JPH0652425B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel photosensitive composition containing a compound capable of generating a free radical by light. More specifically, it relates to a photosensitive composition containing 4,6-bis (halomethyl) -s-triazines or 2-halomethyl-1,3,4-oxadiazoles as a free radical generator.

[Conventional technology]

Compounds that decompose to form free radicals when exposed to light (free radical generators) are well known in the field of graphic arts. They are widely used as photoinitiators in photopolymerizable compositions, photoactivators in free radical photographic compositions and as photoinitiators of reactions catalyzed by photogenerated acids. Such free radical generators are used to make a variety of photosensitive materials useful in printing, reproduction, reproduction and other imaging systems.

Organohalogen compounds are photolyzed to give halogen free radicals such as chlorine and bromine free radicals. These halogen radicals are good hydrogen-abstracting agents and produce acids in the presence of hydrogen donors. For their application to photopolymerization processes and free radical photography processes, see J. By Kosar,
"Light Sensitive Systems
Systems) "J. Wiley & Sons Sons (New York 1965), pages 180-181 and 361-370.

Carbon tetrabromide, iodoform, tribromoacetophenone and the like have been typical examples of compounds that generate a halogen free radical by the action of light of this kind, and have been widely used. However, since these free radical generators have a subliming property or a bad odor, when they are used in a light-sensitive material having a light-sensitive layer provided on a support, the light-sensitive layer is not produced during the production, use or storage of the light-sensitive material. Volatilized from the water to reduce the effect and became an obstacle to hygiene. Further, these free radical generators have a problem in compatibility with other elements contained in the photosensitive layer. Further, since they have low photolysis sensitivity to a light source (metal halide lamp or the like) usually used at the time of producing a printing plate, it has been necessary to add a large amount of them in order to exhibit a sufficient effect. It has been customary that when a large amount is added to the photosensitive layer, the mechanical properties and developability of the photosensitive layer are adversely affected.

[Problems to be solved by the invention]

For such a problem, U.S. Pat.Nos. 3,954,475 and 3,98
Vinyl-halomethyl-s-triazine compounds described in JP-A-7,037 and JP-A-48-36281, JP-A-53-13
Halomethyl-s-triazine compounds described in JP-A No. 3,428, JP-A-55-32070, and 2-halomethyl-5-vinyl-1,3,4 described in JP-A-54-74728.
-Oxadiazole compounds and 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds described in JP-A-55-77742 have been proposed. These free radical generators are certainly suitable for the UV light sources that are usually used.
It has excellent characteristics such as extremely high photodecomposition sensitivity and excellent stability over time.However, when it is used as a component of the photosensitive composition of a lithographic printing plate, the photosensitive composition is applied to the non-image area after development. A part of the product is likely to remain, especially when soaking the developer in absorbent cotton, sponge, etc. and rubbing for development,
The photosensitive composition partially remained in the non-image area, resulting in unevenness and poor appearance, and scumming often occurred when used as a lithographic printing plate.

Therefore, in order to solve this problem, JP-A-60-3626 discloses a 2-halomethyl-1, which has a phenolic hydroxyl group,
3,4-oxadiazole compounds have been proposed. However, these compounds have a problem that when they are added in a large amount to the photosensitive composition in order to generate a large amount of free radicals, the range of appropriate developing conditions is significantly reduced (developing acceptability is poor).

Therefore, an object of the present invention is to provide a photosensitive composition in which a photosensitive composition is less likely to remain in a non-image area after development (less development unevenness) and scumming is less likely to occur when used in a lithographic printing plate. . Another object of the present invention is to provide a photosensitive composition excellent in stability over time (that is, the property of maintaining the same performance as immediately after production even after storage for a long time). Still another object of the present invention is to provide a photosensitive resist-forming composition which exhibits high sensitivity to a commonly used UV light source. Still another object of the present invention is to provide a photosensitive layer having excellent physical properties such as preventing printing defects due to register marks. Still another object of the present invention is to provide a photosensitive composition having excellent development acceptability.

[Means for solving problems]

The present inventors have made various studies as a result of solving various problems described above, and as a result, have made the present invention. The content of the present invention is "Soluble in an alkaline aqueous solution by irradiation with actinic rays. 2,6-bis (halomethyl) -s-triazine free radical generator and / or 2-halomethyl-1,3, which becomes soluble in an alkaline aqueous solution by irradiation with actinic rays.
What is claimed is: 1. A photosensitive composition comprising a 4-oxadiazole free radical generator and a compound that interacts with a photolysis product of the free radical generator, the free radical generator comprising an o-quinonediazide group and / or A photosensitive composition having at least one o-naphthoquinonediazide group ".

The present invention will be described in detail below.

In the present invention, a 4,6-bis (halomethyl) -s-triazine-based compound which becomes soluble in an alkaline aqueous solution upon irradiation with an actinic ray as a free radical generator, and a soluble in an alkaline aqueous solution upon irradiation with an actinic ray 2- Halomethyl-
1,3,4-Oxazole compounds or a mixture thereof are used, and these compounds have at least one o-quinonediazide group and / or o-naphthoquinonediazide group.

The term "actinic ray" as used herein means one that can cause a chemical change in the free radical generator by the ray, and specifically, it may be light having a wavelength of about 250 nm to about 500 nm. The "alkaline aqueous solution" is an aqueous solution having a pH range of 10-14. The alkaline substance is not particularly limited, but sodium hydroxide, sodium silicate and the like are generally suitable. "Soluble in alkaline aqueous solution" means that it is soluble in an alkaline aqueous solution in an amount of 0.005 wt% or more.

As the 4,6-bis (halomethyl) -s-triazine free radical generator, the compound represented by the general formula [I] is preferable.

(In the general formula [I], X and Y may be the same or different from each other and each represents a chlorine atom or a bromine atom,
R represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and A represents an element selected from (a) an aryl group having 1 to 3 o-naphthoquinonediazide groups or (b) oxygen, nitrogen, sulfur and selenium. Represents a heterocyclic group containing at least one, and l represents 0 or 1 and m represents an integer of 0 to 2. ) Further, as the 2-halomethyl-1,3,4-oxazole free radical formation, a compound represented by the general formula [II] is preferable.

(In the general formula [II], X represents a chlorine atom or a bromine atom, R represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and A represents (a) aryl having 1 to 3 o-naphthoquinonediazide groups. Group or (b) oxygen, nitrogen,
It represents a heterocyclic group containing at least one element selected from sulfur and selenium, 1 represents 0 or 1 and m represents an integer of 0 to 2. In the general formulas [I] and [II], R is preferably a chlorine atom when it is a halogen atom, a lower alkyl group having 1 to 4 carbon atoms when it is an alkyl group, and a phenyl group when it is an aryl group. Is preferred. Particularly preferred R is a hydrogen atom. More preferably, X and Y are chlorine atoms. A is more preferably an aryl group having 1 to 2 o-naphthoquinonediazide groups. O is more preferable for m and n.

Next, specific examples of the compounds represented by the general formula [I] and the general formula [II] will be illustrated. (In the formula, Indicates. ) Exemplary compounds The compounds represented by the general formula [I] and the general formula [II] are a compound having a hydroxyl group and o-quinonediazide or o synthesized by dealkylation of the compounds represented by the general formula [III] and the general formula [IV], respectively. It can be synthesized by condensation reaction of naphthoquinonediazide with sulfonyl halide.

(In the general formula [III], A'is (a) an aryl group having 1 to 3 nuclear-substituted alkoxy groups or (b) a heterocyclic ring containing at least one element selected from oxygen, nitrogen, sulfur and selenium. The formula group is shown, and other X, Y, m, n, l and R have the same meanings as those in the formula [I].) (A 'has the same meaning as A'in the general formula [III], and other X,
Y, m, n, l and R have the same meanings as in the general formula [II]. ) The dealkylation reaction of the general formula [III] and the general formula [IV] can be carried out by, for example, Organic Synthesis Collect volume V, 41
2-414 (1973), by M. Gerecke et al., Helevetica Chimica Acta, 59 , 2551-25.
57 (1976), EH Vickery et al., Jou.
rnal of Organic Chemistry, 44 , 4444-444
6 (1979) or by M. Node et al., Jo.
urnal of Organic Chemistry, 45 , 4275-427
7 (1980) and the like.

The condensation reaction of a sulfonyl halide such as a sulfonyl chloride of o-quinonediazide or o-naphthoquinonediazide with a compound having a hydroxyl group synthesized by dealkylation of the compounds represented by the above general formulas [III] and [IV] is described below. Can be done as follows.

That is, for example, sulfonyl chloride of o-quinonediazide or o-naphthoquinonediazide and the compound are dissolved in a solvent such as dioxane, methylethylketone, tetrahydrofuran, dimethylformamide (DMF), and heated at room temperature or 40 to 50 ° C. under stirring with stirring. The compound represented by the general formula [I] or the general formula [II] used in the present invention can be synthesized by reacting by adding an alkali such as sodium carbonate.

The compound represented by the general formula [III] is described in, for example, US Pat.
No. 3,954,475, No. 3,987,037, JP-A-48-3
It can be synthesized according to the method described in 6281 and JP-A-53-133428. Further, the compound represented by the general formula [IV] is described in, for example, JP-A-55-24113, US Pat. No. 4,232,106, and US Pat. No. 4,279,9.
It can be synthesized according to the synthesis method described in Japanese Patent No. 82 or JP-A-60-138539.

Incidentally, U.S. Pat.Nos. 3,954,475 and 3,987,037,
JP-A-48-36281, JP-A-53-133,
The halomethyl-s-triazine-based free radical generators described in JP-A No. 428 and JP-A No. 55-32070,
It is essentially different from the free-radical generator of the present invention in that it is substantially insoluble in alkaline water having a pH of 10 or more. The 2-halomethyl-1,3,4-oxadiazole compounds having a phenolic hydroxyl group described in JP-A-60-3626 described above are treated with alkaline water having a pH of 10 or more before and after irradiation with actinic rays. It essentially differs from the free radical generators of the present invention in that it dissolves.

The free-radical generator in the present invention becomes soluble in an alkaline aqueous solution after irradiation with light, so that the photosensitive composition is unlikely to remain in the non-image area after development, and for example, when used in a lithographic printing plate, scumming hardly occurs. It is presumed that On the contrary, it is presumed that it is water-soluble in an alkaline aqueous solution before light irradiation, and probably because of this, the development acceptability is very excellent.

The free radical generator, when irradiated with an actinic ray in the range of about 250 nm to 500 nm, very efficiently produces a free radical. Therefore, the photosensitizer of the present invention comprising a compound (free radical generator) that generates a free radical upon irradiation with actinic rays and a compound that interacts with a photolysis product of the free radical generator as an essential component. Photosensitive composition (for example, a photosensitive material used for producing a printing plate such as a planographic printing plate, a relief printing plate, an intaglio printing plate, a photoresist composition used for producing a photographic element and other photographic elements, and exposure to A highly sensitive photosensitive composition can be obtained by using the compound as the free radical generator of the photosensitive composition which provides a visible contrast with the unexposed area.

The photosensitive composition of the present invention includes a known free radical generator other than the above free radical generator, for example, the above-mentioned US Pat. No. 3,954,475.
No. 3,987,037, JP-A-53-133,4
No. 28, etc., and halomethyl-s-triazine compounds described in JP-A No. 54-74728, JP-A No. 55-77742, JP-A No. 60-3626, and the like. Free radical generators such as -1,3,4-oxadiazole compounds may also be included.

The free radical generator in the present invention is 0.1 to 50% by weight, preferably 0.3 to 30% by weight based on the total weight of the photosensitive composition of the present invention.
It may be contained in an amount of 1.0% by weight, more preferably 1.0 to 10% by weight.

Next, as the "compound that interacts with the photodegradation product of the free radical generating agent" used in the present invention, a discoloring agent can be mentioned.

The term "color-changing agent" as used herein means an addition-polymerizable ethylenically unsaturated monomer or oligomer, for example, a compound having at least one group capable of being cleaved by an acid such as a coc bond, a color developed by an acid, a color erased or A compound that discolors (hereinafter referred to as a discoloring agent) and the like.

In the present invention, as the color-changing agent, those which are originally colorless and change to a colored state and those which have an inherent color are discolored or decolorized by the action of the photodecomposition product of the free radical-generating agent. There are two types.

Arylamines can be mentioned as typical examples of the discoloring agent layered in the former type. Suitable arylamines for this purpose include so-called leuco dyes in addition to simple arylamines such as primary and secondary aromatic amines, examples of which are as follows.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4'-biphenyldiamine, o-chloroaniline, o-bromoaniline, 4
-Chloro-o-phenylenediamine, o-bromo-N,
N-dimethylaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane,
Aniline, 2,5-dichloroaniline, N-methyldiphenylamine, o-toluidine, p, p'-tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-
Phenylenediamine, 1,2-dianilinoethylene,
p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriphenylmethane, p, p'-tetramethyldiaminodiphenylmethylimine, p, p', p" -triamino -O-methyltriphenylmethane, p, p ', p "-triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-4-anilinonaphthylmethane, p, p',
p ″ -triaminotriphenylmethane, p, p ′, p ″
-Hexapropyltriaminotriphenylmethane.

Further, as a color-changing agent which has an inherently unique color and whose color is discolored or decolorized by a photo-decomposition product of a free-radical generator, diphenylmethane, triphenylmethane-based, thiazine-based, oxazine-based, xanthene-based Various dyes such as anthraquinone type, iminonaphthoquinone type and azomethine type are effectively used.

Examples of these are as follows. Brilliant Green, Eosin, Ethyl Violet, Erythrosin B, Methyl Green, Crystal Violet, Bassy Fuchsin, Phenophthalphthalein, 1,3-Diphenyltriazine, Alizarin Red S, Thymolphthalein, Methylbiolett 2B, Quinaldine Red , Rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange,
Orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, conco red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin,
Oil Blue # 603 [Orient Chemical Industry Co., Ltd.
], Oil Pink # 312 [made by Orient Chemical Industry Co., Ltd.], oil red 5B [made by Orient Chemical Industry Co., Ltd.], oil scale # 308 [made by Orient Chemical Industry Co., Ltd.], oil red OG [Orient Chemical Industry] Co., Ltd.], Oil Red RR [Orient Chemical Co., Ltd.], Oil Green # 502 [Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [Hodogaya Chemical Co., Ltd.], m-cresol purple , Cresol red, rhodamine B, rhodamine 6
G, fast assault iodot R, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p
-Diethylaminophenyliminonaphthoquinone, 2-carbostearylamino-4-p-dihydrooxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p -Diethylaminophenyl iminoacetanilide, 1-phenyl-3-
Methyl-4-p-diethylaminophenylimino-5-
Pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

In the photosensitive composition of the present invention, the free-radical generating agent is stable over time, but among those used as a discoloring agent, leucotriphenylmethane dyes are generally easily oxidized. Therefore, when using these dyes, it is effective to include a certain stabilizer. As the stabilizer for this purpose, amines described in U.S. Pat.No. 3,042,575, zinc oxide, phenols, sulfur compounds described in No. 3,042,516, alkali metal iodides described in No. 3,042,518, Organic acids, organic acid anhydrides described in No. 3082086, antimony described in No. 3377167,
Triaryl compounds of arsenic, bismuth and phosphorus are effective.

The ratio of the discoloring agent to the free radical generating agent as described above is from about 0.01 part by weight to about 10 parts by weight of the free radical generating agent per 1 part by weight of the discoloring agent.
It is used in an amount of 0 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 0.5 to 5 parts by weight. Moreover, you may mix and use a free radical generator.

The composition of the present invention using the above-mentioned color changing agent as a compound that interacts with a photodegradation product of a free radical generating agent is a photosensitive resist forming composition for producing a lithographic printing plate, an IC circuit, a photomask and the like. In particular, it is useful as a printout composition used for imparting a performance (hereinafter, referred to as a printout ability) of immediately providing a visible contrast with an unexposed area without developing by exposure. In this way, by giving the photosensitive resist composition a print-out ability, under a yellow safety light in the exposure operation,
Since the visible image is obtained only by the exposure, it becomes possible to know whether the plate given to the platemaker is exposed, for example, when work is interrupted in the process of exposing many printing plates at the same time. At the same time, for example, when exposing one large plate many times as in the so-called plate printing method when making a lithographic printing plate, the operator can immediately check which part has been exposed. it can.

On the other hand, the photosensitive resist-forming composition as an object to which the printout ability is imparted by the photosensitive composition of the present invention is
As mentioned above, various printing plates such as planographic printing plates, IC circuits,
It includes various items used to make photomasks and the like. Typical examples thereof include (1) a composition comprising a diazo resin, (2) a composition comprising an o-quinonediazide compound or an o-naphthoquinonediazide compound, (3) a composition comprising a photosensitive azide compound, (4) ) A composition comprising a polymer compound containing a —CH═CH—CO— group in the main chain or side chain of the polymer, and (5) a photopolymerizable composition comprising an addition polymerizable unsaturated compound and a photopolymerization initiator. Details of these compositions are included in U.S. Pat. No. 4,279,982, column 8, lines 11 to 1
It is listed at column 1, line 32.

Among them, the composition that can effectively utilize the photosensitive composition of the present invention is a composition (composition (2)) comprising the o-quinonediazide compound or the o-naphthoquinonediazide compound.

As the o-quinonediazide compound or the o-naphthoquinonediazide compound, the free radical generating agent itself used in the present invention can be used, or other commonly used o-quinonediazide compound or o-naphthoquinonediazide compound can be used without limitation. . Particularly preferably used are o-naphthoquinonediazide compounds, for example, U.S. Pat. Nos. 2,766,118, 2,767,092, and 2,772,972.
No. 2, No. 2,859,112, No. 2,907,665, No. 3,046,11
No. 0, No. 3,046,111, No. 3,046,115, No. 3,046,1
No. 18, No. 3,046,119, No. 3,046,120, No. 3,046,
No. 121, No. 3,046, 122, No. 3, 046, 123, No. 3, 06
1,430, 3,102,809, 3,106,465, 3,6
Various species described in many publications including the respective specifications of 35,709 and 3,647,443 can be preferably used. Among these, particularly o-naphthoquinone diazide sulfonic acid ester or o-naphthoquinone diazide carboxylic acid ester of an aromatic hydroxy compound,
And o-naphthoquinone diazide sulfonic acid amides or o-naphthoquinone diazide carboxylic acid amides of aromatic amine compounds are preferred, and o-naphthoquinone diazide sulfone is particularly preferred in the condensate of pyrogallol and acetone described in U.S. Pat. An ester reaction of an acid, a polyester having a hydroxy group at the end described in U.S. Pat. No. 4,028,111
-Naphthoquinone diazide sulfonic acid, or o-naphthoquinone diazide carboxylic acid ester-reacted,
P as described in US Pat. No. 1,494,043
-Hydroxystyrene homopolymers or copolymers thereof with other copolymerizable monomers esterified with o-naphthoquinone diazide sulfonic acid or o-naphthoquinone diazide carboxylic acid, U.S. Pat.
Copolymers of p-aminostyrene with other copolymerizable monomers, as described in Japanese Patent No. 711, are amide-reacted with o-naphthoquinone diazide sulfonic acid or o-naphthoquinone diazide carboxylic acid. Is excellent.

These o-naphthoquinonediazide compounds or o-naphthoquinonediazide compounds can be used alone, but it is preferable to use them in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak type phenolic resins, specifically phenol formaldehyde resins, o-cresol formaldehyde resins,
Included are m-cresol formaldehyde resins and the like.
Further, as described in JP-A-50-125806, a phenol or cresol and a formaldehyde substituted with an alkyl group having 3 to 8 carbon atoms such as a t-butylphenol formaldehyde resin together with a phenol resin as described above and formaldehyde. It is even more preferable to use the condensate of and together. The alkali-soluble resin is included in the photosensitive resist-forming composition in an amount of about 50 to about 85% by weight, more preferably 60 to 80% by weight, based on the total weight of the composition.

The photosensitive composition comprising the o-quinonediazide compound or the o-naphthoquinonediazide compound may further contain a pigment, a dye, a plasticizer or the like which is not a color changing agent, if necessary.

As the solvent used when applying the photosensitive composition of the present invention, ethylene dichloride, cyclohexanone, methyl ethyl ketone, 2-methoxyethyl acetate, monochlorobenzene, toluene, ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl There are cellosolve, ethyl cellosolve, acetone and the like, and these are used alone or in combination of two or more. Further, a fluorochemical surfactant can be added for the purpose of improving the coating property.
3M (Minne
sota Mining Manufacturing) Fluorad
FC-430, FC-431, Megafac F-171, F-173, F-177, F- manufactured by Dainippon Ink and Chemicals, Inc.
183, F-184, Asahi Glass Co., Ltd. Asahi Guard AG
-710 etc. are mentioned. The preferred range of use of these fluorine-based surfactants is 0.03 to 7% of the photosensitive composition, and the more preferred range of use is 0.2 to 2%.

Further, before coating the photosensitive composition of the present invention, an undercoat layer may be provided on the support for various purposes. Examples of the undercoat layer include soluble resins such as carboxymethyl cellulose, low molecular weight compounds having a hydroxy group such as dihydroxyethylglycine and its hydrochloride and triethanolamine hydrochloride, and yellow dyes.

The photosensitive resist forming composition using the photosensitive composition of the present invention is a photosensitive lithographic printing plate presensitized plate (Presensitized plaque) which is particularly used for preparing a lithographic printing plate.
te), also abbreviated as PS version. ) Is preferably used as a photosensitive layer. In this case, as the support,
For example, aluminum (including aluminum alloys)
A metal plate made of zinc, iron, copper or the like, a plastic in which such a metal is laminated or vapor-deposited, and an aluminum plate is most preferable. In the case of a support having a surface of metal, especially aluminum, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment is performed. It is preferable. Also, British Patent No. 851,
819 aluminum sheet that has been grained and then soaked in an aqueous sodium silicate solution or anodized in sulfuric acid; an aluminum sheet as described in U.S. Pat.No. 3,181,461. It is also suitable to use a material obtained by subjecting the above to anodizing treatment and then dipping it in an aqueous solution of an alkali metal silicate. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid,
Alternatively, an aluminum plate is preferably used in an aqueous solution of an organic acid such as oxalic acid or sulfamic acid or a salt thereof, or in a solution of a non-aqueous solution, or a combination of two or more thereof, particularly preferably an aqueous solution of phosphoric acid, sulfuric acid or a mixture thereof. It is carried out by passing an electric current as an anode. In addition, US patent
The silicate electrodeposition as described in the specification of 3,658,662 is also effective. Further, as described in British Patent No. 1,208,224, an aluminum plate obtained by electrolytically electrolyzing an aluminum plate in a hydrochloric acid electrolytic solution and then anodizing in a sulfuric acid electrolytic solution is also preferable. In addition, it is preferable to provide an undercoat layer of a cellulosic resin containing a soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing.

The amount of the photosensitive layer provided on such a support is about 0.1.
To about 7 g / m ^2, preferably in the range of 0.5-4 g / m ^2.

The PS plate thus obtained is exposed to an image, and then an image is formed by a process including development by a conventional method. For example, in the case of a PS plate having a photosensitive layer of a photosensitive composition containing the printout composition in the composition (1) composed of a diazo resin, the unexposed portion of the photosensitive layer is developed by image development after image exposure. It is removed to obtain a lithographic printing plate. A PS having a photosensitive layer formed of a photosensitive composition containing the composition (2) containing the printout composition of the present invention.
In the case of a plate, the exposed portion is removed by developing with an aqueous alkaline solution after imagewise exposure to obtain a lithographic printing plate. No matter what kind of PS plate the photosensitive layer has, no special device for imparting the print-out ability according to the present invention is required, and a conventionally known developing solution suitable for each photosensitive composition is used. , Can be developed.

The photosensitive resist-forming composition having the print-out ability imparted by the composition of the present invention can be used for producing a proofing plate for printing, a film for an overhead projector, and a film for a second original drawing. Suitable supports for these include transparent films such as polyethylene terephthalate film and cellulose triacetate film, and those obtained by chemically or physically matting the surface of these plastic films.

Further, the above composition can be used for producing a photomask film. Suitable supports for this include a polyethylene terephthalate film on which aluminum, an aluminum alloy or chromium is vapor deposited, or a polyethylene terephthalate film provided with a colored layer.

Furthermore, the composition can be used as a photoresist. In this case, various materials such as a copper plate, a copper plated plate, a stainless plate, a glass plate can be used as the support.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, "%" indicates% by weight unless otherwise specified.

Example 1 An aluminum plate having a thickness of 0.30 was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This is V _A =
Electrolytic surface roughening treatment was performed in an aqueous 1% nitric acid solution under an electric current of 160 clones / dm ² using an alternating current having a sinusoidal waveform under a condition of 12.7 V. The surface roughness was measured and found to be 0.6μ (Ra indication), continuing to be 30%.
Of H ₂ SO ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, and then in 20% H ₂ SO ₄ aqueous solution, current density 2 A /
It was anodized to a thickness of 2.7 g / m ² at dm ² .

The following photosensitive solution was applied on the aluminum support thus obtained using a whiler and dried at 100 ° C. for 2 minutes.

Naftoquinone- (1,2) -diazide- (2) -5-sulfonyl chloride esterification reaction product of cresol novolac resin 0.75 g cresol novolac resin 2.10 g tetrahydrophthalic anhydride 0.15 g free radical generator (see Table 1) (Stated) 0.03g
Or 0.15 g Crystal Violet 0.01 g Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.015 g Ethylene dichloride 18 g 2-Methoxyethyl acetate 12 g The coating amount after drying was 2.1 g / m ² . Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a metal halide lamp of 2 KW. The optical densities of the exposed and unexposed photosensitive layers were measured using a Macbeth reflection densitometer.

The image obtained by exposure can be seen more clearly as the difference (ΔD) between the optical density of the exposed portion and that of the unexposed portion increases. In addition, gray scale (the difference in optical density between two adjacent stages is 0.15,
The optical density of the first stage is 0.05 and there are 15 stages. After the exposure under the conditions similar to the above, the resist sensitivity was examined by immersing in 4% sodium metasilicate aqueous solution at 25 ° C. for 1 minute. The sensitivity is indicated by the number of solid steps (the higher the number of steps, the higher the sensitivity). The development acceptability is indicated by the difference in the number of solid steps of the gray scale when exposed through a gray scale under the same conditions and immersed in a 4% sodium metasilicate aqueous solution at 25 ° C. for 5 minutes and for 1 minute (the difference in the number of steps). The smaller the value, the better the development acceptability).

Also, after exposing in the same way as above through a positive transparent original image,
It was rubbed with a sponge containing a 4% aqueous solution of sodium metasilicate and developed to examine the non-image area for unevenness (unevenness). Table 1 shows that there is almost no unevenness of appearance, ○,
Items with uneven appearance are shown with an X.

On the other hand, in order to examine the ease of getting dirt (scumming),
These photosensitive lithographic printing plates were treated with a fatigued developer, and the presence or absence of stains was examined with a printing machine. The result is first
Shown in the table.

As is apparent from Table 1, according to the present invention, a print-out image (printout) can be provided, and further, the sensitivity of the resist is not lowered, and unevenness of the non-image area during development can be prevented. .

Further, when the free-radical generating agent given as a comparative example is used, it is found that there are problems such as soiling with a fatigued developer, uneven appearance, and poor development tolerance. . In particular, in the composition of the present invention, when a large amount of the free radical generator (0.15 g) was used, a very clear printout was obtained, and the disadvantages as listed in Comparative Examples did not occur. You can see how excellent it is.

Example 2 In the same manner as in Example 1, the following photosensitive solution was applied to an aluminum plate and dried.

Copolymer of methyl methacrylate and methacrylic acid (copolymerization molar ratio = 9: 1) 0.60 g trimethylolpropane triacrylate
35 g 2-benzoylmethylene-3-methyl-β-naphthothiazoline 0.02 g free radical generator (Exemplified compound No. 1) 0.07 g leuco crystal violet 0.02 g methyl ethyl ketone 15 g coating amount after drying was 2.5 g / m ² . . When this photosensitive lithographic printing plate was exposed through a transparent negative image in the same manner as in Example 1, the exposed portion developed a purple color and a printout having a high contrast was obtained.

Then caustic soda 1.2g, isopropyl alcohol 30
A lithographic printing plate was obtained by removing the unexposed area with a developer containing 0 ml and 900 ml of water. When a photosensitive solution obtained by removing the free radical generator (Exemplified Compound No. 1) from the photosensitive solution was used, a print-out image hardly appeared even when exposed in the same manner.

Example 3 The unsensitized aluminum plate used in Example 1 was coated with the following photosensitizing solution by using a whaler and dried at 100 ° C. for 2 minutes.

p-Toluenesulfonic acid salt of a condensate of p-diazodiphenylamine and paraformaldehyde 0.2 g Polyvinyl formal 0.75 g Free radical generator (Exemplified compound No. 16) 0.02 g Crystal violet 0.02 g 2-Methoxyethanol 20 g Methanol 5 g Dry The coating amount was 1.0 g / m ² . When this photosensitive lithographic printing plate was exposed with a metal halide lamp of 1 KW from a distance of 70 cm for 30 seconds, an exposed portion was discolored and a clear printed image rich in contrast was obtained.

In the photosensitive liquid, a free radical generator (Exemplified Compound No. 1
When the photosensitive solution except for 6) was used, a clear printout image could not be obtained.

Example 4 In the same manner as in Example 1, the following photosensitive solution was applied to an aluminum plate and dried.

1,4-Equimolar to ethyl p-phenylene diacreate
Polyester synthesized by condensation with bis-β-hydroxyethoxycyclohexane (molecular weight about 8,000)
0.5 g 2-benzoylmethylene-3-methyl-β-naphthothiazoline 0.03 g Free radical generator (Exemplified Compound No. 2) 0.022 g Leuco Crystal Violet 0.012 g Monochlorobenzene 9 g Ethylene dichloride 6 g Coating amount after drying is 1.5 g / It was m ² . When this photosensitive lithographic printing plate was exposed through a transparent negative image in the same manner as in Example 1, a printout image rich in contrast was obtained. Then, the surface was wiped with a developing solution having the following composition so as to be developed to obtain a lithographic printing plate. In comparison with the case where the free radical generator (Exemplified Compound No. 2) was not used in the above-mentioned photosensitive solution, the print-out image was clearly clear and the resist sensitivity was almost the same. It was

Developer composition γ-butyrolactone 1000 ml Glycerol 100 ml Methyl abiate 10 ml [Effect of the invention] The photosensitive composition of the present invention is less likely to leave the photosensitive composition in the non-image area after development, and has less unevenness in the appearance. Scumming is less likely to occur when used for printing plates. Efficiently and instantly discolors when exposed to light,
As a result, a clear boundary is obtained between the exposed portion and the unexposed portion, and it can be recognized as a visible image having a high contrast.

Furthermore, since the free radical generator used in the present invention is stable over time, when the photosensitive composition of the present invention is used in, for example, a PS plate, the shelf life of these articles is improved.

Further, the free radical generator in the present invention does not significantly inhibit the photodecomposition of the photosensitive resist-forming composition, for example, the above-mentioned compositions (1) and (2), so that the photosensitivity of the photosensitive resist-forming composition (resist Photosensitivity of) does not decrease so much. In particular, the composition (2) has excellent development acceptability.

Further, since the free radical generator used in the composition of the present invention is effective even in a small amount, it does not deteriorate the physical characteristics of the resist image obtained after imagewise exposure and development of the photosensitive resist-forming composition. For example, when the photosensitive resist-forming composition provided with the print-out ability according to the present invention is used as the photosensitive layer of a photosensitive lithographic printing plate, the developing property of the printing plate obtained is Various characteristics such as residual hardness, oil sensitivity, printing stain, and printing durability are the same as those when the free radical generator is not added.

Further, the free radical generator according to the present invention is effective even if added in a small amount, but the o-quinonediazide or o-quinone of the composition (2) is used.
In the case of a composition comprising a naphthoquinonediazide compound, since the free-radical generator itself of the present invention has resist-forming properties, it can be added in a large amount, so that the image of the printout can be made surprisingly sharp.

Claims (4)

[Claims] 1. A 4,6-bis (halomethyl) -s-triazine free radical generator which becomes soluble in an alkaline aqueous solution upon irradiation with actinic rays and / or becomes soluble in an alkaline aqueous solution upon irradiation with actinic rays 2. -Halomethyl-1,
What is claimed is: 1. A photosensitive composition comprising a 3,4-oxadiazole free radical generator, and a compound which interacts with a photolysis product of the free radical generator, wherein the free radical generator is an o-quinonediazide group. And / or at least one or more o-naphthoquinonediazide groups. 2. A 4,6-bis (halomethyl) -s-triazine free radical generator is represented by the general formula [1]. (In the general formula [1], X and Y may be the same or different from each other and each represents a chlorine atom or a bromine atom,
R represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and A is selected from the group consisting of (a) an aryl group having 1 to 3 o-naphthoquinonediazide groups or (b) oxygen, nitrogen, sulfur and selenium. A heterocyclic group containing at least one of the above elements, l is 0 or 1 is m, and n is 0
Indicates an integer of 2. ) And a 2-halomethyl-1,
3,4-oxadiazole free radical generator is represented by the general formula [II] (In the general formula [II], X represents a chlorine atom or a bromine atom, R represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and A represents (a) aryl having 1 to 3 o-naphthoquinonediazide groups. Group or (b) oxygen, nitrogen,
It represents a heterocyclic group containing at least one element selected from sulfur and selenium, 1 represents 0 or 1 and m represents an integer of 0 to 2. ) The photosensitive composition according to claim (1), which is a compound represented by the formula (1). 3. The photosensitive composition according to claim 1, wherein the compound that interacts with the photodegradation product of the free radical generating agent is a color changing agent. 4. The photosensitive composition according to claim (2), wherein the compound that interacts with the photodegradation product of the free radical generating agent is a color changing agent.