JPS61110135A - Dye transfer method - Google Patents

Abstract

PURPOSE:To prevent the generation of uneven transfer by superposing a movable dye-contg. photosensitive material and a material having a dye fixed layer on the base of either of which is coated paper on each other and transferring the dye to the dye fixed layer. CONSTITUTION:The base of at least either of the photosensitive material contg. the movable dye on dye fixed material is formed of the coated paper in the stage of superposing the photosensitive material contg. the movable dye on the die fixed material having the dye fixed layer and transferring the dye to the dye fixed layer. The coated paper is the paper formed by coating a paint prepd. by mixing a mineral pigment such as clay and adhesive agent such as casein to one or both surfaces of raw paper. The thickness thereof is about 20-200g/m<2> in basis weight and the relatively light paper of about 50-100g/m<2> is particularly preferable.

Description

BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to a method for transferring imagewise mobile dyes from a photosensitive element having formed thereon to a dye-fixing element, and in particular to a method for transferring dyes substantially free of water. Evenly transferring the mobile dye from a heat-developable color photosensitive material containing a dye-providing substance that reacts with photosensitive silver halide to generate or release a mobile dye by heating to a dye-fixing material in a state free of It is about the method.

Prior art and its problems Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. It is used in

In recent years, a technology has been developed that allows simple and rapid Kam images to be obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer, etc. to a dry processing using heating, etc. has been done.

Heat-developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, please refer to Tatoba Fundamentals of Photographic Engineering (1272, published by Corona Publishing Co., Ltd.), No. 3, 30/, No. 471, No. 3 JP Ko, O, Zo No. 3. Hiro! 7, 07J-, British Patent No. i, i3i, i
or No. 1. /17゜777 issue and Research Disclosure magazine lli7j June issue 2-l! Page (R
I)-/70λ) VC is described.

Regarding how to obtain color images by heat development,
Many proposals have been made. U.S. Patent No. J, J3/, 2
No. 16, No. 3, 74/, No. 270, No. 3, Ocol.
Ko I/-O, Belgian Patent No. 102.172, Research Disclosure Magazine 7! Year issue 3t, 3x
A method of forming a color image by combining an oxidized form of a developer with a coupler, and various developing agents used for its removal are described in the pages.

In addition, a final method in which a nitrogen-containing heterocyclic group is introduced into a dye, a silver salt is formed, and the dye is released by heat development was published in Research Disclosure Magazine in 2017! Monthly issue! μ~jr page (RD-
#ri A4).

Further, regarding the method of forming a positive color image by thermal silver dye bleaching method, for example, Research Disclosure magazine / 276 φ month issue, pages 30-3 (RD-/Hirohiro 33)
), same magazine IP December 76 issue/4C-/J page (RD-/
J Cocoa), U.S. Patent No. 23! ,? ! No. 7 describes a useful method for bleaching dyes.

Further, regarding the method of forming color images using leuco dyes, for example, US Pat. Rirz.

rtz, No.≠, 02λ, No. 677, etc.

However, in these color image forming methods, during long-term storage of the formed color image, discoloration and coloring of the white background occur due to coexisting silver halides, silver complexes, developing agents, etc. A new method of forming a color image by thermal development that has improved these drawbacks is disclosed in Japanese Patent Application Laid-open Nos. J7-/7R≠O, J7-1167741, 17-1Pilljr, and Sho! No. 7-207210, No. 3l-J-Ij4'j, No. 7-207210, No. 7-207210, No. 3l-J-Ij4'j, Same! ! −7 Octopus ≠ No. 7,
Dojo 5r-ii No. 137, Dojoj-/, ≠ri Ohiro No. 6,
same! ? -4tlr7444, jP-4JrJW,
same! Turf 10 Hiro No. 6, JP-47I/-j 0
Same issue! 11730, etc.

When photosensitive silver halide and/or organic silver salts are reduced to silver by heat development, a mobile dye is generated or released in response to or inversely to this reaction, and the mobile dye is This is a method in which the dye is transferred to a dye-fixing element.

These methods provide excellent color images without fading or coloring of white areas, but the transferred dye concentration is extremely low in the areas of the dye-fixing material where the dye should originally be transferred. An inconvenience may occur in which seven irregular circular portions are scattered (hereinafter, this phenomenon is referred to as transfer unevenness).

Such inconveniences occur in conventional dye image forming methods (for example, color diffusion transfer methods) in which wet processing is performed using a developer, etc., and are caused by the presence of water when transferring a mobile dye to a dye fixing material. This is a problem that occurs specifically in dye image forming methods such as the present invention, where the amount of dye is very small. It has also been found that the extent of this transfer unevenness depends on the thickness of the photosensitive material used and the support of the dye-fixing material, and the thinner the support is used, the more conspicuous it occurs. This makes it possible to make the support thinner and store a large amount of dye-fixing material in a small swipe after transfer.
This poses a serious problem when trying to increase the amount of light-sensitive material or dye-fixing material that can be wrapped in a 70-layer roll, to make it easier to cut, or to reduce the cost of the product.

(2) Purpose of the Invention Another object of the present invention is to provide a dye transfer method in which the above-mentioned transfer unevenness does not occur.

■ Structure of the Invention The present inventors conducted various studies to achieve the above object, and found that the support used when the coating surface of a photosensitive material and the coating surface of a dye fixing material are overlapped for transfer. It was discovered that due to the unevenness of the body, there are areas where the two do not come into close contact, which prevents transfer of the mobile dye and causes the above-mentioned failure.The team searched for and selected various materials for the support, and found that the thickness of the material could be increased. We have discovered a material that does not cause the transfer unevenness even if it is thin, and have accomplished the present invention.

That is, the present invention provides a dye transfer method in which a photosensitive material containing a mobile dye is superimposed on a dye fixing material having a dye fixing layer, and the dye is transferred to the dye fixing layer. Or a dye transfer method, characterized in that at least one support of the dye fixing material is made of coachite paper.

The Coachite A- used in the present invention is a mineral pigment such as clay and an adhesive (e.g. casein, starch, latex, polyvinyl alcohol or a combination thereof).
VCf11 coating on one or both sides of base paper (e.g., high-quality paper, medium-quality paper, etc.) is treated with paint mixed with
2), coated paper (approximately 111 cloth weight/ioy per 1n2), lightweight coated paper (approx. - Contains cast-coated paper that is crimped onto a finished dryer and dried to give it a strong gloss.
T/! page,! (See pages Jj to J-34, etc.).

This coated paper has a high surface smoothness even if the base paper is thin (especially cast coated paper has a very high surface smoothness), so the photosensitive layer, dye fixing layer, etc. The membrane surface also becomes smooth.
The adhesion between the light-sensitive material and the dye-fixing material is extremely high, making it possible to prevent uneven transfer.

The thickness of the coachite hard material used in the present invention is 2 to 2 oz/m in terms of basis weight.
s patent j Of / m 2 ~ / 00 f / @
2, which is relatively thin (light), is preferable.

In the present invention, a coating layer for a photosensitive material or a dye fixing layer, which will be described later, may be directly coated on the coated veneer. Coating or laminating with polymers such as
The coating layer for photosensitive materials or the dye fixing layer described above may be applied. If necessary, a white pigment such as titanium dioxide may be kneaded into the polymer such as polyethylene to form a white reflective layer. Also, what is the preferred range of coating or runner thickness for this polymer such as polyethylene? μ to jOμ, especially when the film thickness is relatively thin, ≠Oμ or less, the effect of relying on the support of the present invention becomes remarkable.

Although the present invention is equally effective in preventing transfer unevenness when transferring mobile dyes from one material to another, it particularly provides at least (1) a photosensitive silver halide (
2) a binder; (3) correspondingly or inversely when the photosensitive silver halide is reduced to silver under high temperature conditions;
Imaging a light-sensitive material having a dye-providing substance on a support that produces or releases a mobile dye, and at the same time,
Alternatively, in a dye transfer method, the mobile dye is then heated to form an image, and then the mobile dye is transferred to the dye fixing layer by overlaying the dye fixing material having a dye fixing layer on the support. Demonstrates excellent effects. In this case, as a support for at least one of the light-sensitive material and the dye-fixing material, particularly as a support for the dye-fixing material, the above-mentioned Kochitoy-/4- is used.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the particles may be uniform or may have a multiple structure with different compositions on the surface and inside (JP-A-17-111-232, JLR-/01R, 733, Ibid. !tar≠t7!! No. !tar!-237, US Patent No. ≠, 4tJJ,
No. 04'1 and European Patent No. IOOO, RIO). In addition, the thickness of the particles is 0.2 μm or less, and the diameter is at least o, t.
In the μ door, the average aspect ratio is 5 or more tabular grains (US Pat. .2 Hiro/.

A 444 people/etc.), or a monodisperse emulsion with a nearly uniform particle size distribution (JP-A-17-171231, same jt
-ioorat No. 31-/ll-129, International Publication No. 13102JJIA/, European Patent No. 6≠, II/J
Aj and Aj No. 13, j 77A/etc.) may also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing monodisperse emulsions of 2's or more with different grain sizes.

The grain size of the silver halide used in the present invention preferably has an average grain size of o, ooi μm to lOμ,
More preferably, the thickness is from 0.00/μm to 1 μm. These 7-silver halide emulsions may be prepared by any of the acidic method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt is the one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used. Back-mixing method where particles are formed under silver ion excess, or pA
The Chondral double jet method, which keeps g constant, can also be used. In addition, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (% Kaisho!!-/Hiroko No. 32, same j
r-izriλ≠ No., US Patent No.! ,4jO,717
No. etc.).

Epitaxially bonded silver halide grains can also be used (Japanese Patent Application Laid-open No. A-/A/2, Japanese Patent Application Publication No. 2003-11002, Of-Hiro, +, r).

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, silver chloroiodide, silver iodobromide, chloride, etc. Preference is given to using silver iodobromide.

Such a silver salt can be obtained by adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide to obtain silver iodobromide having the above characteristics.

In the stage of forming the silver halide grains used in the present invention, ammonia and Japanese Patent Publication Akihiro 7-i are used as silver halide solvents.
Organic thioether derivatives described in No. i3rt or sulfur-containing compounds described in JP-A No. 14!3/R can be used.

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Further, for the purpose of improving illuminance failure and low illuminance failure, water-soluble iridium salts such as iridium chloride (■, ■) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or the precipitation method can be applied.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. for emulsions for ordinary light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A No. 61-/Ko-41 Colo No., No. 11-2/16 Hirohiro).
.

The silver halide emulsion used in the present invention may be of the surface IS type in which IW images are mainly formed on the grain surfaces, or may be of the internal A image type in which IW images are formed inside the grains. Direct inversion emulsions in combination with internal a-image deaf emulsions and nucleating agents may also be used. The internal latent image emulsion suitable for this purpose is the first US patent! riλ.

λ! No. O, No. 3.7t/, Koa No., Tokuko Akiyo r-J
! JIA No. and Japanese Patent Application Laid-Open No. 1996-7-36611-/. A preferred nucleating agent for combination in the present invention is US Patent No. 3.2λ7°! Yokogo, Dodaihiro, λ≠! , No. 037, Hiroshi.

2! J, No. 111, g+, x+'a, oJi
No. ≠, = 76, Jt No. 3 and OLS No. 2, 63
1.316 etc.

The coating amount of photosensitive silver halide used in the present invention is silver equivalent/IR9 to IR9/0? / 7FL 2
is within the range of

In the present invention, an organic metal salt that is relatively stable against one light can be used together with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance. Among such organic metal salts, organic silver salts are particularly preferably used. When an organic metal salt is used in combination in this way, the photothermographic material has a ro oc or higher, preferably an i
o.

When heated to a temperature of 0C or higher, it is thought that the organometallic oxidizing agent also participates in redox activity using the silver halide latent image as a catalyst.

Examples of organic compounds that can be used to form the breeding silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Can be mentioned.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylunic acid, and oleic acid. Typical examples include silver salts derived from adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, or camphoric acid.

Halogen atoms or hydroxyl group substituted products of these fatty acids,
Alternatively, silver salts derived from aliphatic carboxylic acids and the like with thioether groups can also be used.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, J,j-dihydroxybenzoic acid, 0-lm- or p-methylbenzoic acid, -
14t-dichlorobenzoic acid, acetamidobenzoic acid, p
-Phenylbenzoic acid, gallic acid, tannic acid, heptalacid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-≠-methyl-≠-
Typical examples include silver salts derived from thiazoline-corchion. Examples of the silver salt of a compound having a mercapto or thiocarbonyl group include J-mercapto≠-phenyl-/, λ, ≠-triazole, comelcabutobenzimidazole, λ-mercapto! -aminothiadiazole, λ-mercaptobenzothiazole, S
- dithiocarboxylic acids such as alkylthioglycolic acid (number of carbon atoms in alkyl group/co-2), dithioacetic acid,
Thioamides such as thiostearamide! -Carboxy7-methyl-2-phenyl-≠-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-! −
Examples include silver salts derived from mercapto compounds such as benzylthio 7,2°-triazole and the like described in US Pat.

As a silver salt of a compound having an imino group, Tokuko Sho 4c!
-40270 or the same pt-7rait, benzotriazole or its derivatives, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole,! -Halogen-substituted benzotriazoles such as chlorobenzotriazole, carboimidobenzotriazoles such as butylcarboimidobenzotriazole, nitrobenzotriazoles described in JP-A No. 1-//1432, and nitrobenzotriazoles described in JP-A No. 1-//1432; sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or μ-droxybenzotriazole, /, λ, 4t-) lyazole, /H-tetrazole, carbazole, saccharin, etc. described in U.S. Patent No. 2, 0,702; Representative examples include silver salts derived from imidazole and its derivatives.

1fe-B, D/7029 (June 1971) Organometallic salts other than silver salts such as silver salts and copper stearate described in K, phenylpropiol described in Japanese Patent Application No. 11-2-2/J-31 Silver salts of carboxylic acids having alkyl groups, such as acids, can also be used in the present invention.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
o, oi to io mole, preferably Ooi to 1 mole can be used in combination. Is the total coating amount of photosensitive silver halide and organic silver salt ron9 to 10? /m2 is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopocyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei are Kf on carbon atoms
It may be illuminated.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, λ-thioxazolidine-λ
, Hiro-dione nucleus, thiazolidine nucleus, Hiro-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

Along with sensitizing dyes, these colors do not have any spectral sensitizing effect on their own! The emulsion may contain a substance that does not substantially absorb X or visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. horns - No. 1 33, 3 0, No. J, 43
No. 1,7λ1, etc.), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. No. 3,7μJ, j1
0 isobaric), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3.4/j, 41
No. 3, same No. 3. Buij, tea≠/issue, same No. 3. Otsu/7
．． Kota! Particularly useful are the combinations described in No. J, 631,721.

These sensitizing dyes can be incorporated into a silver halide photographic emulsion by directly dispersing them in the emulsion, or by dispersing them in water, methanol, ethanol, acetone, etc.
It may be added to the emulsion after being dissolved in a solvent such as methyl celonorb alone or in a mixed solvent. Alternatively, they may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol, then dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion. Further, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. In addition, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately,
Alternatively, a mixture may be dissolved. When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives.

It may be added to the emulsion at the time of chemical ripening or before or after chemical ripening.
It may be carried out before or after the nucleation of silver halide grains according to No. 44 of Ko JJ-, No. 44.

The amount added is generally about 10" to 10 moles of F) per mole of silver halide.

In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a mobile dye in response to or inversely to this reaction; That is, it contains a dye-donating substance.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. The method using this coupler is that the oxidized product of the developer produced by the redox reaction between the silver salt and the developer reacts with the coupler to form a dye, and is described in many literatures. 2ri l~33≠niji, and 35 Hiroshi~36/Bage, Makoto Kikuchi-author, Photo Chemistry' 3rd edition (Kyoritsu Shuppan) Ko Jr4t~Uta! It is described in detail on the page.

(9) A dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of a dye-donating substance. Specific examples of dye silver compounds can be found in Research Disclosure magazine, J. 1971 issue! It is described in Da-sr Page, (RD-/l, P41.), etc.

Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances.

Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No. Hiroshi, λ
3! , No. 57, Research Disclosure Magazine, / No. 7, Hirotsuki issue, No. 30-3 (RD-Hari 33), etc.

Also, US Patent No. 3.7r! , ltj issue, same≠.

Leuco dyes described in No. 0-2,617 and the like can also be cited as examples of dye-donating substances.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner.

This type of compound can be represented by the following general formula CLI.

(Dye-X) n-Y (L I
] Dye represents a dye group or a dye precursor group, X represents a simple bond or a linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image in the form of an image (Dye-X)
A difference is created in the diffusivity of the compound represented by n-Y, or Dye is released, and the released Dye and (Dy
e-X) represents a group having a property that causes a difference in diffusivity between n-Y, n represents lt or λ, and when n is 2, λ D y e-X is Specific examples of the dye-donating substance represented by the general formula [L], which may be the same or different, include a dye developer in which a hydroquinone developer and a dye component are linked, as described in U.S. Pat. ．． /JIA, 7
6≠ No. 3.362,112, 1gJ, 197,200, 3. Hatu, r hiro! No. 3. ≠Described in No. 12,274, etc. 'In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was discovered in JP-A-Sho! /-63.
61r etc., a substance that releases a diffusible dye by an intramolecular rewinding reaction of the inoxacilone ring was disclosed in JP-A-41-
///, No. 421, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

Furthermore, in these methods, development and dye release or diffusion occur in parallel, so it is very difficult to obtain an image with a high S/N ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have the ability to release a color patch, and is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains unoxidized. A system has also been devised in which a diffusible dye is released using a method of releasing a diffusible dye, and a specific example of a dye-donating substance used therein is disclosed in JP-A No. 13-13-lt0. Hiro-730. Octopus No. 7, same! Otsu-/buμ, 34tλ, same jJ-3! , No. 133.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. , 330. Jλ≠ No. 761, U.S. Patent No. 3. ≠≠3. In addition, a substance that generates a diffusible dye through the reaction of a coupler having a diffusion-resistant group as a leaving group and an oxidized developer is disclosed in U.S. Patent No. 3. It is described in λλ7, jJO issue, etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised. Representative examples are shown below along with literature. Definitions in the general formula are described in each literature.

U.S. Patent No. J, Ykot, 37λ, etc. U.S. Patent No. 013,312 etc. Issue Ba1last Tokukai Sho! Tar tyr3y JP 13-JrIP JP JP/-104L, J Ko 3 JP JP/-10 pi, 3≠3 Ba1list JP JP/-10 HI, 3G 3 NH302 -Dye Research Disclosure Magazine / 74At J Issue H US Patent No. 3.7! , No. 062H U.S. Patent No. 3,721.11J Ballast U.S. Patent No. 3. ≠≠3. All of the dye-donating substances described above can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents cited above. Since it is not possible to list all the preferred compounds here, some of them will be shown as examples. For example, the dye-donating substances represented by the general formula (LI) include those described below.

LI-I LI-2 LI-4 LI-s LI-a LI-7 LI-a l-9 LI-1o
] L knee 1 t H JI-12 The compounds described above are examples, and the present invention is not limited thereto.

In the present invention, the dye-donating substance is U.S. Patent No. 1.3λ
It can be introduced into the layer of Jg optical material by known methods such as the method described in λ, No. 027.

In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthanolic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate),
a high boiling point organic solvent such as (for example, tributyl trimesate) or an organic solvent with a boiling point of 300C to 1to0C,
For example, after dissolving in lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary dithyl alcohol, methyl in butyl ketone, β-ethoxyethyl acetate, methylseron rub acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. be done. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

The dispersion method using polymers described in ``19 Japanese Patent Publication Shoj/-JWrjJ No. 19 and JP-A No. 1999/1999 Tatako No. 3 can also be used.Also, when dispersing a dye-providing substance in a hydrophilic colloid, Various surfactants can be used, including those listed as surfactants elsewhere in this specification.

The amount of the high boiling point organic solvent used in the present invention is IO? Below, preferably! ?
It is as follows.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include sulfite (I)
Inorganic reducing agents such as Jium and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, aminophenols, catechols, p-phenylenediamines, J- Pyrazolidinones, hydroxytetronic acid, ascorbic acid, Hiro-Amino-! - pyrazolone, etc., as well as T. H. James, 'T
hetheory of the photogr
Reducing agents described in aphicprocess' 4AHi, Ed, 2/~JJu pages can also be used. Also,
Tokukai Akira! Bu-/No. 31,736, same as 7-30,,Z
4AJ, US Patent No. ≠, JJO, t/7, etc., may also be used.

US Patent lxJ, OJ2. Combinations of various developers can also be used, such as those disclosed in No.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
, 0/-20 mol, particularly preferably 017 to 70 mol.

Image formation accelerators can be used in the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive material layers. It has functions such as promoting the movement of dye from the dye fixation layer to the dye fixing layer, and from a physicochemical function, it has the function of base or base precursor, nucleophilic compound, oil, hot solvent, surfactant,
It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound may have multiple functions. many.

(a) Bases Examples of preferred bases include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides,
317 phosphates, borates, carbonates, quinolates, metaborates; ammonium hydroxides; ≠-grade alkylammonium hydroxides; hydroxides of other metals, etc.; are aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis(p-( dialkylamino) phenylcomethanes)
, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, especially p K
It is preferable that a is greater than or equal to t.

Base precursors include salts of organic acids and bases that decompose by decarboxylation upon heating, compounds that decompose to release amines through reactions such as intramolecular nucleophilic substitution, Rossen rearrangement, and Beckmann rearrangement. Preferably used are those which cause some kind of reaction upon heating and release a base. Preferred base precursors include the salts of trichloroacetic acid described in British Patent Nos. Meta t, 2≠R, etc.; US Patent Nos. ≠ and ot;
Salt of α-sulfonylacetic acid described in O9≠-〇, patent #
E! ? -! r, salts of propiolic acids described in No. 700, cocarboxycarboxamide derivatives described in U.S. Pat. Hydroxamic carbamates described in the Patent rHHr-It Otsu θ utilizing Rossen rearrangement (Special Application No. 97), Hydroxamic carbamates can be converted into nitrile by heating. Generated patent application Sholl-37,414! Examples include aldoxime carbamates described in item -. Other British Patent No. y
yr, yar issue, US patent @j, 2,20゜14, JP-A-Sho! No. O-λλg2, British Patent No. λ, 07, ≠t
The base precursors described in No. Q etc. are also useful.

(c) Nucleophilic compounds water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols In addition, salts or precursors of the above-mentioned compounds can also be used.

(d) Oil A high-boiling organic solvent (so-called star-blurring agent) used as a solvent during emulsification and dispersion of hydrophobic compounds can be used.

(e) Hot solvents Solid at ambient temperature, melting near the development temperature and acting as solvents, such as ureas, urethanes, amides, pyrudines, sulfonamides, sulfones, sulfoxides, esters, and ketones. and ether compounds.
Those that are solid at 0C or lower can be used.

(f) Pyridinium salts described in surfactant %Q Shoj9-701j≠7,
Ammonium salts, phosphonium salts, Tokukaisho! Examples include the polyalkylene oxides described in No. 7λ3/.

Examples include imides, nitrogen-containing heterocycles described in Japanese Patent Application No. 1983-ZITR No. 7, thiols, thioureas, and thioethers described in Japanese Patent Application No. 7-λλ2≠7.

The image formation accelerator may be incorporated into either the light-sensitive material or the dye-fixing material, or may be incorporated into both.The layers in which it is incorporated may also be included in the emulsion layer, intermediate layer, protective layer, dye-fixing layer, and the like. It may be built into any layer adjacent to the . The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support.

The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases formic acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, and mercar/) compounds that undergo a substitution reaction with a coexisting base when heated. For example, the acid precursor used in the patent application Shoj1-
17422 and the oxime esters described in Patent Application Shoj P-t! Examples of electrophilic compounds that cause a substitution reaction with a base when heated include compounds that release an acid through Rossen rearrangement as described in No. 13≠; Examples include.

The above-mentioned development stoppers are particularly effective when a base precursor is used, which is preferable.

In that case, the value of the base precursor/acid precursor ratio (molar ratio) is preferably //2Q-λ0//, //j-
j/I is more preferred.

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.

Among them, isothiuroniums typified by co-hydroxyethyl isothiuronium trichloroacetate described in US Pat. No. 3,117/671, US Pat. Bis(intiuroniums) such as i, r-(3,6-thioxaoctane)bis(isothiuronium trichloroacetate) described in No. 670, West German Patent Publication No. 670;

Thiol compounds described in No. 7/4A, US Patent No. ≠.

Thiazolium compounds such as λ-amino-cortiazolium trichloroacetate and λ-amino-fluoromoethyl-2-thiazolium trichloroacetate described in U.S. Patent No. 260, U.S. Pat. ≠ Compounds with acidic moiety and λ-carboxycarboxamide, such as bis(co-amino-cortiazolium) methylene bis(sulfonylacetate), λ-amino-cortiazolium phenylsulfonyl acetate, etc. with symbol a is often used.

Furthermore, azole thioethers and blocked azolinthionic compounds described in Belgian Patent No. 761.07/,
U.S. Patent No. J, lr 3. ? ! ≠-Arylu/-Carbamylucochitrazoline-! -thione compounds, etc. U.S. Patent No. 3.131.0+1/, U.S. Patent No. J
, rti, tt, 7ry No. J, r77.
Compounds described in No. 2, No. 0 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are l and co.

Compounds such as μ-triazole, /H-tetrazole, thiouracil and /,J,4L-thiadiazole. Examples of preferred toning include j-amino-/, 3.
≠-thiadiazole-corchiol, 3-mercapto-
/, 2,4L-) lyazole, bis(dimethylformumi/L-)disulfide, 6-methylthiouracil, /-
Phenyl-cochtraazoline-! -Thion, etc. Particularly effective toning agents include compounds capable of forming black images.

The concentration of the toning agent contained varies depending on the type of heat-developable photosensitive material, processing conditions, desired image, and other factors, but generally it is about 0.00% to 1 mole of silver in the photosensitive material.
/~0.1 mole.

The binders used in the present invention can be contained alone or in combination. A hydrophilic binder can be used for this binder.

Typical hydrophilic binders include transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives, starch, etc.
These include natural substances such as polysaccharides such as gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

The coating weight of the binder of the present invention is 1 m269)01 or less, preferably 10y or less, more preferably 71 or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is binder/? less than or equal to solvent/CC, preferably 0
, jcc or less: more preferably 0.3 mark or less.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (co, 3-dihydroxy dioxane, etc.) ), activated vinyl compound (1, J, j-
triacryloyl-hexahydro-3-)' riazine, /, 3-vinylsulfonyl-λ-blocknol, 1
．． 2-bis(hinylsulfonylacetamido)ethane, etc.), active halogen compounds (,,?, 4t-dichloro-6
-hydroxy-s-1-riazine, etc.), mucohalogen flfl, (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

In the present invention, when a dye-donating substance that releases an imagewise mobile dye is used, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer.

In a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. Also used are low-boiling solvents such as methanol, N,N-dimethylformamide, acetone, and diimbutylketone, or solutions of these low-boiling solvents with water or a basic aqueous solution.

The dye transfer aid may be used by moistening the image-receiving layer with the transfer aid.If the transfer aid is incorporated into the light-sensitive material or dye fixing material, there is no need to supply the transfer aid from the outside.

The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. Furthermore, it is preferable to incorporate a hydrophilic thermal solvent, which is solid at room temperature and dissolves at high temperature, into the light-sensitive material or dye-fixing material. The hydrophilic thermal solvent may be incorporated into the photosensitive material and the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/l or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
/) When containing a dye-donating substance,
Since the dye-donating substance is colored, it is not so necessary to include an anti-irradiation substance, an anti-halation substance, or various dyes in the light-sensitive element, but in order to improve the sharpness of the image, To, special public ShoμI-
JJ Octopus Publication, U.S. Patent No. 3. Ko! 3. No. 27, No. 2. ! 27, J-13, same No. 2. ri74, 17
Filter dyes, absorbent substances, etc. described in each specification such as No. 2 can be contained.

In addition, it is preferable that these dyes are thermally decolorizable.
For example, U.S. Patent No. 3,762. Oi Ri issue, same number 3.7 da! , No. 002, No. J, t/j, II3λ are preferred.

The photosensitive material used in the present invention may optionally contain various additives known for use in heat-developable photosensitive materials, layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer,
It can contain an AH layer, a release layer, etc. As for each additive, research disclosure magazine vol.1. /
Additives described in No. 4/7022, June 2015, 7Q, /27r, such as plasticizers, dyes for improving sharpness, A) (dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening) There are additives such as anti-fading agents and anti-fading agents.

The photosensitive material or the dye fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan, the photosensitive material used in the present invention has at least three layers, each of which is sensitive to a different density range. It is necessary to have a silver halide emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers having mutually different optical properties include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, a green-sensitive emulsion layer Emulsion layer, combination of red-sensitive emulsion layer and infrared-sensitive emulsion layer, combination of blue-sensitive emulsion layer, green-sensitive emulsion layer and infrared-sensitive emulsion layer, blue-sensitive emulsion layer, red-sensitive emulsion layer and infrared There are combinations of light-sensitive emulsion layers, etc.

In addition, an infrared light-sensitive emulsion layer is 700 nm or more, especially 700 nm or more.
It has an emulsion layer that is sensitive to light of μonm or more.

The light-sensitive material used in the present invention may have two or more emulsion layers having photosensitivity in the same wavelength region, depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer has a dye-donating substance that releases or forms a hydrophilic color 'X of yellow, and a hydrophilic dye that releases or forms a magenta hydrophilic dye. It is necessary to contain at least one of a dye-providing substance that forms and a dye-providing substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues.

If desired, λ or more dye-providing substances having the same hue may be mixed and used. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention can be provided with auxiliary layers such as a protective layer, an intermediate layer, an anti-static layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

In particular, the protective layer (PC) K usually contains an organic or inorganic matting agent to prevent adhesion.

Further, this protective layer may contain a mordant, a UV absorber, and the like. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate NlIC may contain a reducing agent to prevent color mixing, a UV absorber, and a white pigment such as TiO2. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart the above-mentioned color sensitivities to the silver halide emulsions, K may be used to dye-sensitize each silver halide emulsion with a known sensitizing dye so as to obtain the desired spectral sensitivity.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting semiconductivity, and the other uses a thin film of an organic material in which conductive fine particles are dispersed in a binder.

Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide, and transparent or opaque thin films are made using known methods. be able to. In the latter method, conductive particles such as metal particles, carbon black, and graphite are dispersed in rubber, base polymer, and gelatin to create a resistor with desired temperature characteristics. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, etc.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat-generating element/support/photosensitive element support 7 Heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating III layer support/photosensitive element/intermediate layer/heat-generating element according to the present invention The dye fixing material used has at least one layer containing a mordant, and if the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In addition to the above-mentioned layers, the dye fixing material used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

Seven or more of the above layers include a base and/or base precursor to promote dye transfer, a hydrophilic heat solvent, an anti-fading agent to prevent color mixing of dyes, a UV absorber, Dispersed vinyl compounds, fluorescent brighteners, etc. may be included to increase stability.

The binder in the above layer is preferably hydrophilic, and is typically a transparent or translucent hydrophilic colloid. For example, gelatin, gelatin derivatives, polyvinyl alcohol, proteins such as cellulose g-conductors, natural substances such as starch, polysaccharides such as gum arabic, dextrin, pullulan,
Synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In addition to the above, the dye fixing material may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated not only in the dye fixing material but also in the photosensitive material. The structures of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer are described in, for example, U.S. Pat. Jt2. r/ri No. 3,362. l'2/No. 3. It/j,
la'A≠, Canadian Patent No. P21.112, etc.

Furthermore, it is advantageous for the dye fixing material of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer.

The image receiving layer in the present invention includes a dye fixing layer used in heat-developable color light-sensitive materials, and can be arbitrarily selected from commonly used mordants, among which polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these μ-class cation groups, and the like.

For polymers containing one unit of vinyl monomer having a tertiary amino group, see Japanese Patent Application No. 11-/J-072.
! -/At/J! Specific examples of polymers containing one unit of a vinyl monomer having a tertiary imidazole group include Japanese Patent Application No. 12J417 and JR No.
-23u077, U.S. Patent No. μ, Cor r2. JOA- issue, same issue ≠, I/j, /kohiro issue, same issue z ar, oti
It is written in the number etc.

Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No. λ, 0.
1 &, 10/ issue, same issue, Qri3゜Oμ/ issue, same issue,
1? ≠, Ri No. 47, U.S. Patent No. a, Ixa, Jr.
Same No. 41. //j, No. 12≠, No. 1, 273, 113
No., same No. ≠, ≠! 0.22≠ issue, Akihiro Tokukai! -21. λ
Ko! It is stated in the number etc.

Other preferred specific examples of polymers containing one vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. , Sho JR-/lt/No. 31, No. 11-/4PO12, Same! l-λ3ko No. 070,
Same 71-23 07 issue and same! It is written in Tata Lbu No. 20, etc.

In the present invention, similar to the heat-developable gR photosensitive layer, the aR is maintained.

For the intermediate layer, undercoat layer, pack layer, and other layers, each coating solution is prepared and applied using the dipping method, air knife method, curtain coating method, or U.S. Patent No. J, trl, Kota specification symbol specification. A light-sensitive material can be prepared by sequentially coating on a support by various coating methods such as the described coating method and drying.

Additionally, if necessary, US Pat. It is also possible to apply two or more layers simultaneously by the method described in W 1.

Supports other than the supports of the present invention may be used for either the light-sensitive material or the dye-fixing material in the present invention.

Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinylacetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and The films associated therewith include resin materials.

Shoe supports laminated with polymers such as polyethylene can also be used. U.S. Patent No. 3.63
≠, orri No. 3, 7λr,.

The polyester described in No. 70 is preferably used.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used. In general, various light sources such as tungsten lamps, halogen lamps such as mercury lamps and iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, light emitting diodes + LEDs, etc., are used for normal color printing. I can do it.

The heating temperature in the heat development process is about to'c to about 0.
It can be developed at about /1O00 to about /Ir00.
C is useful, and within this range, 7≠00C or higher is preferable, and VC/JO''C or higher is preferable.The heating temperature in the transfer process can be transferred in the range from the temperature in the heat development process to room temperature. is more preferably about 10°C lower than the temperature in the thermal development process.Heating means in the development and/or transfer process may include a simple hot plate,
An iron, a hot roller, a heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. It is also possible to superimpose the two after applying a dye transfer aid to both.

Examples of methods for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include a roller coating method or a wire per coating method as described in JP-A No. 07-07; A method of applying water to a dye-fixing material using a water-absorbing member as described in Japanese Patent Application No. A method of applying a dye transfer aid by forming beads between the beads, patent application! T-! ! 10, in which a bead is formed between a water-repellent roller and a dye fixing layer to apply a dye transfer aid; other methods include a dipping method, an extrusion method,
A method of applying by jetting it out from the IIA hole,
Various methods can be used, such as a method of applying pounds in the form of crushing.

The dye transfer auxiliary agent may be provided in a pre-measured amount within the range as described in Japanese Patent Application No. Shoyo R-37F02.
The amount can be adjusted and used by applying sufficient amount and then squeezing it out by applying pressure with a roller or the like or drying it by applying heat.

For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the material is superimposed on a photothermographic material.

Heating means in the transfer process include heating by passing between hot plates, heating by contacting with the hot plates (for example, Japanese Patent Application Laid-Open No. 0-4263!
), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. Akihiro J-10721), heating by passing through hot air (for example, Japanese Patent Publication No. Akihiro J-4273)
7), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a roller, belt, or guide member (for example, Special Publication No. 14 L-2! Hiro wo), etc. can be used. In addition, graphite, carbon black,
Layers of electrically conductive material such as metal may be applied one upon another, and electrical current may be passed through the electrically conductive layers to heat them directly.

The heating temperature applied in the transfer step can be transferred in the range from @ degree to room temperature in the heat development step, but %tl
ctO'c or more, 10% higher than the temperature in the heat development process
A low response temperature of 'C or higher is preferable.

The pressure when the heat-developable photosensitive material and the dye-fixing material are overlapped and brought into close contact varies depending on the embodiment and the materials used.
0, /-/00kli/cIIL"preferably/
~jOkg/cm2 is appropriate (for example, Tokugansho!r-
tt Otori No. 1〈Record! the law of nature. .

Various methods can be used to apply pressure to the photothermographic material and the dye-fixing material, such as passing it between a pair of rollers or pressing it using a plate with good smoothness. Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

■　Example The present invention will be explained in more detail with reference to Examples below.

Example 1 This article describes how to make benzotriazole silver emulsion.

Ze2 dick l? and benzotriazole 13.22 J
It melts into OOgo. Keep this solution at 0'C and stir. Add silver nitrate/7 to this solution? Add a solution of 70Q- of water dissolved in 2 minutes.

The pH of the benzotriazole silver emulsion is adjusted, allowed to settle, and excess platform is removed. Then pH'frt, JO
A benzotriazole silver emulsion with a yield of 4 AOOf was obtained.

Describe how to make the first layer and the silver halide emulsion for the first layer.

A well-stirred aqueous solution of 2 chlorides (containing 7000 d of water and 2 Of gelatin and sodium chloride JP, 7!0C)
An aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (600 tons of water) were kept warm at
tiltlC silver nitrate 0. Dissolved Jr Tamol)
was added at equal flow rates over a period of 10 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine!Omolti) having an average grain size of 000 μm was prepared.

After washing with water and desalting, sodium thiosulfate II! Da and≠-Hydroxy-6-methyl-/,! , 3a,7-chitrazaindene 20119 was added to perform chemical sensitization to 0c. The yield of the emulsion was tooy.

Next, I will explain how to make a silver halide emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing gelatin O1 and sodium chloride 3f in water/000g, 7j0C
(Vc kept warm) K 600% aqueous solution containing sodium chloride and potassium bromide and silver nitrate aqueous solution (water 400%
m1VC silver nitrate O0! (dissolved tamol) was simultaneously added at an equal flow rate over 30 minutes. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion (bromine 10 mole) of μm size was prepared.

After washing with water and desalting, sodium thiosulfate! Datobiichi Hydroxy-4-Methyl-/,! , Ja, 7-chitrazaindene 20 ~ was added to perform chemical sensitization at to 0c.

The yield of emulsion was toor.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-donating substance (A) was used as a surfactant, and succinic acid-λ-ethylhexyl ester sulfonic acid was used as a surfactant. jt, t+) isononyl 7 phosphate 10? Weigh out, add 30% of ethyl acetate, and add about 30% of ethyl acetate.
Dissolve with RTC heating to make a homogeneous solution. This solution and 100% solution of 70% lime-treated gelatin were stirred and mixed, and then mixed with a homogenizer for 10 minutes to 100100001p.
and disperse. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-donating substance was prepared in the same manner as above, except that the magenta dye-donating substance (B) was used and tricresyl phosphate was used as a high boiling point solvent. .

A cyan dye-providing substance (C) was used in the same manner as the yellow dye dispersion.

Using these materials, color photosensitive materials having a multilayer structure as shown in the following table were prepared.

Dye-donating substance (A) (B) (C) (D-/) ID-2> (D-J) t A method for producing a dye-fixing material having a dye-fixing layer will be described.

First, gelatin hardener () (-/) 0.7! f.

(H-1) θ, cojf, water/j 0111 and io
100ff of lime-treated gelatin was mixed uniformly. This mixed solution was laminated with polyethylene in which titanium oxide was dispersed on the paper supports (a), (c), respectively; nK
% It was applied with a uniform pressure so as to have a wet film thickness of 60μ, and then dried.

Next, polymer /jf with the following structure was dissolved in 20011t of water, mixed uniformly with 100f of 10% lime-treated gelatin, and this mixed solution was uniformly applied onto the above coating material to a wet film thickness of t to μ. and dry, dye fixing material (I),
Obtain (If), [III)9.

A tungsten light bulb is used in the multi-layered color photosensitive material, and a G, R, IR three-color separation filter (GVij00-600nm, R is 400nm, whose density changes continuously)
~700nm band/miss filter, IR is 700
(constructed using a filter that transmits at least nm),
Exposure was made for 7 seconds at 100 lux.

Then, place it on a heat block heated to 10°C for 30 minutes.
Heat evenly for seconds.

Next, the film side K/m2 of the dye fixing material is equivalent to itd
After supplying water, the heat-treated photosensitive coatings were stacked on a fixing material so that their film surfaces were in contact with each other.

When the dye fixing material is peeled off from the photosensitive material after heating for 6 seconds on a rooC heat block, %G% is left on the fixing material.
Compatible with R and IR three-color separation filters, yellow, magenta, and cyan color images can be obtained respectively.

The maximum density (Dmax) of each color is measured using a Macbeth reflection type densitometer (
The degree of uneven transfer of each dye fixing material was visually evaluated.

From the above table, when using the coated paper or cast coated paper of the present invention, even when the basis weight is small (thin l/1), the occurrence of transfer unevenness is significantly reduced. It can be seen that the occurrence of unevenness can be almost completely eliminated.

Example 2 A color photosensitive material having a multilayer structure shown in Table 3 was prepared.

In Table 3, the silver chlorobromide emulsion for the first layer is Example 1.
It is the same as the silver chlorobromide emulsion for the third layer.

Dye-donating substances (A), (B), (C) used in Table 3
) are the same as those used in Example 1, respectively.

The benzo) IJ azole silver in Table 3 is also the same as in Example 1.

The method for preparing the emulsion for the third layer in Table 3 will be described.

A well-stirred gelatin water bath solution (containing 20f of gelatin and 3t of sodium chloride in water/000g, 7j”CV)
(C kept warm) K An aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (too much water)
A solution of silver nitrate (o, r) in rtt) and the following dye solution (I) were added at equal flow rates over a period of simultaneous VCC participation. In this way, the average particle size is 0.3
! A monodisperse cubic silver chlorobromide emulsion (tO moles of bromine, qIa) on which μ dye was adsorbed was prepared.

A monodispersed cubic silver chlorobromide emulsion (smelling to morch) was prepared, on which a dye of size 0.3 μm was adsorbed.

After washing with water and desalting, chemical sensitization was carried out by adding 20 m9 of sodium thiosulfate j1#9 and 1-hydroxy-t-methyl/, J, Ja, 7-titrazaindene.9.

The yield of emulsion is 400? Met.

Dye Solution CII Next, how to prepare the emulsion for the fifth layer in Table 3 will be described.

In a well-stirred gelatin water bath solution (20% gelatin and ammonia dissolved in 1000ml of water and kept warm at jo'C), add 10100O of an aqueous solution containing potassium iodide and potassium bromide and an aqueous solution of silver nitrate (water). 100011
1 mol of silver nitrate dissolved in Lt width)
pA g was added while keeping it constant. In this way, the average particle size is 0. jμ monodispersed silver iodobromide octahedral emulsion (
Iodine (mol%) was prepared.

After washing with water and desalting, gold and sulfur sensitization was performed by adding chloroauric acid (≠water salt) t■ and sodium thiosulfate 2■. The yield of the emulsion was i.okg.

*1 Nitricresyl phosphate *3:≠-Methylsulfonyl-phenylsulfonylacetate guanidine N (C2H5) a OO Next, the method of making the dye fixing material will be described.

Dissolve the lime-treated gelatin saw t in 200 dl of water, add 0 part of zinc acetate and 1 part of jM aqueous solution to it, and evenly dissolve:
Mixed. This mixed solution was applied to the same paper supports (a), (b), and (c) as used in Example 1, each with a wet film thickness r! Then, apply the coating solution with the following formulation evenly on top of it to a wet film thickness of Oμ, and dry.
Dye fixing materials (IV), (V), and [■] were prepared.

Prescription of Coating Solution for Dye Fixing Layer The multilayered color photosensitive material was exposed to light for 1 second at λOOOO lux using a tungsten light bulb through a three-color separation filter of B, G, and R whose densities were continuously changing. Then 3 on the heat block heated l≠0'CK.
Make sure to heat it evenly for 0 seconds.

This photosensitive material and the previously prepared dye fixing material were placed one on top of the other so that their coating surfaces were in contact with each other, and after applying pressure, they were passed between nine heat rollers (/JO'CIC heating), and then immediately placed on a heat block. 20'C.

Heat for 30 seconds and then. Immediately after heating, the dye-fixing material was peeled off from the light-sensitive material, and yellow, magenta, and cyan color images were obtained on the dye-fixing material, corresponding to the three colors BlG and R1, respectively. The maximum density (Dmax) of each color was measured using a Macbeth reflection type densitometer (RD-JL), and the degree of transfer 2 was evaluated visually using a button.

From the table above, when using the coated paper or cast coated paper of the present invention, uneven transfer hardly occurs even when transfer is performed using a hydrophilic hot solvent in the absence of water. It can be seen that when coated paper is used, transfer unevenness completely disappears.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Statement ■Showa Otsu rh Month/11/-day

Claims (2)

[Claims] (1) A dye transfer method in which a photosensitive material containing a mobile dye is superimposed on a dye fixing material having a dye fixing layer, and the dye is transferred to the dye fixing layer. A dye transfer method characterized in that at least one support of the dye fixing material is made of coated paper. (2) The dye transfer method according to claim 1, wherein the coated paper is cast coated paper.