible with water, or may be added using an oil-in-water dispersion method using a high-boiling organic solvent, a solid dispersion method, or the like. Can be.

The photographic useful group releasing coupler in the light-sensitive material used in the present invention may be used alone or in combination of two or more. Further, the same compound can be used in two or more layers. Furthermore, it can be used in combination with other known compounds that release a photographically useful group or a precursor thereof, or can be used in the presence of a coupler or other additives described later. These are appropriately selected according to the performance required for the photosensitive material.

The non-color coupler used in the present invention has been described above. Next, a developing apparatus and a developing process including image processing used in the present invention will be described. First, a development processing apparatus including image processing and usage of terms related to the development processing will be described.

In the present invention, the standard development processing refers to the development processing that is standard in the photographic market on a daily basis.
That is, a process that is substantially internationally common (specifically,
CN16, a color negative film development process
Series (Fuji Photo Film Co., Ltd.), C41 series (Eastman Kodak Company, USA), etc., although the names are different, they are practically compatible) or This refers to a development process in which substantially the same finish is obtained even if there is a slight change. Regarding the standard processing, each photosensitive material maker provides information and technical services to developing laboratories regarding development specifications, developing agents, developing processing apparatuses, and related development management.

In the above description and the following description, the term “processing” is used to refer to “development processing” performed on a photographed photographic photosensitive material and computer processing performed on an image on the developed photosensitive material. Since it is used for both sides of "image processing", the latter is called "image processing" and the former is called "development processing". However, when it is clear which one to indicate, it may be simply referred to as “processing”. Further, “development processing” may be broadly referred to as a bath treatment throughout the entire process from the development step to the washing or stabilizing bath step, or may be narrowly referred to as a bath treatment in the development step. Unless otherwise apparent, they are used for each meaning without further explanation.

Further, in the present invention, the term "developing apparatus" is used when the apparatus for performing the color image forming method of the present invention is generally referred to, and when the developing apparatus is a specific developing machine, Is sometimes referred to as a developing machine. Also,
A component of each function of the development processing apparatus is referred to by a term "means" such as "image reading means". However, when the means is described in a specific description of the development processing apparatus, May be referred to as an “apparatus” such as “image reading apparatus”.

In the following, the developing apparatus used in the image forming method of the present invention and the steps of developing and image processing will be further described in the following order. 1. 1. Configuration of development processing apparatus and flow of photosensitive material and image information 2. Film detection means Developing means 4. 4. Means for reading image information from developed film 5. Image processing means for read image information Output of processed image information from the development processor, especially output to printer

1. FIG. 1 shows the basic components of the developing apparatus of the present invention, the flow of the photosensitive material (hereinafter represented by a color film) and the flow of image information in the apparatus. It is a conceptual diagram. Before the photographed color film F enters the developing means 0, the type of film to be processed is detected and recorded by a film detecting device. This recording information is input to the image processing means 5 so that image processing according to the photosensitive material can be performed.

Subsequently, development is performed by the developing means 0.
There are several processing steps, from a standard processing step consisting of development, bleaching, fixing, washing or stabilizing bath and drying, to a simple processing step consisting of only a stabilizing bath or washing bath followed by a developing step. It can take the form, but details will be described later. The developed color film is
The image information is conveyed to the image reading means 1, the image information is photoelectrically read and digitized, and sent to the image processing device 5 as digital image information carried by time-series electric signals. On the other hand, the color film is discharged from the developing device. However, the image reading unit 2 does not always need to be after the drying step, and it is also possible to select an appropriate reading portion between the end of the developing step and the end of the drying step according to the function to be provided in the developing device. .

In the image processing device 5, image processing is performed on image information read photoelectrically and converted into a digital signal, and in the case of a standard developed image, a correction for further improving the image quality is performed. In the case of an image that has been subjected to development processing other than the standard development such as simplification and speeding up, the image quality to be obtained by the standard development is corrected.

The electrical digital image information corrected by the image processing is output from the development processing apparatus of the present invention to the image output means, where it is D / A converted and the image information is carried by the printing light. The image is exposed to color paper or other color copy material to produce a color print. The outline of the function and operation of each component of the developing apparatus of the present invention has been described above. Next, each component will be further described in accordance with the above flow.

[0111] 2. Film detection means The film detection device is, specifically, a contact reading method in which the sensor contacts the edge of the film sent on the film transport path and detects the length of the film while recording it, and a non-contact infrared sensor that detects by infrared light Method, magnetic recording information reading method for reading information on the magnetic recording layer of the film in APS film, DX code reading method for knowing the type by perforation symbol for film identification such as DX code, side printing of film edge after development process Is carried out by a method of reading photoelectrically.

[0112] 3. Developing processing means The film that has passed through the film detecting means is sent to a developing processing unit (0 in FIG. 1) (as described in the preceding section, there is also a mode in which the film enters the developing step before passing through the film detecting means). The developing section (0 in FIG. 1) is preferably of a roller transport type because it is well connected to the preceding and following steps, but is not limited thereto. The development processing method applicable to the development processing apparatus of the present invention is the above-mentioned standard processing which is widely used worldwide and is commonly used internationally, that is, development processing methods of CN16 system, C41 system and CNK4 system (hereinafter, this system is abbreviated as system A). ), A developing method in which at least one of the bleaching, fixing and washing steps is omitted, a desilvering step is omitted, and a residual color reducing agent is added to a stabilizing bath to prevent an increase in residual color. The development processing method added, the method in which the bleaching and fixing steps are replaced with the bleaching and fixing step, and other methods described in JP-A-11-52527 and JP-A-11-52527
Any of the simplified processing methods disclosed in JP-A Nos. 52528 and 11-52526 (hereinafter, these latter methods are collectively referred to as a method B) may be used.

A general-purpose color developing machine can be used for the developing section in the case of the method A. On the other hand,
FIG. 2 is a view showing a specific embodiment of the developing section of the developing apparatus according to the method B of the present invention, and shows the configuration of a processing section comprising two developing tanks 112 and a stabilizing bath 113 and a drying section 114. FIG. The processing unit 111 includes the developing tank 11
2. The developing bath 112 includes a stabilizing bath 113 and a drying unit 114. The developing bath 112 includes an upper jacket 128 and a lower jacket 129.
The developing bath is a bath tub bulk part B surrounded by this conveying path and a lower mantle member 129 below the conveying path, and there is a gap between the bath tub bulk part B and the conveying path. , And can flow freely through a gap between the lower outer cover member 129 and the opposing roller 127.

In the transport path, opposing rollers 126 and 127 for transporting the photosensitive material are provided. The photosensitive material F to be developed is inserted into the transport path from the left side of the developing tank 112 in FIG. Is developed while being sent along the slit-shaped conveyance path, and is conveyed to the stable bath layer via the seal blade 130. The seal blade 130 has a structure in which two flexible blades are in contact with each other directly or with a film interposed therebetween to maintain airtightness. The liquid level L of the developing bath indicated by the dotted line is maintained at a constant level by the liquid supplied from the replenishing port 150 based on the information detected by the liquid level sensor 116. The developer near the liquid level in the bath tub that has flowed in from the circulating liquid intake port 121 provided near the liquid level is sent upward through the liquid supply pipe 124 by the circulation pump 123 through the circulation pipe 122 and reaches the slit-shaped conveyance path. To form a circulation system for returning to the developing bath.
The temperature of the developer is controlled to a predetermined temperature by a developer circulation system in the developer tank, a heater 125, and a temperature controller (not shown). The film F after the development process is
In this embodiment, the developing solution brought in from the developing step is washed out in the subsequent stabilizing bath 113 to stabilize the image. The stabilizing bath 113 has the same structure and mechanism as the developing tank 112, and includes an upper jacket member 138 and a lower jacket member 13.
Reference numeral 9 designates a slit-shaped photosensitive material conveying path, and a stabilizing bath is formed by the conveying path and the lower jacket member 139. The conveying path is provided with opposing rollers 136 and 137 for conveying the photosensitive material. If the photosensitive material F is conveyed along the conveying path of the stabilizing bath, the photosensitive material F is stabilized and sent to the drying unit 114 via the seal blade 140. . The liquid level L of the stabilizing liquid bath is maintained at a constant level by the stabilizing liquid supplied from the replenishing port 151 when the liquid level sensor 117 detects the liquid level, and the circulating liquid intake port 131 and the circulating pipe 132 , Circulation pump 1
A circulation system in the stable bathtub is constituted by 33 and the liquid sending pipe 134. The temperature of the stabilizer is controlled by the stabilizer circulation system and heater 1
The temperature is adjusted by a temperature controller (not shown).

After the stabilizing solution processing step, the photosensitive material is conveyed to a drying unit, where it is heated by contact with a heat roller 141, further sent upward through a shielding plate 142, and is perpendicularly projected from the blowing nozzle 143 to the photosensitive material surface. It is further dried by warm air blown in the direction, and sent out from the developing unit to the next step.

The film F processed according to the method B in the developing apparatus of this embodiment is omitted in the processing steps such as desilvering and stabilizing bath. It also contains silver, and it is necessary to read out image information by an image processing device mounted on the development processing device of the present invention. From another point of view, by providing an image processing device, photoelectrically reading image information from a screen of a photosensitive material that has been subjected to non-standard development such as not performing desilvering to obtain image information that should be obtained by standard development processing Can be converted.

4. Image information reading means from developed film Measures the image of the developed film and takes it out as electrical image information Reading of the image is performed by a small area unit (hereinafter referred to as a pixel) constituting the image of the developed film
This is performed by measuring the density of each pixel and reading the image information as the density of each pixel. Reading can be done either by transmitted light or by reflected light,
It is preferable from the viewpoint of sensitivity that the measurement is performed by transmitted light when the development processing is performed by the method A and by reflected light when the development processing is performed by the method B.

Image reading can be performed mainly by the following three methods. (I) While irradiating a measuring film combined with a color separation filter by wrapping a film around a rotating drum, the drum is rotated, and at the same time, sub-scanning is performed in the direction of the drum, and the reflection density of each pixel is photoelectrically converted by a photomultiplier tube. (Ii) using a line CCD in which light-receiving elements are arranged one-dimensionally to determine the transmission or reflection density while sub-scanning the image on the developed film. A line CCD scanning method in which a line CCD receives and converts it into a time-series electric signal by electric scanning, and (iii) an area CCD which reads pixel density in two dimensions using an area CCD. Any of the area CCD systems in which electric signals are converted into electric signals rearranged in chronological order by electric scanning from the apparatus may be adopted. The area CCD system is particularly preferred, and the following description will be made on the premise of this system. However, the present invention can be implemented without any problem in the other two systems.

FIG. 3 is a schematic diagram of a transmission type image reading apparatus 10 which measures the transmission density of an image of a developed film and takes out the transmission density as electrical image information. The transmission image reading apparatus 10 is preferable because the reading sensitivity is high when the processing method is the method A. As shown in FIG. 3, the transmission type image reading apparatus 10 converts a color image recorded on the film F into a color image.
By irradiating light and detecting light transmitted through the film, a color image can be read photoelectrically, and the light source 11 is a light amount adjustment unit capable of adjusting the light amount of the light emitted from the light source 11. 12, a color separation unit 13 for separating light emitted from the light source 11 into three colors of R (red), G (green) and B (blue), and the light emitted from the light source 11 is applied to the film F. A diffusion unit 14 for diffusing light, a CCD area sensor 15 for photoelectrically detecting light transmitted through the film F, and an electric motor for forming an image of the light transmitted through the film F on the CCD area sensor 15 so that the light is uniformly irradiated. A zoom lens 16 is provided. The transmission type image reading apparatus 10 can read various kinds of films such as 135 negative film, 135 positive film, and advanced photo system (APS) film by exchanging a film carrier (not shown).

As the light source 11, a halogen lamp was used.
The light amount adjustment unit 12 moves the two aperture plates,
The amount of light changes exponentially with respect to the moving distance. The color separation unit 13 performs color separation into three colors in a plane sequence by rotating a disk having three filters of R, G, and B. The CCD area sensor 15 has a light receiving element of 920 pixels long and 1380 pixels wide,
Image information on film can be read with high resolution. When reading a color image, the CCD area sensor 15 sequentially converts odd-field image data consisting of odd-line image data and even-field image data consisting of even-line image data of the photoelectrically read image. It is configured to transfer.

The transmission type image reading apparatus 10 further includes a CC
An amplifier 17 amplifies the R, G, B image signals photoelectrically detected and generated by the D area sensor 15, an A / D converter 18 for digitizing the image signals, and digitization by an A / D converter 18. The image processing apparatus includes a CCD correction unit 19 for performing a process of correcting variations in sensitivity and dark current for each pixel with respect to the obtained image signal, and a log converter 20 for converting image data of R, G, and B into density data. Log converter 2
0 is connected to the interface 21.

The film F is held by the carrier 22, and the film F held by the carrier 22 is
The driving roller 24 is driven by the driving roller 24 and is fed to a predetermined position, is pressed and held in a stopped state, and is fed by one frame when reading of one frame of a color image is completed. As an auto carrier for handling a negative film, a carrier used in a conventional minilab such as NC135S manufactured by Fuji Film is used. It is possible to read an image in a range corresponding to a print mode, such as a full size, a panorama size, and a powerful size. In addition, when a carrier used in a conventional minilab is used as a trimming carrier, the magnification can be increased by about 1.4 times around the center.

The screen detection sensor 25 detects the density distribution of the color image recorded on the film F, and transmits the detected density signal to the CPU 26 for controlling the transmission type image reading apparatus 10.
The CPU outputs a signal based on the density signal.
26 is configured to calculate the screen position of the color image recorded on the film F, and stop the driving of the motor 23 when determining that the screen position of the color image has reached a predetermined position. The image reading device may be at any location such as an entrance or an exit of a drying unit of the developing machine, an independent reading / image processing device or attached to a printer unit.

On the other hand, when the developing process is carried out by the method B, a large amount of silver remains in the film, and in that case, a reading means for reading with reflection density is advantageous. FIG. 4 shows the configuration of the reflection type image reading device 30. The reflection-type image reading device 30 is configured to detect a reflected light image having a high contrast from a silver halide having a high reflectance and a dye image having a large light absorption by a bleaching process, and to be capable of photoelectrically reading the light. A mirror 32 for reflecting light emitted from the light source and reflected on the film surface;
Color balance filter 33 for adjusting G and B sensitivities, light amount adjustment unit 34, CCD for photoelectrically detecting reflected light
It comprises a line sensor 35 and a lens 36 for imaging the reflected light on the licensor.

The CCD line sensor 35 comprises R, G, B
The light source 31 and the mirror 32 are moved in the directions of the arrows, and the reflected light is detected by the CCD line sensor 35 to read the image information two-dimensionally.

The reflection type image reading device 30 further includes an amplifier 37 for amplifying the detected R, G, B image signals.
A / D converter 38 for digitizing an image signal, CCD correction means 39 for correcting variations in sensitivity and dark current for each pixel of the digitized image signal, and R, G,
A log converter 40 for converting the image data into density data is provided. The log converter is connected to the interface 41. This reflection type image reading device has a CPU
46.

[0127] 5. Image processing means of read image information Image information read by a transmission type or reflection type image reading device is sent to the image processing device in the form of a time-series digital electric signal. As described above, gradation and color balance of a film developed by the method A can be corrected by a simple image processing operation of performing a correction corresponding to a density point for each color (gradation correction for each color). Thus, the fluctuation of the development processing and the fluctuation of the photosensitive material lot are corrected to restore the image to the normal standard development image. On the other hand, for example, the developed film in the case of selecting the development processing of the method B such as omitting the desilvering step has developed silver and silver halide remaining,
There is a deviation from the image quality of standard development of gradation, color balance or Dmin (density value of an unexposed portion). Therefore, in the image processing for correcting the bias, correction exceeding the gradation correction is performed. In the following description, both the method A and the method B will be described together by taking the apparatus of the present invention capable of coping with the development processing of the method B as an example. The image processing operation shown here is described in
146247 and JP-A-10-20457. The following description is also based on these two examples, but the development processing apparatus of the present invention is not limited to using the apparatuses described therein.

FIGS. 5 and 6 are block diagrams showing the structure of the image processing apparatus 5 divided into two figures. As shown in these figures, the image processing apparatus 5 is provided with an interface 2 of the transmission type image reading apparatus 10.
1 or an interface 48 connectable to the interface 41 of the reflection type image reading device 30 and the value of two adjacent pixel data of the image data generated by the image reading device 1 and transmitted for each line, Averaging means 49 for averaging and making one pixel data;
A first line buffer 50a and a second line buffer 50b for alternately storing pixel data in each line of image data sent from the averaging means 49.
And the line data stored in the line buffers 50a and 50b are transferred, and the line data recorded on the film F (FIG. 3)
A first frame memory unit 51, a second frame memory unit 52, and a third frame memory for storing image data corresponding to a color image of a frame or a color image recorded on one color print P (FIG. 4). A unit 53 is provided. Here, the first line buffer 50a and the second line buffer 50b alternately store odd-numbered pixel data of each line of image data in one line buffer and even-numbered pixel data in the other line buffer. It is configured as follows.

In this embodiment, first, for one frame of color image recorded on the film F, first reading (hereinafter referred to as pre-reading) by the image reading device 1 and digital image of the read image are performed. Conversion to data is performed. At this time, based on the image data obtained by the pre-reading, the image processing device 5 performs a second
An image reading condition for reading (hereinafter referred to as main reading) is set. Then, based on the set reading conditions, the reading of the color image, that is, the main reading, is executed again, whereby digital image data to be subjected to image processing for reproduction is generated. To perform such processing, the image processing device 5 stores the image data obtained by the pre-reading in the first frame memory unit 51, and stores the image data obtained by the main reading in the second frame memory unit 52, The third frame memory unit 53 is configured to store the information.

Before describing the other components shown in FIGS. 5 and 6, these frame memory units will be described in detail. FIG. 7 is a block diagram showing details of the first frame memory unit 51, the second frame memory unit 52, and the third frame memory unit 53. As shown in FIG. 7, the image processing apparatus 5 processes a first frame memory unit 51, a second frame memory unit 52, and a third frame memory 52 for processing image data generated by reading a color image.
Of the frame memory units 53
R data memory 51R, G data memory 51G, B data memory 51B, R data memory 52R, and G for storing image data corresponding to (red), G (green), and B (blue).
A data memory 52G, a B data memory 52B, an R data memory 53R, a G data memory 53G and a B data memory 53B are provided. Note that, as described above, the first frame memory unit 51 stores the image data obtained by prefetching, and stores the second and third image data.
In FIG. 7, the image data obtained by prefetching is input from the input bus 63 to the first frame memory unit 51, and the second frame data is stored in the first frame memory unit 51. The state where the image data stored in the memory unit 52 is output to the output bus 64 is shown.

The configuration of the image processing apparatus 5 will be described again with reference to FIGS. The image processing device 5 includes a CPU 60 that controls the entire image processing device 5. When the image reading device is of a transmission type, the CPU 60 can communicate with a CPU 26 (FIG. 3) for controlling the transmission type image reading device 10 via a communication line (not shown). It is configured to be able to communicate with a controlling CPU via a communication line (not shown). When the image reading device is a reflection type, the CPU 60 can communicate with a CPU 46 (FIG. 4) for controlling the transmission type image reading device 30 via a communication line (not shown), and an image output device described later. It is configured to be able to communicate with a CPU controlling the CPU 8 via a communication line (not shown). With this configuration, the CPU 60 changes the image reading conditions for performing the main reading of the color image based on the image data obtained by the pre-reading stored in the first frame memory unit 51, and further reads as necessary. It is possible to change image processing conditions for image processing to be performed on a subsequent image.

That is, based on the image data obtained by the pre-reading, the CPU 60 sets the image reading conditions for the main reading so that the dynamic range of the CCD area sensor 15 or the CCD line sensor 35 can be used efficiently at the time of the main reading. Is determined, and a reading control signal is output to the CPU 26 of the transmission type image reading device 10 or the CPU 46 of the reflection type image reading device 30. At this time, when the CPU 26 of the transmission type image reading device 10 or the CPU 46 of the reflection type image reading device 30 receives the read control signal, the CPU 26 of the light amount adjustment unit 12 or the light amount adjustment unit 3
Light amount and CCD area sensor 15 adjusted by 4
Alternatively, the storage time of the CCD line sensor 35 is controlled. At the same time, based on the obtained image data, the CPU 60 makes it possible to reproduce a color image having an optimum density, gradation and color tone on a color paper by a first
A control signal for changing image processing conditions such as parameters of image processing by the image processing means and the second image processing means is output to the first image processing means and the second image processing means as necessary. At this time, the image reading conditions or image processing conditions determined by the CPU 60 are stored in the memory 66.
Is stored.

When the CPU 60 performs the above control, if the image reading condition or the image processing condition is held by the instruction of the operator, the CPU 60 does not determine the condition based on the pre-read image data as described above. And outputs various control signals based on the held conditions. When the operator sets various conditions by using an input device such as the keyboard 69, and further instructs to hold them,
These conditions are stored in the memory 66. If the operator subsequently instructs to release the holding of these conditions, the conditions stored in the memory 66 become invalid. Therefore, when performing the above-described control, the CPU 60 first refers to the condition stored in the memory 66, and if the condition is stored, it follows the condition. Determine these conditions based on the data. Therefore, the operator can read from the DX code, instruct the condition setting according to each film type according to a special order of the customer, or automatically set the conditions for each film type in advance and automatically set the conditions. It is also possible to perform processing according to the instruction. It is not always necessary to hold such conditions in large units, such as image reading conditions or image processing conditions. For example, the setting of the saturation may be maintained, and the sharpness may be set using an automatically determined condition.

The configuration of the image processing apparatus 5 in the range shown in FIG. 5 has been described above. Here, the image data generated in the image reading apparatus 1 is input to the image processing apparatus 5 through the interface 48, and the first The processing performed on the image data from the time when the image data is stored in the third frame memory unit to the third frame memory unit has been described in detail. The configuration of the image processing apparatus 5 for performing image processing on the image data stored in the third frame memory unit 53 will be described with reference to FIG. FIG. 6 is a diagram illustrating a configuration of a portion that performs image processing on image data stored in the frame memory units 52 and 53 of the image processing device 5.

In the portion of the image processing device 5 shown in FIG.
The look-up table is stored in the image data stored in the second frame memory unit 52 and the third frame memory unit 53 so that a color image can be reproduced on a color paper with a desired density, gradation and color tone. The image data stored in the first image processing means 61 (FIG. 6) and the first frame memory unit 51 for performing image processing such as gradation correction, color conversion, density conversion, and the like by a matrix operation as desired. A second image processing unit 62 that performs image processing such as gradation correction, color conversion, and density conversion by a look-up table or a matrix operation so that a color image can be reproduced on a CRT screen described later with high image quality.
(FIG. 6). The outputs of the second frame memory unit 52 and the third frame memory unit 53 are connected to a selector 55, and the selector 55 stores the output in one of the second frame memory unit 52 and the second frame memory unit 53. The image data is selectively inputted to the first image processing means 61.

FIG. 8 is a block diagram showing details of the first image processing means 61. As shown in FIG. 8, the first image processing unit 61 includes a color density gradation conversion unit 100 that converts density data, color data, and gradation data of image data, and a color conversion unit that converts saturation data of image data. Digital conversion unit 102 for converting the number of pixel data of image data, frequency processing unit 103 for performing frequency processing on image data, and dynamic range conversion unit 104 for converting the dynamic range of image data. I have. Each of these conversion means,
Since each processing means operates at the same time and the next processing is performed after the operation is completed, as generally called a pipeline processing, high-speed processing is possible.

The image processing means shown in FIG. 8 can perform not only processes such as gradation correction, color conversion, and density conversion, but also suppress film graininess as shown in Japanese Patent Application Laid-Open No. 9-22460. At the same time, processing for improving sharpness can be performed. Further, Japanese Patent Laid-Open No. 9-1
An automatic dodging process that provides good image reproduction can also be performed on an image having a large contrast between light and dark, as shown in Japanese Patent No. 8704.

A description will now be given of the image processing only for the gradation correction of the film developed by the method A by the above-mentioned image processing apparatus. In this case, since the correction of the development processing conditions and the variation of the film lot in the development processing of the method A,
As described above, the correction amount is relatively small, and the gradation correction can be completed. The read values with slight gradation disturbance and color balance distortion of the film are the standard density values obtained for each color of cyan, magenta, and yellow when processing in the standard state for each density point. Is converted to The conversion is performed by a matrix operation for adding a correction coefficient for each density point for each color. Each correction coefficient is input to the memory 66 as a set of coefficient matrices.

On the other hand, even in the development processing of the method A, in order to improve the image quality by performing more advanced image processing in addition to the correction by the matrix operation described above, the development processing of the method B described below will be described. The same method as the image processing for the processing may be used.

In the method B in which one or more steps of bleaching, fixing, stabilizing bath, washing with water, etc. are further omitted on top of the underreplenishment development, (i) the dye image, the silver image and the silver halide overlap. (Ii) a decrease in the readable range and a decrease in saturation due to an increase in Dmin (minimum density value), and (iii) a decrease in the readout accuracy of a high exposure area due to an increase in Dmax (maximum density value). The above three factors differ depending on the type of film. Therefore, this CP
In U, the condition setting of the image processing for correcting the read image information digitized with respect to the three photographic characteristic factors to the image characteristic value at the time of the standard development processing is performed.
As can be seen from the above, the items of the image processing conditions to be set for the development method A or B are as follows.

1) a process of correcting a tone deviating from the tone of the standard development process, 2) a process of converting color balance data into a color balance value when processed under the standard process conditions, and 3) a development process of method B Processing for correcting the resulting non-linearity of the relationship between exposure amount and density to correct the relationship between exposure amount and density when the photographic material is processed under the standard processing conditions (especially high density portion and low density portion), and 4). Dmin significantly higher than standard development
There is a correction process for the effect of the so-called clogs.

The correction of these four characteristic factors by image processing is as follows.
The correction is made in two main ways. One is a method of directly inputting the density value information of the read image to the image processing apparatus described above to perform image reproduction processing, and the other is an operation of converting the read image information into an analysis density. This is a method of performing the above-described image reproduction processing on the analysis density information after performing the processing. It is considered that grasping the image is more accurate if the conversion to the analysis density is performed. However, in the present invention, the former method has been found to be sufficient. A method for directly inputting to the image processing apparatus will be described.

In this series of image processing for image reproduction, the most important image processing for image reproduction is, in particular, the correction of the soft gradation described in (i) to the gradation at the time of reference development. That is, the gradation conversion means 100 has a function of correcting the gradient of the input density value versus the exposure amount to an appropriate value obtained by the standard development processing. At the same time, a large part of the correction of the color balance described in (ii) is performed by adjustment of each color for the high contrast, but is finely adjusted by a combination of the following image processing functions. The further softness of the high-density portion and the elongation of the foot in the low-density portion described in (iii) are set by setting the level of the saturation emphasis of the saturation conversion unit 101 high, and the dynamic range conversion unit 104 and the gradation conversion unit 100 This is performed by modifying the shape of the characteristic curve of the leg and the high-density portion by a combination of changing the density amplification degree according to the spatial frequency described below. In this case, the conditions must be set so that the correction process to the standard value of the saturation (a set of density values corresponding to the processing amount "zero" or a set of density values in the case of standard development) is performed at the same time. Needless to say. The increase in Dmin due to residual silver or the like does not appear in the output image characteristics because it is included in the background level and erased in the so-called clogs during image processing. The operation contents of the device of the image processing apparatus used for the above image processing are described in JP-A-9-146247.
And JP-A-10-20457.

As described above, the accuracy of the correction of the image information by the above-mentioned image processing may be within 10% of the reference value as the density value, preferably within 8%. If the color balance and the gradation characteristics are within the above ranges as the density values, it is determined that the image has been reproduced.

The information obtained by performing image processing on the image information read from the film processed in this manner and correcting it to the characteristic values corresponding to the standard development processing is temporarily stored, and then output to a printer for forming a positive image. You will proceed to the stage.

The conversion to the characteristic values corresponding to the standard development processing is performed by setting conversion conditions for each type of film.
The conditions may be automatically selected by reading the type of the film to be processed, or the operator may specify the conversion processing conditions for each film to be processed.

In addition to the above, the image processing apparatus 5 has a data bus in addition to the input bus 63 and the output bus 64 of the first frame memory unit 51, the second frame memory unit 52 and the third frame memory unit 53. 65
The data bus 65 includes a CPU 60 for controlling the entire color image reproduction system, a memory 66 for storing an operation program of the CPU 60 or data relating to image processing conditions, and a hard disk capable of storing and storing image data. 67, CRT68, keyboard 6
9, a communication port 70 connected to another color image reproduction system via a communication line, and a C of the transmission type image reading apparatus 10.
A communication line with the PU 26 is connected.

6. Developing Unit of Developing Apparatus The flow of a film, reading of image information and handling thereof in the developing apparatus according to the present invention have been described. In the processing tank and the replenisher tank, the area where the liquid comes into contact with air (opening area) is preferably as small as possible. For example, assuming that the value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank is the opening ratio, the opening ratio is 0.01 (c
m ^-1 ) or less, more preferably 0.005 or less, and most preferably 0.001 or less.

In the development processing apparatus of the present invention, in order to perform processing quickly, the air time, that is, the crossover time, when the light-sensitive material moves between processing solutions is preferably as short as possible, preferably 20 seconds or less. More preferably, it is 10 seconds or less, further preferably, 5 seconds or less. In order to achieve the short-time crossover as described above, it is preferable to use a cine-type automatic developing machine, and particularly preferable is a leader transport system or a roller transport system. Such a system is available from Fuji Photo Film Co., Ltd. automatic developing machine FP-560B and PP1820V.
May be modified so that the processing step of the present invention can be performed. Also, it is preferable that the linear velocity of the conveyance is high, but it is 30 cm / min.
３０30 m is common, and preferably 50 cm to 10 m. As a reader and a means for transporting photosensitive material, JP-A-60-191257, JP-A-60-191258, and JP-A-60-191258
The belt conveyance system described in JP-A-191259 is preferred. Further, in order to shorten the crossover time and prevent the treatment liquid from being mixed, a crossover rack structure having a mixing prevention plate is preferable.

It is preferable to perform so-called evaporation correction, in which water corresponding to the amount of evaporation of the processing liquid is supplied to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution.
As a specific method for replenishing such water, an evaporation correction method using a liquid level sensor or an overflow sensor is preferable. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and the amount of water calculated by a coefficient obtained in advance based on information on the operation time, stop time, and temperature control time of the automatic developing machine. Is added.

It is also necessary to take measures to reduce the amount of evaporation, and it is necessary to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable aperture ratio of the color developing solution is as described above, but it is preferable to similarly reduce the opening area in other processing solutions. The exhaust fan is installed to prevent condensation during temperature control.
Preferred emissions, per minute 0.1 m ³ to 1 m ^3,
Particularly preferred engine displacement, a 0.2m ³ ~0.4m ^3. The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The heating prevention thermostat of the ceramic hot air heater is preferably operated by heat transfer, and the mounting position is preferably mounted on the leeward or upwind side through a radiation fin or a heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed. For a film having a width of 35 mm, 45 to 55 ° C., for a brownie film, 55 to 65 ° C.,
For printing materials, 60-90 ° C. is optimal. A replenishing pump is used for replenishing the processing solution, and a bellows type replenishing pump is preferable. As a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent a backflow when the pump is stopped. A preferred inner diameter is 1 to 8 mm, and a particularly preferred inner diameter is 2 to 5 mm.

In the automatic developing machine, various component materials are used in addition to the above-mentioned driving section. Preferred materials are described below. Tank material such as processing tank and temperature control tank is made of denatured PP
O (modified polyphenylene oxide) and modified PPE (modified polyphenylene ether) resins are preferred. Modified PP
O is "Noryl" manufactured by Nippon GE Plastics, and "Modified PPE" is "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd., "Iupiece" manufactured by Mitsubishi Gas Chemical Co., and the like. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers.

The drying time is preferably from 10 seconds to 2 minutes, more preferably from 20 seconds to 80 seconds. As described above, the continuous processing by the replenishment method has been mainly described. In the present invention, the processing is performed without performing the replenishment with a certain amount of the processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid and the processing is performed again. A batch processing method to be performed can also be preferably used.

[0154] 7. Output of Image-Processed Image Signal to Printer Above, the configuration of the image processing device 5 has been described in detail. Next, an image output apparatus that receives time-series digital image information output from the development processing apparatus of the present invention and outputs the digital image information to a color print will be described. FIG. 9 is a schematic diagram of an image output device 8 for a color image reproduction system that reproduces a color image on image data output from an image processing apparatus according to a preferred embodiment of the present invention.

In FIG. 9, the image output device 8 includes an interface 78 connectable to the interface 77 of the image processing device 5 and a CPU 79 for controlling the image output device 8.
And an image data memory 80 composed of a plurality of frame memories for storing image data input from the image processing device 5.
A D / A converter 81 for converting image data into an analog signal; a laser light irradiation means 82; and a modulator driving means 83 for outputting a modulation signal for modulating the intensity of the laser light. The CPU 79 is configured to be able to communicate with the CPU 60 of the image processing apparatus 5 via a communication line (not shown).

FIG. 10 is a schematic diagram of the laser light irradiating means 82 shown in FIG. 9. The laser light irradiating means 82 includes semiconductor laser light sources 84a, 84b, and 84c, and emits laser light emitted from the semiconductor laser light source 84b. The light is converted into green laser light having a wavelength of 532 nm by the wavelength conversion means 85, and the laser light emitted by the semiconductor laser light source 84 c is converted by the wavelength conversion means 86 into blue laser light having a wavelength of 473 nm.

6 emitted from the semiconductor laser light source 84a
Red laser light of any wavelength between 70 nm and 690 nm,
The green laser light whose wavelength has been converted by the wavelength converting means 85 and the blue laser light whose wavelength has been converted by the wavelength converting means 86 are respectively converted into an acousto-optic modulator (AO).
M) and the like so as to be incident on the optical modulators 87R, 87G, 87B.
B is configured to receive a modulation signal from the modulator driving unit 83 and to modulate the intensity of the laser light according to the modulation signal. At this time, if the semiconductor laser light source 84a can operate at high speed, the light modulator 87R can be omitted by directly modulating the semiconductor laser light source 84a.

The laser light whose intensity has been modulated by the optical modulators 87R, 87G, 87B is reflected by the reflection mirror 88R,
The polygon mirror 89 is reflected by 88G and 88B.
Incident on. Here, the paper is conveyed at a speed of about 75 mm per second, the scanning line density is 600 lines per inch, and each pixel is modulated every 100 nsec.

The image output device 8 includes a magazine 91 in which color paper 90 is stored in a roll. The color paper 90 having a paper width is conveyed at a speed of about 110 mm per second in the sub-scanning direction along a predetermined conveyance path. It is configured to: A color paper with a width of 89 mm to 210 mm can be used, and it may be a color paper used in ordinary minilabs or the like, or a special color suitable for high-illuminance short-time exposure unique to laser exposure. Paper may be used. As the magazine 91, a magazine used in a normal minilab, for example, Japanese Patent Application No. Hei 4-317051
Use the one described in the item. The transport path of the color paper 90 is provided with perforation means 92 for perforating a reference hole at a side edge of the color paper 90 at intervals corresponding to the length of one color print. In the device 8, according to the reference hole, the color paper 90
Is synchronized with the driving of other means.

The laser light modulated by the light modulators 87 R, 87 G, and 87 B is scanned in the main scanning direction by the polygon mirror 89, and exposes the color paper 90 via the fθ lens 93. Here, color paper 90
Is transported in the sub-scanning direction, so that the entire surface is exposed by laser light. Here, the transport speed of the color paper 90 in the sub-scanning direction is the main scanning speed of the laser light,
That is, it is controlled by the CPU 79 so as to synchronize with the rotation speed of the polygon mirror 89.

The color paper 90 exposed by the laser beam is sent to the development processing section 94 at a speed of about 29 mm per second, and is subjected to predetermined color development processing, bleach-fixing processing, and water washing processing. A color image is reproduced on the color paper 90 based on the image data subjected to the image processing. The color paper 90 that has been subjected to the color development processing, the bleach-fixing processing, and the water-washing processing by the color developing tank 94, the bleach-fixing tank 95, and the washing tank 96 is sent to the drying unit 97, where the color paper 90 is dried. Based on the reference holes formed in the side edges, the color paper 9
By the cutter 98 driven in synchronization with the conveyance of 0, the cutter 98 is cut into a length corresponding to a color image recorded on one frame of the film F or one color paper P, sent to the sorter 99, and The number of sheets corresponding to the film F of the book or the number of customers is accumulated. A well-known sorter is used.

The development processing apparatus including the image processing apparatus and the development processing machine has been described above. Next, the development processing of the light-sensitive material containing a colorless coupler used in the present invention will be further described. The processing method in the present invention is a standard processing, a rapid development type or a low replenishment type or a rapid development type and a low replenishment type processing method, and the processing method itself is widely used for processing a general silver halide color photographic light-sensitive material. Although the present invention can be applied, the effect of the present invention is remarkably exhibited when the photosensitive material is a photosensitive material containing the achromatic coupler. The standard processing is a processing generally used internationally for silver halide color photographic processing, and a rapid development type or a low replenishment type or a rapid development type and a low replenishment type processing method is internationally known. It means a rapid development type or low replenishment type or a rapid development type and low replenishment type processing with respect to commonly used processing.

More specifically, since the color photographic market is internationalized and the products of major photographic material manufacturers are distributed internationally, each photographic material manufacturer has We provide development specifications (prescriptions) that enable common processing (interchangeable processing) so that products of manufacturers can undertake development, and the specifications are most commonly used internationally. For example, color negative film development processing specifications include CN16 series (Fuji Photo Film Co., Ltd., C41 (Eastman Kodak Company)), etc., which are common development processing specifications even though the processing specifications have different brand names. In addition, at each photofinishing lab, processing has been unified within a range that can be said to be substantially common, although there may be slight changes according to the circumstances. Information and technical services are provided to the lab about prescriptions, developing agents, processing equipment and related development management, so in the present invention, rapid processing or low replenishment processing is referred to as The internationally standardized C-
This indicates that the processing specifications are faster or lower than the processing specifications of 41 and CN-16.

The development processing performed in the present invention is repeated, but the standard processing is the processing described above as the method A, and comprises a color development step, a desilvering step, a washing or stabilizing bath step, and a drying step. Auxiliary steps such as a rinsing step, an intermediate washing step, and a neutralizing step can be inserted between them. The desilvering step is a combination of a bleaching step, a fixing step, and a bleach-fixing step, and is a step including at least one of a step having a bleaching ability and a step having a fixing ability. An image stabilizing bath for stabilizing an image may be provided between the washing or stabilizing bath step and the drying step, in addition to the washing alternative stabilizing bath instead of the washing step. As described above, the method B is a step in which at least one step other than the color developing step in the processing of the method A is omitted.

The developing system applied to the processing apparatus of the present invention may be either system A or system B. In the case of system A, after the desilvering process such as fixing or bleach-fixing, the system B is used. In most cases, after color development, rinsing,
It is common to perform one or more of the washing and stabilizing treatments.

In the method B, the effect of image quality relief by the image processing apparatus is great. In particular, the application of the present invention to a two-step process of performing a stabilizing bath after color development is a preferred embodiment. Also, since there is little need to preserve the film image, a simple rinsing bath step may be performed following the development step without performing an image stabilizing bath.

As a means for speeding up the development processing, a method of changing the factors of the development processing to speed up the processing may be adopted in addition to omitting the processing steps as in the method B. Various factors can be used for this kind of speeding up. For example, the following method can be used. However, the speeding-up means applicable to the present invention is not limited to these. Higher Development Temperature The development conditions for color labs in the market are usually about 38 ° C., but can be accelerated by raising the temperature to about 65 ° C. Although it is possible to develop at higher temperatures,
The occurrence of fogging and uneven processing becomes remarkable. Higher concentration of color developing agent If there is room for further increasing the concentration of the color developing agent, it is necessary to extend the washing time, and the concentration can be increased within a range that is not disadvantageous. Use of a Highly Active Color Developing Agent As the color developing agent, the above-mentioned N-hydroxypropyl derivative can be used, or it can be used when the use of a non-versatile developing agent is not restricted.

Increasing pH of Developer Solution As long as the supply of the color developing agent is not a factor controlling the speed, it is effective means to increase the pH as long as fogging can be controlled. Use of a development accelerator A development accelerator, such as thiocyanate, which promotes the development of the lower layer is particularly preferable. Addition of a Development Inhibitor Many development accelerating means increase the development speed, but have a greater accelerating property with respect to the surface layer, so that their effects are limited in terms of the balance of the development speed between the layers. Therefore, development can be accelerated by using a known development inhibitor having an effect of suppressing development of the surface layer in combination with the development accelerating means. Specific examples include a method in which 1-phenyl-5-mercaptotetrazole and the like are used in combination with sodium thiocyanate.

Among these development processing methods, the following are advantageous means because the development accelerating property with respect to the lower layer, in which the development speed is easily delayed, is relatively large. Although the degree of speeding up of the processing method of the present invention is shorter than the time of each step of the international standard processing corresponding to the time of each step of the above-mentioned processing specifications, it is preferably 0. 05-
The processing is performed at a factor of 0.8, and more preferably at a factor of 0.1 to 0.7. The more specific time saving range is
Since it differs depending on each processing step, it will be described in the description of each step.

The case where the present invention is applied to low replenishment processing will be described. “Replenishment” in the development processing is a processing liquid added to a processing tank in order to maintain the constant performance of the processing liquid even during processing of the compound material or during suspension of the processing.
When the processing of the photosensitive material is continued, the reaction components (for example, a developing agent) in the processing solution are consumed, so that the concentration in the processing solution decreases, and at the same time, the reaction products and the elution products from the photosensitive material are contained in the processing solution. Accumulation, which changes (deteriorates) the performance of the developing solution. To continue processing stably while maintaining normal image quality, replenish the components consumed in the processing solution and simultaneously produce reaction products and Replenishment is performed so that the accumulated components are diluted to such an extent that the effect of the accumulation of the eluate does not appear. An appropriate replenishment amount is a threshold value at which the mass balance of the consumption and supply of the reaction components in the processing tank is correctly obtained, and the amount of the accumulated component of the liquid in the processing tank causes deterioration of the processing liquid performance. Refers to the replenishment performed so that it is not exceeded.

Low replenishment is therefore constrained from two aspects. The first is the mass balance of the reaction components.If the replenishment is reduced, it is necessary to supply the reactant components in proportion to the amount of consumption even with small replenishment by increasing the concentration accordingly. The solubility of the reaction components cannot be higher than the solubility thereof, and therefore, the solubility of the reaction components in the processing solution is one determinant of the limit of low replenishment.
Another factor is the limit accumulation level at which the degree of accumulation of reaction products and eluates in the processing solution in the processing tank does not affect image performance.

The limit of low replenishment in the developing step will be described. Conventionally, when a non-colored coupler is used, the amount of the accumulation increases due to the second factor, that is, the continuation of the processing, and the deterioration of the processing solution in the processing tank proceeds to reach the threshold of the accumulation amount, As described above, the effect of improving the sharpness and color reproducibility originally required by the colorless coupler is not exhibited,
Adverse effects such as a decrease in sensitivity and changes in gradation and color balance have appeared, and this has been a constraint on reducing the replenishment amount.

In the case of a light-sensitive material containing a colorless coupler used in the present invention, unlike the case of using a conventional colorless coupler, accumulation of reaction products and elution products in a developing solution in a developing tank is different. Since the adverse effect of the accumulation is small, the accumulated concentration is unlikely to be a factor that determines the limit of the low replenishment (it is presumed that the threshold value of the accumulation amount is high), and the high replenishment is enabled.

Even if the replenisher is highly replenished, insolubles are not generated and the replenishment can be further reduced if the developer does not deteriorate, but the ultimate level of the replenishment is as follows.
It is "reduction of weight loss". "Reduction in weight loss" refers to replenishment in which the overflow from the developing tank is reduced to zero, and only the volume of the developing solution that has been lost by being attached to the photosensitive material and taken out to the next bath or evaporating is replenished. . In general, when replenishment is carried out, the amount of reaction components decreases and the accumulation of products and eluted components is remarkable, so that the liquid deteriorates greatly and reaches the above-mentioned threshold value with a small amount of treatment. In addition to the processing of black-and-white photosensitive materials, the replenishment method is considered to be disadvantageous because a large amount of the degradation processing solution is discarded. However, in the present invention, the replenishment of weight loss is made a processing system of practical value by adjusting the amount of silver halide applied in the light-sensitive material, the amount of the colorless coupler of the present invention, the dissolution inhibitor, etc. Can be.

In the low replenishment process according to the present invention, the concentration of the reaction component in the replenisher is higher than the concentration of the reaction component in the replenisher for the standard process, and the replenishment amount per area of the photographic material is smaller than that for the standard process. Although the processing is smaller than the replenishing amount of the replenisher, the concentration of the reaction component is preferably 1.1 to 20 times the concentration of the component in the replenisher for standard processing, and a more specific concentration range is as follows. Since it differs depending on the type of the processing liquid, it will be described in the individual processing liquid section described later.

[0176] The following describes the standard processing called method A,
The composition, concentration, replenishment, and the like of each treatment bath of the treatment of the present invention are described for the treatment of the present invention, including the method B treatment such as rapid treatment, low replenishment treatment, and step omission treatment. The following description applies to the missing steps.

The color developing step is a step of immersing the photosensitive material in a color developing solution. The color developing solution is an alkaline continuous phase liquid containing constituent components in a dissolved state. Among them, a color developing agent is contained, and a preferred example is a known aromatic primary amine color developing agent, particularly a p-phenylenediamine derivative. Representative examples are shown below, but are not limited thereto. is not. In recent years, in black-and-white photosensitive materials, a coupler has been added so as to form black.
Although there are some which form black and white images using a general-purpose general color developing solution, the color developing solution of the present invention is also applicable to processing of this type of photosensitive material.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline 6) 4-amino- N-ethyl-N- (3-hydroxypropyl) -3-methylaniline 7) 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline 8) 4-amino-N-ethyl- N- (β-methanesulfonamidoethyl) -3-methylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-N-ethyl-N- (β -Methoxyethyl) -3 methyl-aniline 11) 4-Amino-N- (β-ethoxyethyl) -N-
Ethyl-3-methylaniline 12) 4-amino-N- (3-carbamoylpropyl-
Nn-propyl-3-methylaniline 13) 4-amino-N- (4-carbamoylbutyl-N
-N-propyl-3-methylaniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Of the above-mentioned p-phenylenediamine derivatives, particularly preferred are the exemplified compounds 5), 6), 7), 8) and 12), among which the compounds 5) and 8) are preferred. Also, these p-phenylenediamine derivatives are
In the state of solid material, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The processing agent composition is used as a working solution in the form of a development replenisher (or a further diluted developing solution) by mixing it with water at a predetermined ratio at the time of use. The concentration of the developing agent is preferably 2 to 40 mmol per liter of the developer, but in the processing method of the present invention, the concentration is 2 to 200 mmol, more preferably 12 to 200 mmol.
200 mmol, more preferably 12 mmol to 150
Millimoles.

The color developing solution may or may not contain a small amount of sulfite ion depending on the kind of the light-sensitive material to be treated. However, in the present invention, it is preferable to contain a small amount of sulfite ion. Although sulfite ions have a remarkable preservative action, if they are in excess, they may have an unfavorable effect on photographic performance during color development. Further, a small amount of hydroxylamine may be contained.
When it contains hydroxylamine (usually used in the form of hydrochloride or sulfate, the salt form is omitted below), it acts as a preservative in the developer as well as the sulfite ion, but at the same time, Since the photographic properties may be affected by silver development activity, the amount of addition must be kept small.

An organic preservative may be added to the color developing solution in addition to the hydroxylamine and the sulfite ion as a preservative. The organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being included in a processing solution for a photosensitive material. That is,
Organic compounds having a function of preventing air oxidation and the like of color developing agents, among others, including the above-described hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxyketones, α-aminoketones, Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235, JP-A-63-30845, and JP-A-63-21647.
Nos. 63-44655, 63-53551, 63-43140, 63
-56654, 63-58346, 63-43138, 63-146041
No. 63-44657, No. 63-44656, U.S. Pat.
No. 3, 2,494,903, JP-A-52-143020, JP-B-48
No. -30496 and the like.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, it is preferable to add an alkanolamine such as triethanolamine or triisopropanolamine, a substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine or diethylhydroxylamine, or an aromatic polyhydroxy compound. Among the organic preservatives, the details of the hydroxylamine derivative are described in JP-A-1-97953, JP-A-1-86939, JP-A-1-186940,
No. 1-187557, and the like. In particular, the use of a hydroxylamine derivative and an amine in combination is more preferable in terms of improving the stability of the color developing solution and the stability during continuous processing. Examples of the amines include:
Cyclic amines described in JP-A-63-239447 and amines described in JP-A-63-128340 and others disclosed in JP-A-1-186939 and 1-187557. Examples include amines as described.

If necessary, chloride ions may be added to the color developer, for example, for color paper. Color developer (especially developer for color print materials)
Usually contains 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l of chlorine ion, but chlorine ion is usually released into the developer as a by-product of development, so it is added to the replenisher. Often unnecessary. The amount of chloride ions in the replenisher is set so that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. When the chloride ion concentration is more than 1.5 × 10 ⁻¹ mol / liter, the developer for printing materials has a disadvantage that the development is delayed, and the speed and color density are unfavorably deteriorated.
On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, it is often not preferable in preventing fog. The developing solution for a photosensitive material for photographing which is preferable in the present invention may not contain chlorine ions.

Regarding the content of bromine ions, the color developer
The bromine ion in the processing of the material for photography is 1-5 × 10
^-3About 1.0 mol / l, 1.0 for processing printing materials
× 10 ^-3It is preferably at most mol / liter. bromine
Replenisher as necessary so that ion concentration is within this range
Sometimes bromine ions are added. Target photosensitive material
The fee is color negative film or color reversal film
Is obtained from a silver iodobromide emulsion such as
Is the same for iodine ions, but usually
Iodine ions are released from the photosensitive material and 1 liter of developer
0.5 to 10 mg of iodine ion
Therefore, it is usually not contained in the replenisher. Present
As an additional component in the image solution and replenisher, a chloride ion supply
Sodium chloride, potassium chloride, ammonium chloride
, Lithium chloride, nickel chloride, magnesium chloride
Manganese chloride, calcium chloride,
Preferred are sodium chloride and potassium chloride
It is. Sodium bromide as a source of bromine ions
, Potassium bromide, ammonium bromide, lithium bromide,
Calcium bromide, magnesium bromide, manganese bromide, odor
Nickel bromide, cerium bromide, thallium bromide
But preferred are potassium bromide and sodium bromide.
Um. As a source of iodine ions, sodium iodide
Lium and potassium iodide.

The p of the color developing solution and replenisher used in the present invention
H is preferably pH 9.0 to 13.5 in a developing solution, pH 9.0 to 13.5 in a replenisher, and more preferably 9.9 to 12.5 in a replenishing solution. PH usually higher than the pH of the developer to compensate for
Is set to a value. In order to maintain the above pH, it is preferable to use various buffers. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent buffering capacity in the high pH range of pH 9.0 or higher, and have an adverse effect on photographic performance (such as fog) even when added to color developers. )
The use of these buffers is particularly preferred because they have the advantage of being inexpensive and inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.
Since the buffer is not a component that is reacted or consumed, the concentration of the buffer is 0.01 per liter for both the developer and the replenisher.
To 2 mol, preferably 0.1 to 0.5 mol, in the composition. The concentrations in the replenisher and the developer may be the same, or may be as high as at most 10%.

The color developing solution may contain other color developing solution components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or which are also agents for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, ,
2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediaminedisuccinic acid (SS form), N-
(2-carboxylateethyl) -L-aspartic acid, β-alanine diacetate, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid,
1,2-dihydroxybenzene-4,6-disulfonic acid and the like. These chelating agents may be used as needed.
More than one species may be used in combination. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developer. For example, it is added so as to be about 0.1 g to 10 g per liter. Also, the concentration in the replenisher and the developer may be the same, or may be at least as high as 10%.

The color developing solution used in the present invention can be added with an optional development accelerator as needed to impart rapid developability. As development accelerators, JP-B-37-16088,
Nos. 37-5987, 38-7826, 44-12380, 45-90
No. 19, U.S. Pat.No. 3,813,247, etc. and thioether compounds described in the specification, JP-A-52-49829 and p-phenylenediamine-based compounds disclosed in JP-A-50-15554, No. 137726, Japanese Patent Publication No. 44-30074
Quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
Nos. 3,128,182, 4,230,796, 3,253,919
No., JP-B-41-11431, U.S. Pat.No. 2,482,546,
Nos. 596,926 and 3,582,346, etc., the amine compounds described in each gazette or in the specification, JP-B-37-16088, JP-B-42-25201
No., U.S. Pat.No. 3,128,183, JP-B-41-11431, 42
No. -23883 and U.S. Pat. No. 3,532,501.
-Phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. The concentration in the replenisher and the developer is the same, or the concentration of the replenisher is increased by 5 to 60%.

An optional antifoggant can be added to the color developer used in the present invention, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5
-Nitrogen-containing compounds such as -nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Heterocyclic compounds can be mentioned as typical examples. In particular, in the case of rapid processing, since the developing solution is activated by increasing the pH, increasing the concentration of the main agent, or using a development accelerator, it is preferable to add an antifoggant accordingly. The concentration in the replenisher and the developer is the same,
Preferably, the concentration of the 20% replenisher is increased. In addition to the surfactant in the present invention, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.
The concentration in the replenisher and the developer is the same,
It is preferable to increase the value within 0%.

When the photosensitive material to be developed is a photographic material such as a color negative, the temperature is 38 ° C. in the standard processing.
The processing temperature of color development applied to the present invention is 38 to 70.
° C, preferably 38-55 ° C. In the case of a color negative film, the development processing time is 195 seconds in the standard development, but is 15 to 1 in the processing of the present invention.
It is 95 seconds, preferably 20 to 150 seconds. The replenishment amount is 600 ml in the standard development per 1 m ² of the photosensitive material, but is 390 ml or less, preferably 30 to 390 ml in the processing of the present invention.
Particularly preferably, it is 50 to 200 ml. The color developing replenisher and the developer in the developing method of the present invention have been described above.

In the case of system A, a desilvering step is carried out following the developing step with the color developing solution, and the processing with the bleaching solution and the bleach-fixing solution is performed.

In the case of system B, for example, a mode in which a washing step, a rinsing step or a stabilizing bath step is performed following the developing step and the desilvering step is omitted is preferably performed. However, after the development step using the color developing solution, the desilvering step may be performed, the processing using the bleaching solution and the bleach-fixing solution may be performed, or the fixing step may be performed after the color developing step. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, a known bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid Organic acids, such as persulfates and hydrogen peroxide, are preferred.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of the following are listed: biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-asparagine Acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3
-Diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl)
-L-aspartic acid, β-alanine diacetate, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt such as ferric sulfate,
A ferric ion complex salt may be formed in a solution using ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate and a chelating agent such as aminopolycarboxylic acid. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, an aminopolycarboxylate iron complex is preferred.

The bleaching agent is added in an amount of 0.01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l, more preferably 0.10 to 0.50 mol / l, and still more preferably. Is 0.15 to 0.40 mol / liter.

The bleaching time is from 10 seconds to 6 minutes 30 seconds, preferably from 15 seconds to 60 seconds, particularly preferably from 15 seconds to 40 seconds.
Seconds. Various known organic acids (eg, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.) and organic bases (eg, imidazole, dimethylimidazole, etc.) are used in the bleaching solution, bleach-fixing solution or fixing solution. ) Or 2-picolinic acid or the like.
It is preferable to contain a compound represented by the general formula (A-a) described in Japanese Patent No. 211819 or a compound represented by the general formula (B-b) described in the same publication, such as cordiic acid. The addition amount of these compounds is preferably from 0.005 to 3.0 mol, more preferably from 0.05 to 1.5 mol, per liter of the treatment liquid.

The fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco-formation of the cyan dye are promoted. Conversely p
If H is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6.
If the pH is lower than this, the deterioration of the solution and the leuco conversion of the cyan dye are promoted, and if the pH is higher than this, desilvering is delayed,
Stain is likely to occur. To adjust the pH,
If necessary, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfinic acids such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It is preferable to contain the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or a carbonyl compound may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fix processing according to the present invention requires a processing time of 5
２４０240 seconds, preferably 10-60 seconds. The processing temperature is from 25C to 60C, preferably from 30C to 50C.
The replenishing rate is ²⁰ ml to 250 per m ² of the photosensitive material.
ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 60 ml.

The developing system applied to the processing apparatus of the present invention may be either system A or system B. In the case of system A, after the desilvering process such as fixing or bleach-fixing, the system B In most cases, after color development, rinsing,
It is common to perform one or more of the washing and stabilizing treatments.

In the method B, the effect of image quality relief by the image processing apparatus is great. In particular, the application of the present invention to a two-step process of performing a stabilizing bath after color development is a preferred embodiment. Also, since there is little need to preserve the film image, a simple rinsing bath step may be performed following the development step without performing an image stabilizing bath.

The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Soc).
(iety of Motion Pictureand Television Engineers)
Volume 4, p.248-253 (May 1955)
You can ask. Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. Occurs. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively.
Further, chlorinated fungicides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, copper ion, and others described in the official gazette.
1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) Can be used.

Further, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent fading of the dye and generation of stain, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609
And azolylmethylamines described in JP-A Nos. 519190 and 519190 may be added. It can be said that the stabilizing bath using such an additive has the function of an image stabilizing bath which may be provided subsequent to the washing step, in addition to the function of a stabilizing bath alternative to washing.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, it can be directly processed in an image stabilizing bath without going through a washing step. A compound having an image stabilizing function is added to the image stabilizing bath, and examples thereof include an aldehyde compound typified by formalin, a buffer for adjusting a film pH suitable for stabilizing a dye, and an ammonium compound. .
Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener can be added. In the treatment method of the present invention, when the stabilization is directly performed without going through a washing step,
All known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. Others
Chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid,
It is also a preferred embodiment to use a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Drying is performed following the washing and / or stabilizing step. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and removing the exhaust air.

[Other Descriptions Relating to the Image Forming Method of the Present Invention] (1) Positive Image Material for Output The image characteristic values equivalent to the reference processing obtained by the method of the present invention are output to a positive material. Obtained in the form of a positive image.
As described above, the output materials for obtaining a positive image include ink jet, sublimation-type thermal transfer, color diffusion transfer, color electrophotography, heat-developable silver salt color diffusion transfer, heat-developable multilayer color diazo, and silver salt. Any type of image signal, such as color paper, can be input as long as it is an electric or optical signal that is time-series.

Among them, color paper is particularly preferable. All of the photosensitive silver halide emulsions in the light-sensitive material preferably have silver chloride content of at least 95 mol%, the balance being silver bromide, and preferably comprise silver halide grains substantially free of silver iodide. Here, “substantially free of silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, more preferably 0 mol%. From the viewpoint of rapid processing, the above silver halide emulsion is particularly preferably a silver halide emulsion having a silver chloride content of 98 mol% or more. Among such silver halides, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The silver halide emulsion contained in at least one photosensitive silver halide emulsion layer has a coefficient of variation in grain size distribution (standard deviation of grain size distribution divided by average grain size) of 15% or less. Some are preferred and 1
Monodispersed emulsions of 0% or less are more preferred. It is preferable to use two or more of the above monodispersed emulsions in the same layer for the purpose of obtaining a wide latitude. At this time, the monodispersed emulsions preferably differ in average grain size by 15% or more, more preferably differ by 20 to 60%, and particularly preferably differ by 25 to 50%. The sensitivity difference between the monodispersed emulsions is preferably from 0.15 to 0.50 logE, more preferably from 0.20 to 0.40 logE, even more preferably from 0.25 to 0.35 logE. .

The silver halide photographic light-sensitive material for output used in the present invention contains silver chlorobromide having a silver chloride content of 95 mol% or more, which does not substantially contain silver iodide, and iron and / or ruthenium and / or The osmium compound is contained in an amount of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per mol of silver halide, and 1 × 10 ⁻⁵ mol per mol of silver halide in the localized silver bromide phase.
It is effective to use a silver halide emulsion containing ^-7 to 1.times.10.sup.- ⁵ mol of an iridium compound. As the silver halide photographic light-sensitive material for output used in the present invention, conventional photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (N
A material in which an information recording layer such as a magnetic layer is provided on a polyester of DCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. For the purposes of the present invention, a paper-based reflective support is particularly preferred, especially laminated with a plurality of polyethylene or polyester layers and at least one such water-resistant resin layer (laminated layer) such as titanium oxide. The reflective support containing the white pigment is preferred.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. A body in which a hydrophilic colloid layer containing a white pigment is provided on the body may be used. Also,
The reflective support may be a support having a specular or second-class diffusely reflective metal surface. In order to make the image reproducing system of the present invention compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) in which a semiconductor laser or a solid laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The maximum wavelength of the spectral sensitivity of the output color photosensitive material can be arbitrarily set depending on the wavelength of the scanning exposure light source to be used. In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in Table 1 below. To process color light-sensitive materials for output,
JP-A-2-207250, page 26, lower right column, lines 1 to 3
Page 4, upper right column, ninth line, and JP-A-4-97355 No. 5
The processing materials and processing methods described in the upper left column of the page, line 17 to the lower right column of page 18, line 20 can be preferably applied. As the preservative used in this developer, compounds described in the patents listed in Table 1 below are preferably used.

(2) Supplementary explanation of photographic light-sensitive material Regarding the photographic light-sensitive material used in the present invention, the contactless coupler has been described above, but the structure of the other light-sensitive materials will be described.

The color negative film used in the present invention has at least one photosensitive layer on a support.
As a typical example, the support has at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities (referred to as a unit photosensitive layer). It is a silver halide photographic material. This photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

These may contain, in addition to the coupler and the colorless coupler of the present invention, other DIR compounds, color mixing inhibitors and the like. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of two layers, a high-speed emulsion layer and a low-speed emulsion layer, which are directed toward a support. It is preferable to arrange them so that the sensitivities become lower sequentially. Also, Japanese Patent Application Laid-Open Nos. 57-112751, 62-200350, 62
As described in JP-A-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support and a high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, the low-sensitivity blue-sensitive layer (BL) /
High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH)
/ Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (R
H) / low-sensitivity red-sensitive layer (RL), or BH / B
L / GL / GH / RH / RL or BH / BL /
They can be installed in the order of GH / GL / RL / RH. As described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. For various purposes, color negative films having other layer constitutions are also disclosed in, for example, JP-A-59-202264,
U.S. Pat. Nos. 4,663,271; 4,705,744; 4,707,436;
It is described in each specification such as 3-89850.

As the silver halide used in the photographic light-sensitive material according to the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. It is preferable to use a polycrystalline emulsion of silver chloroiodobromide or silver iodobromide in order to achieve a balance between rapid processing. In particular, tabular grains having a silver iodobromide internal structure and non-tabular multi-structure grains are used. Preferred silver halides for use in color negative films are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Examples of the silver halide photographic emulsion usable in the present invention include Research Disclosure (hereinafter abbreviated as RD) N
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ", and No. 18716 (November 1979)
Mon.), p. 648, ibid. 307105 (1989 l
January, pp. 863-865, and Grafkid, "Physics and Chemistry of Photography," published by Paul Montell (P. Glafkides, C.
hemie et Phisique Photographique, Paul Montel, 1
967), "Photographic Emulsion Chemis" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemis)
try, Focal Press, 1966), Zeligman et al., "Manufacture and Coating of Photographic Emulsion," Focal Press (VLZelikm)
an, et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are written by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and Eng).
ineering, Vol. 14, pp. 248-257 (1970)
Years); US 4,434,226, 4,414,31
0, 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, or the inside and outside may be composed of different halogen compositions,
It may have a layered structure. Silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
This preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table.

[0221]

[Table 1]

Although various dye-forming couplers can be used in the light-sensitive material used in the present invention, the following couplers are particularly preferred. Yellow coupler: Formula (I) of EP502,424A,
A coupler represented by formula (1) or (2) of EP513,496A (particularly Y
-28); couplers of the formula (I) in claim 1 of EP 568,037A; US 5,066,576
A coupler represented by the general formula (I) in the column 1 of the line 45 to 55; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; EP 498,381
The couplers described in claim 1 on page 40 of A1 (especially 18
D-35 on page 4); Couplers represented by formula (Y) on page 4 of EP447,969A1 (especially Y-1 (page 17),
Y-54 (p. 41)); couplers represented by formulas (II) to (IV) in columns 36 to 58 of column 7 of US Pat. No. 4,476,219 (particularly II-17, 19 (column 17), II-24).
(Column 19)). Magenta coupler: Japanese Patent Application Laid-Open No. 3-39737 (L-57)
(Page 11, lower right), L-68 (page 12, lower right), L-77
(Page 13, lower right); A-4-63 of EP456,257
(Page 134), A-4-73, -75 (page 139); E
P486,965, M-4, -6 (p. 26), M-7
(Page 27); M-45 of EP 571,959A (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631.

Cyan coupler: JP-A-4-208443
CX-1,3,4,5,11,12,14,15 (1
4 to 16); JP-A-4-43345, C-7,10
(P. 35), 34, 35 (p. 37), (I-1), (I-1)
7) (pages 42 to 43): a coupler represented by the formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385. Polymer coupler: P-1, P of JP-A-2-44345
-5 (page 11).

Other known couplers having an appropriate diffusibility of a coloring dye, couplers for correcting unnecessary absorption of a coloring dye, among which a colorless masking coupler, and a compound which is photographically useful by reacting with an oxidized developing agent A compound that releases a residue (including a coupler) can be added to the light-sensitive material. In addition, a known bleaching accelerator releasing compound, a leuco dye releasing compound, a fluorescent dye releasing compound, a development accelerator or a fogging agent releasing compound, and a compound which releases a group which becomes a dye only after being released may be added to the photosensitive material. it can.

Examples of additives other than couplers include a dispersion medium of an oil-soluble organic compound, a latex for impregnation of an oil-soluble organic compound, an oxidized scavenger of a developing agent, a stain inhibitor,
Materials that reduce the amount of anti-fading agents, color development enhancers or color mixture inhibitors, formalin scavengers, hardeners, precursors for development inhibitors, preservatives, fungicides, chemical sensitizers,
Dyes, UV absorbers and the like are also added as appropriate.

The developing method of the present invention can be applied to general-purpose or movie general-purpose color negative films. In addition, Tokuhei 2-32615, Jitsuhei 3-397
84 can be applied to a film unit with a lens. Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; As described on page 879 of 307105, it is preferred to use a polyester support.

The color negative film used in the present invention preferably has a magnetic recording layer. The magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles used in the present invention are γFe
Ferromagnetic iron oxide such as ₂ O ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co such as γFe ₂ O ₃
Deposited ferromagnetic iron oxide is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-160332. JP-A-4-259911, 5
Magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-81652 can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,25 for photosensitive materials having a magnetic recording layer
0,404, 5,229,259, 5,215,8
74, EP 466,130.

For details including the polyester support, photosensitive material, processing, cartridges and examples of the photosensitive material according to the present invention, refer to Published Technical Report, Official Technical Publication No. 94-6023.
(Invention Association; 1994. 3.15.). Polyester is formed with a diol and an aromatic dicarboxylic acid as essential components.
6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid,
Examples of the diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,0
00. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
Particle size of at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. .00
Fine particles of crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), furthermore, sol-like metal oxides or composite oxides thereof Particles. 5 to 5%
500 mg / m ² is preferred, particularly preferably 10 to 350 mg / m ²
a m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material used in the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% PH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polystyrylmethyl. Siloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material used in the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. 0.8 ~
Preferably, the particle size distribution is narrower, and 90 to 90 of the total number of particles is 0.9 to 1.1 times the average particle size.
% Is preferably contained. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property.
m), poly (methyl methacrylate / methacrylic acid = 9)
/ 1 (molar ratio), 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm)
Is mentioned.

[0234]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example-1 (Preparation of photosensitive material sample) (1) Sample 101 A sample 101 was coated on an undercoated cellulose triacetate film support.
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.10 Silver Iodobromide Emulsion P Silver 0.03 Gelatin 0.44 ExC-1 0.004 ExC-3 0.006 Cpd-20 0.001 HBS-1 0.008 HBS-2 0.004

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.117 Gelatin 0.691 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.015 solid disperse dye ExF-3 0.020

Third layer (intermediate layer) ExC-2 0.045 Polyethyl acrylate latex 0.20 Gelatin 0.515

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.20 Silver iodobromide emulsion B silver 0.40 ExS-1 2.7 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExS-4 2.7 × 10 ^-4 ExC-1 0.18 ExC-3 0.036 ExC-4 0.12 ExC-5 0.018 ExC- 6 0.003 Cpd-2 0.025 HBS-1 0.17 Gelatin 1.26

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.20 Silver Iodobromide Emulsion D Silver 0.60 ExS-1 2.2 × 10 ^-4 ExS-2 8 × 10 ^-5 ExS-3 2.3 × 10 ^-4 ExS-4 2.2 × 10 ^-4 ExC-1 0.18 ExC-2 0.040 ExC-3 0.042 ExC-4 0.12 ExC-50 .015 ExC-6 0.010 Cpd-2 0.055 Cpd-4 0.030 HBS-1 0.15 Gelatin 1.04

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.17 ExS-1 4.0 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 2.1 × 10 ^-4 ExC-1 0.08 ExC-3 0.09 ExC-6 0.037 ExC-7 0.010 Cpd-2 0.046 Cpd-4 0.03 HBS-1 0.22 HBS-2 0.10 Gelatin 1.14

Seventh layer (intermediate layer) Cpd-1 0.094 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 0.89

Eighth Layer (Layer that Gives Layered Effect to Red Sensitive Layer) Silver Iodobromide Emulsion F Silver 0.40 Silver Iodobromide Emulsion G Silver 0.90 ExS-6 2.0 × 10 ^-4 ExS-10 8.4 × 10 ^-4 Cpd-4 0.030 ExM-2 0.23 ExM-3 0.049 ExY-1 0.054 HBS-1 0.20 HBS-3 0.007 Gelatin 1.29

Ninth Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.16 ExS-4 2.4 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-2 0.13 ExM-3 0.047 HBS-1 0.10 HBS-3 0.04 Gelatin 0.38

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver iodobromide emulsion H silver 0.08 silver iodobromide emulsion I silver 0.21 silver iodobromide emulsion J silver 0.08 ExS-4 3.3 × 10 ^-5 ExS-5 3.0 × 10 ^-5 ExS-6 1.4 × 10 ^-4 ExS-7 7.2 × 10 ^-4 ExS-8 1.6 × 10 ^-4 ExC-6 0.015 ExM-2 0.093 ExM-3 0.037 ExM-4 0.045 ExY-5 0.004 HBS-1 0.08 HBS-3 4.0 × 10 ^-3 Gelatin 0.41

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion K Silver 1.10 ExS-4 4.3 × 10 ^-5 ExS-7 1.0 × 10 ^-4 ExS-8 4.7 × 10 ^-4 ExC-6 0.005 ExM-3 0.070 ExM-4 0.028 ExM-5 0.026 Cpd-3 0.010 Cpd-4 0.050 HBS-1 0.23 Polyethyl acrylate latex 0.15 gelatin 1.18

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.18 Solid Disperse Dye ExF-5 0.060 Solid Disperse Dye ExF-6 0.060 Oil-soluble Dye ExF-7 010 HBS-1 0.094 Gelatin 1.204

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.15 silver iodobromide emulsion M silver 0.20 silver iodobromide emulsion N silver 0.15 ExS-9 8.0 × 10 ^-4 ExC-1 0.067 ExC-8 0.013 ExY-1 0.047 ExY-2 0.50 ExY-3 0.20 ExY-4 0.010 Cpd-2 0.10 Cpd-34 0.0 × 10 ⁻³ HBS-1 0.23 gelatin 1.45

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion O silver 0.96 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.42 ExY-30 .05 ExY-6 0.104 Cpd-2 0.07 Cpd-3 1.0 × 10 ^-3 HBS-1 0.14 Gelatin 1.20

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion Q Silver 0.10 UV-1 0.12 UV-2 0.10 UV-3 0.16 UV-4 0.025 HBS-10 .10 HBS-4 4.0 × 10 ^-2 gelatin 2.0

Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 Gelatin 0.75

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains palladium, iridium and rhodium salts.

Table 2 below shows the AgI content, grain size, and the like of the emulsions represented by the above-mentioned abbreviations.

[0254]

[Table 2]

In Table 2, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to O were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The compounds used for forming each of the above layers are as shown below.

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(2) Preparation of Samples 102 to 112 Samples 102 to 112 were prepared in the same manner as in Sample 101 except that ExC-6 of the 10th and 11th layers of Sample 101 were equimolarly substituted with other development inhibitor releasing couplers as shown in Table 3. Samples 102 to 112 having the same composition were produced. Compounds added to samples 101 to 105
Comparative DIR couplers, samples 106-112
Has a colorless coupler used in the present invention added thereto (the numbers in the compound column of Table 3 are the numbers of exemplary colorless couplers). Samples 101 to 112 are 6
After aged at 8% RH for 8 days to advance the dura to a dura degree comparable to that of the product, the specimen was subjected to the following test.

[0278]

[Table 3]

(Development Test) (1) Exposure <Samples for Image Quality Evaluation> Each sample film is a color patch and a gray image containing an actual technician image for comprehensive image quality evaluation, each minimum density part (Dmin) and maximum density part (Dmax). The Macbeth color chart on which the stair patch was burned was photographed under a standard C light source to obtain a sample for image quality evaluation. <Running Processing Test Samples> In addition to the sensitometric exposure described above for Samples 101 to 112, films processed to 35 mm each for a running test were exposed so that 25% of the silver halide in the film was exposed. . The exposure amount of 25% is the average exposure amount received from the subject in the average use of the color negative film. Therefore, a test for continuously developing a film having this exposure amount is a running development test that approximates the normal operating state of a commercial lab.

(2) Developing Processing Apparatus The developing processing apparatus was modified from an automatic developing machine FP-363SC manufactured by Fuji Photo Film Co., Ltd. for developing a negative film, and the processing time, temperature and replenishment amount in each immersion step were changed. Using an experimental machine that can change the image data, a frontier 350, a printer processor manufactured by Fuji Photo Film Co., Ltd., is used to output the image processing device and image signal to a printer and develop color paper for print production. These were combined and used as a developing apparatus of the present invention. Also,
For color paper development for print production, Fuji Color Paper SUPER FA Type D is used for color paper, and color paper processing prescription CP48S and its preparation agent are used for the processing prescription and processing agent (both are Fuji Photo Film Co., Ltd.)
Manufactured). This combination of the film developing machine and the printer processor constitutes a development processing apparatus equipped with an image reading / image processing apparatus that can also support the method B described in this specification. The image reading apparatus uses the transmission type reading apparatus shown in FIG. Sample 10 above
In each test of Nos. 1 to 112, the corresponding running samples were processed in accordance with the following development prescription, and then processed by a Macbeth color chart photographing sample for image quality evaluation. After the drying process, the image processing was performed. Was performed and output to the line printer described above to obtain a color print. For comparison, samples 101 to 11 were used.
2. A Macbeth color chart photographed sample for image quality evaluation was processed in the same manner, but a commercially available color printer processor having no image processing function (PP manufactured by Fuji Photo Film Co., Ltd.)
-1250) to obtain a color print.

(3) Development Processing Specifications Processing was performed using the following processing specifications. Processing-1 (Standard Processing) This processing is processing based on so-called standard processing used internationally in the color photographic market. The processing specifications are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 15 ml 10.3 liter Bleaching 50 seconds 38.0 ° C 5 ml 3.6 liters Fixing (1) 50 seconds 38.0 ° C-3.6 Liters Settlement (2) 50 seconds 38.0 ° C 7.5 ml 3.6 liters Stability (1) 20 seconds 38.0 ° C-1.9 liters Stability (2) 20 seconds 38.0 ° C-1.9 liters Stability (3) 20 seconds 38.0 ° C 30 ml 1.9 1 liter Drying 1 minute 30 seconds 60 ° C * Replenishment amount is 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1 bottle) Stabilizing solution is a counter-current method from (2) → (2) → (1)
The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleached liquid brought into the fixing step, and the amount of the fixer brought into the water washing step were 2.times.
5 ml, 2.0 ml, and 2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.4 0.5 Hydroxylamine 10.0 15.0 Sodium sulfite 4.0 9.0 Diethylene glycol 10.0 17.0 Potassium carbonate 39.0 59.0 Ethylene urea 3.0 5.5 Potassium bromide 1.4-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 11.4 Add water and add 1.0 liter 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (g) Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 128 180 Ammonium bromide 50 70 Succinic acid 30 50 Imidazole 20 30 Maleic acid 40 60 Add water 1.0 liter 1.0 liter pH (prepared with ammonia water) 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium bisulfite (72% solution) 20 80 Aqueous ammonium thiosulfate (750 g / L) 280 mL 1000 mL Imidazole 5 45 2- (N, N-dimethyl) ) Ethylaminomercaptotetrazole 1.0 3.0 Ethylenediaminetetraacetic acid 8 12 Add water and add 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.0 7.0

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 1.0 liter with water pH 8.5

(Evaluation) With respect to the obtained Macbeth chart for image quality evaluation and the color print containing a human image, 15 standard observers confirmed that the gradation was hard and soft and linear, the color balance, the whiteness and color stain of Dmin, and the color gradation of Dmax. Comprehensive evaluation, focusing on the darkness and color balance, etc. Scores are given on a 5-point scale, with 5 points being particularly excellent, 3 points being satisfactory, and 1 being unacceptable. Was evaluated.

(Results) The results are shown in Table 3. In Table 3, Samples 107 to 112 use the colorless coupler for the present invention, and Samples 101 to 105 use the development inhibitor releasing coupler for comparison. For reference, the results of the samples that were not subjected to image processing are also shown. Therefore, the portion surrounded by the thick frame (samples 107 to 112, with image processing) is the result of the method of the present invention. Sample 1
From a comparison between 07-112 and Samples 101-105, the colorless coupler used in the present invention is superior or at least maintains the same image quality as the conventional development inhibitor releasing coupler without performing image processing. (Right column in Table 3) When subjected to image processing, Samples 107 to 112 have higher evaluation points, and the effect of the image processing is clear (left column in Table 3, inside a bold line). On the other hand, Samples 101 to 105 show that the effect of improvement by image processing was extremely poor as described above as a weak point of the conventional colorless coupler (left column of Table 3,
Top).

[Embodiment 2] 1. Tested color negative film Of samples 101 to 112 used in Example 1, samples 101 to 103 using a development inhibitor releasing coupler other than the non-color coupler for the present invention and non-color coupler for the present invention were used. The following tests were performed using the samples 106 and 107 that were used.

[0290] 2. Method of photographic property test Exposure of photosensitive material sample The same method as in Example 1 was employed for exposure of the sample for image quality judgment and for exposure of the sample for running processing test.

Developing Processor and Processing As the developing processor, a two-bath experimental automatic developing machine comprising a developing process of the system B and a stabilizing bath process shown in FIG. 2 was used.
This developing machine is of a type capable of changing the processing time and having a developing tank equipped with a liquid level sensor, and capable of reducing and replenishing the ink. The liquid level sensor detects that the liquid level is lower than the level L of FIG. 2 by one replenishing unit (in this case, 15 ml) and gives an operation signal to the pump of the developer replenishing tank, and as a result, 15 ml And the liquid level is restored to the level L in FIG. The standard replenishment rate is 135-24Ex format film 1
A book is replenished with 15 milliliters, but a weight-reduced refill requires only about 2.5 milliliters for one film. When the processing amount detection means determines that the integrated processing amount is 40
When it is detected that the number is zero, the developing solution in the developing tank is discharged and replaced with a new solution. The replenishment tank is 3.6 liters for both the developer replenishment tank and the stabilizing bath replenishment tank. In the test of each sample, the following test was performed on a sample which was subjected to sensitometric exposure after 300 films subjected to exposure for running processing were processed. That is, the samples 101 to 103 subjected to the sensitometric exposure
, And 106 and 107, after passing through the drying section of the development processing section,
Image processing, output of image information, and printing were performed in combination with the frontier 350, and evaluation was performed in the same manner as in Example 1. However, in the image reading device,
The reflection type reader shown in FIG. 4 was used. As a comparative print, Frontier 350 was used, but the print was produced without passing through an image processing apparatus.

The processing steps and the composition of the processing solution are shown below. (Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 20 seconds 65.0 ° C Weight loss replenishment 1.0L Stabilization bath 20 seconds 40 ° C Weight loss replenishment 1.0L Drying ** 20 seconds 60 ° C Is a photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1 bottle 2.5ml.) ** Drying is a heat roller (Tungsten Halogen heater, surface temperature 55 ° C) with Teflon coated aluminum roller and hot air at 60 ° C. Spray drying was also used.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution Replenisher solution Diethylenetriaminepentaacetic acid 2.0 g 2.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.4 g Disodium-N, N-bis (sulfonateethyl 9.) Hydroxylamine 13.2 g 13.2 g Sodium sulfite 4.0 g 4.0 g Potassium bromide 20.0 g-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 0 g 10.0 g Potassium carbonate 39 g 39 g Add water 1.0 L 1.0 L pH (adjusted with sulfuric acid and KOH) 10.10 11.10

(Stabilization bath) Common to tank liquid and replenisher 50.0 g of succinic acid Water was added to 1.0 L pH (prepared with aqueous ammonia and nitric acid) 3.5

[0295] 4. Test results The results are shown in Table 4. Since it is a simplified process of two steps, the image quality is inferior unless any sample is subjected to image processing, but it is shown that the image quality can be considerably relieved by the image processing. However, to the extent that samples 101-103 using conventional development inhibitor releasing couplers were still inadequate, samples 106 and 107 using the colorless coupler according to the present invention provided satisfactory image quality.

[0296]

[Table 4]

Example 3 Example 2 was the same as Example 2 except that the bleaching solution of Example 1 was used instead of the stabilizing bath, and after the stabilizing bath was completed, the image was read without drying. A color print was obtained in the same manner. The image reading device was the reflection type image reading device shown in FIG. 4, and an image was read from a sample in which developed silver and undeveloped silver halide coexisted by bleaching. Table 5 shows the results. It is shown that the image quality of each sample is inferior unless image processing is performed, but the image quality is considerably relieved by the image processing. However, to the extent that samples 101-103 using conventional colorless couplers were still inadequate, samples 106 and 107 using colorless couplers according to the present invention provided satisfactory image quality.

[0298]

[Table 5]

[0299]

According to the present invention, a developed silver halide color photographic light-sensitive material using a colorless coupler is photoelectrically read from a developed image, converted into time-series digital image information, and image quality is improved by image processing. When processed by a development processing device that performs correction and output, the effect of improving the original sharpness and color reproducibility is reduced with gradation distortion, but the colorless coupler described above used in the present invention is used. In this case, there is no such gradation distortion, and the original effect of the DIR coupler such as the effect of suppressing the development of the adjacent layer and the effect of suppressing the development of the own layer is sufficiently exhibited. Taking advantage of this feature, it is possible to omit a part of the development processing step or to perform rapid processing using a high-temperature or high-activity processing solution to achieve both rapid development processing and high image quality.

[Brief description of the drawings]

FIG. 1 is a block diagram showing a basic configuration of a developing apparatus according to the present invention and an overall flow of a developing process.

FIG. 2 illustrates an embodiment of a development processing apparatus according to the present invention.
It is a schematic structure figure of a process development processing device.

FIG. 3 is a diagram schematically showing a transmission type image reading apparatus.

FIG. 4 is a diagram schematically illustrating a reflection type image reading apparatus.

FIG. 5 is a block diagram showing a part of the configuration of the image processing apparatus 5 shown in FIG. 2;

FIG. 6 is a book diagram showing another part of the configuration of the image processing device 5 shown in FIG. 2 which is not shown in FIG. 5;

FIG. 7 is a block diagram showing details of a first frame memory unit, a second frame memory unit, and a third frame memory unit shown in FIG. 5;

FIG. 8 is a block diagram showing details of the first image processing means shown in FIG. 6;

FIG. 9 is a diagram schematically illustrating an image output device that outputs an image from time-series image information input from a development processing device.

FIG. 10 is a schematic view of a laser beam irradiation unit of the printer.

[Explanation of symbols]

 Description of reference numerals in FIGS. 1 to 10 F film P color print or color paper L liquid level 1 image reading device 5 image processing device 8 image output device 10 transmission type image reading device 11 light source 12 light amount adjustment unit 13 color separation unit 14 diffusion unit Reference Signs List 15 CCD area sensor 16 Lens 17 Amplifier 18 A / D converter 19 CCD correction means 20 Log converter 21 Interface 22 Carrier 23 Motor 24 Drive roller 25 Screen detection sensor 26 CPU 30 Reflective image reader 31 Light source 32 Mirror 33 Color balance Filter 34 light intensity adjustment unit 35 CCD area sensor 36 lens 37 amplifier 38 A / D converter 39 CCD correction means 40 log converter 48 interface 49 averaging means 50 a first line buffer 50b second line buffer 51 first frame memory unit 51R R data memory 51G G data memory 51B B data memory 52 second frame memory unit 52R R data memory 52G G data memory 52B B data memory 53 third frame memory unit 53R R data memory 53G G data memory 53B B data memory 55 selector 60 CPU 61 first image processing means 62 second image processing means 63 input bus 64 output bus 65 data bus 66 memory 67 hard disk 68 CRT 69 Keyboard 70 Communication port 75 Data synthesizing means 76 Synthetic data memory 76 R R data memory 76 G G data memory 76 B B data memory 77 Interface 78 Inter Reference numeral 79 CPU 80 Image data memory 81 D / A converter 82 Laser light irradiation means 83 Modulator driving means 84 a, b, c Semiconductor laser light source 85 Wavelength conversion means 86 Wavelength conversion means 87 R, G, B Light modulator 88 R, G , B Reflecting mirror 89 Polygon mirror 90 Color paper 91 Magazine 92 Perforation means 94 Color developing tank 95 Bleaching and fixing tank 96 Washing tank 97 Drying section 98 Cutter 99 Sorter 100 Color density gradation conversion means 101 Saturation conversion means 102 Digital magnification conversion means 103 Frequency processing means 104 Dynamic range conversion means 111 Processing section 112 Developing tank 113 Stabilizing bath 114 Drying section 116 Liquid level sensor 117 Liquid level sensor 121 Circulating fluid intake 122 Circulating pipe 123 Circulating pump 124 Fluid feeding pipe 125 Heater 126 opposing roller 127 opposing roller 128 upper outer member 129 lower outer member 130 seal blade 131 circulating liquid intake 132 circulating pipe 133 circulating pump 134 liquid feeding pipe 135 heater 136 opposing roller 137 opposing roller 138 upper outer member 139 lower outer member 140 seal Blade 150 Refill port 151 Refill port

Claims (5)

[Claims] 1. A color image forming method using a silver halide color photographic light-sensitive material for photography containing at least one coupler which releases a photographically useful group or a precursor thereof by a coupling reaction with an oxidized developing agent, The coupler is a coupler which releases a photographically useful group or a precursor thereof with ring formation by an intramolecular nucleophilic substitution reaction by a nitrogen atom directly derived from the developing agent in the product of the coupling reaction and directly bonded to the coupling position. The color image forming step comprises: (1) subjecting the photosensitive material to a development process; and (2) photoelectrically reading image information of an image obtained by the development process and converting the image information into electrical image information.
(3) A color image forming method including a series of steps of performing image processing on the electrical image information. 2. A color image forming method using a silver halide color photographic light-sensitive material for photography containing at least one coupler which releases a photographically useful group or its precursor by a coupling reaction with an oxidized developing agent, The coupler is a coupler which releases a photographically useful group or a precursor thereof with ring formation by an intramolecular nucleophilic substitution reaction by a nitrogen atom directly derived from the developing agent in the product of the coupling reaction and directly bonded to the coupling position. The color image forming step comprises: (1) subjecting the photosensitive material to a development process; and (2) photoelectrically reading image information of an image obtained by the development process and converting the image information into electrical image information.
The method according to claim 1, further comprising: (3) a series of steps of performing image processing on the electrical image information, and (4) outputting the image-processed electrical image information to a printer to obtain a color print. The color image forming method as described above. 3. The color image forming method according to claim 1, wherein the coupler is represented by the following general formula (I). General formula (I) COUP-AEB (wherein COUP represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents
In the coupling product of COUP and oxidized developing agent, a 4- to 8-membered ring is formed by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and the electrophilic site E. It represents a divalent linking group or a single bond capable of releasing B, and may be bonded to COUP at the coupling position of COUP, or may be bonded to COUP at a position other than the coupling position of COUP.
B represents a photographically useful group or a precursor thereof). 4. The development processing includes at least one of (1) a bleaching step comprising at least one of bleaching and bleach-fixing processing, and (2) a fixing step comprising at least one of fixing and bleach-fixing processing. The color image forming method according to any one of claims 1 to 3, wherein the developing process is not performed. 5. The developing process according to claim 1, wherein the color development is performed at 45 ° C.
The color image forming method according to any one of claims 1 to 4, wherein the development process is performed as described above or performed within one minute.