JPH0469658A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve storage stability and exposure visualizability and to reduce deterioration of sensitivity and to enlarge development allowance by incorporating a dye for changing the tone of a specified triazine compound and a specified oxadiazole compound and their photodecomposition products through the interaction with them. CONSTITUTION:The dye to be added changes the tone of the triazine compound represented by formula I and the oxadiazole compound represented by formula II and their photodecomposition products through the interaction with them. In formulae I and II, each A and B is a carbon ring or a hetero ring both having aromaticity; and each of (l), (m) and n is 0, 1, or 2; and (a) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition that can be used in photosensitive lithographic printing plates and the like.

[Background of the Invention] Photosensitive compositions using an 0-quinonediazide compound as a photosensitive substance are widely used, for example, in the production of positive-working photosensitive lithographic printing plates and printed circuits.

A photosensitive lithographic printing plate is one in which an ink-receptive photosensitive layer is provided on a hydrophilic support. For example, in a positive-working photosensitive lithographic printing plate, the hydrophilic support is exposed to actinic rays such as ultraviolet rays. An ink-receptive photosensitive layer is formed which is solubilized by the ink-receiving method. When the photosensitive layer of such a positive photosensitive lithographic printing plate is subjected to imagewise exposure and then developed, the photosensitive layer in the non-image area is removed and the surface of the hydrophilic support is exposed, while the photosensitive layer in the image area is removed. The layer remains on the support to form an ink-receiving layer.

In planographic printing, the difference in properties is utilized in that the non-image areas are hydrophilic and the image areas are lipophilic.

Usually, the photosensitive layer of a positive photosensitive lithographic printing plate contains an 0-quinonediazide compound as a photosensitive component and an alkali-soluble resin as a component for increasing film strength and alkali solubility.

These photosensitive planographic printing plates are required to have high sensitivity in order to improve workability.

For this reason, among the 0-quinonediazide compounds described in 1.1, 1,2-naphthoquinone-2 is particularly preferred from the viewpoint of sensitivity and cost.
-diazide-5-sulfonic acid ester compound and 1,
2-naphthoquinone-2-diazide-4-sulfonic acid ester compounds are commonly used as useful compounds.

In plate making, exposure operations such as so-called "multi-sided printing" are performed, for example, changing the position of the film original and printing one after another.In these exposure operations,
If it is not possible to distinguish between exposed and unexposed areas, the position of the exposed areas cannot be confirmed, making the exposure work difficult and leading to incorrect exposure. In order to avoid these problems, photosensitive compositions are required to form a visible image upon exposure that can be recognized even under the yellow safety light used for exposure work (exposure visible image property). It is being

The 0-quinonediazide compound photodecomposes and fades when exposed to light, so in a photosensitive composition using the 0-quinonediazide compound, a visible image can be obtained by exposure, but the resulting visible image The contrast was so low that it was almost unrecognizable under the yellow safety lights used for exposure work.

The disadvantage of not being able to obtain a visible image with contrast upon exposure to light can be improved by adding 0-naphthoquinone cyacito-4-sulfonic acid halide and an organic compound having a salt-forming ability as a dye to the photosensitive composition. ,
Although it becomes possible to obtain a visible image that can be clearly recognized even under a yellow safety light, the storage stability is poor, and this effect disappears within 3 months after production.

In addition, by adding oxadiazole compounds and color-changing dyes, a visible image that can be clearly recognized even under yellow safety lights is obtained, it is resistant to safety lights, and has improved storage stability and Although good exposed visible image quality can be obtained over time, there is a significant decrease in sensitivity, and this often occurs when developing with a tired developer or in systems that develop while replenishing the developer. When there is a decrease in developer concentration, there are problems such as plate surface staining.

Triazine compounds and color-changing dyes are added to obtain visible image quality when exposed to light, but those that have excellent visible image quality when exposed to light are difficult to use because they have poor resistance to safety lights, and they are difficult to use when exposed to light. Those that were resistant to light had the disadvantage of poor exposure visibility.

[Object of the Invention] Accordingly, an object of the present invention is to provide a photosensitive composition that has good storage stability and improved visible imageability upon exposure.

Another object of the present invention is to provide a photosensitive composition with little decrease in sensitivity and high development tolerance.

[Structure of the Invention] The object of the present invention described in item 1 is at least (a) the following - general formula [
1], (b) a triazine compound represented by the following general formula [
II] and (c) the triazine compound represented by the above general formula N] or the photodecomposition product of the oxadiazole compound represented by the above general formula [n]. This was achieved by a photosensitive composition characterized by containing a dye that changes its tone.

General Formula N] [In the formula, A represents a homocyclic group or a heterocyclic group having aromaticity, and mSn represents an integer of 0 to 2. ] General formula [rI] [wherein B represents an aromatic homocyclic group or heterocyclic group, g represents an integer of O to 2, and a represents an integer of 1 to 3. ] Hereinafter, the present invention will be explained in detail.

Examples of the orthoquinonediazide compound used in the present invention include ester compounds of O-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include phenol, 0-
Cresol, m-cresol, p-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, I-nosorcin, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin.

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde,
Examples include furfural.

Preferred among these aldehydes are formaldehyde and benzaldehyde.

Furthermore, examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, m-,p=mixed cresyl/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like.

The condensation rate of 0-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the 0-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 80%.
is preferable, and more preferably 20 to 45%.

Considering the coating properties, the polymer compound containing 0-quinonediazide used in the present invention has a weight average molecular weight of 1.
,000 or more, more preferably 1
, has a molecular weight of 500 or more.

Furthermore, examples of the O-quinonediazide compound used in the present invention include the compounds described in JP-A-58-43451.

Also, 2,3. , l trihydroxybenzophenone, 2
, 3.4.4'-tetrahydroxybenzophenone,
2 3.4.2', 4'-pentahydroxybenzophenone, 2.3,4.3'.

Condensation compounds of 4'5' -hexahydroxybenzophenone and the like with orthoquinone diazide groups can also be used.

Among the above 0-quinonediazide compounds, the 0-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazide sulfonyl chloride or 12-naphthoquinonediazide sulfonyl chloride with pyrogallol acetone condensation resin or 2,3゜4-trihydroxybenzophenone is Most preferred.

As the O-quinonediazide compound used in the present invention, each of the above compounds may be used alone, or two or more types of compounds may be used in combination.

The preferred amount of the 0-quinonediazide compound used is 10 to 40% by weight of the nonvolatile components of the photosensitive composition.

Further, particularly preferred as the 0-quinonediazide group are the 4- or 5-sulfonic acid group of 1,2-quinonediazide or the 4- or 5-carboxyl group of 1,2-quinonediazide.

Said above. - The quinonediazide compound is preferably used in combination with an alkali-soluble resin. Examples of alkali-soluble resins include novolac resins, vinyl polymers having 71-nor hydroxyl groups, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841M.

Examples of the novolak resin include phenol formaldehyde resin, cresol formaldehyde resin, phenol pot I nosol polar hehyde octacondensation resin as described in JP-A-55-57841, and JP-A-55-127553. Examples include copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde as described in the above publication.

In addition, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and includes at least one structural unit of the following general formula [II] to general formula [Vll]. Polymers containing the following are preferred.

General formula [II] -HCRt R2-CR3 mode C0NR4-(A→-B-OH General formula [111F %formula% General formula [IV] ---(CRIR2-CR5→- -0H General formula [V] General formula [Vll -(CL CR4→- C.C.

02 \ 7/-〇 [In the formula, R1 and R2 each represent a hydrogen atom, an argyl group, or a carboxyl group5, preferably a hydrogen atom. R3 represents a hydrogen atom, a halogen atom, or an alkyl group17, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkyreso group which may have a substituent and which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B has a substituent. represents a phenylene group that may have a substituent or a naphthylene group that may have a substituent. ] The polymer used in the photosensitive composition of the present invention preferably has a copolymer type structure, and the polymer can be used in combination with the structural units represented by the general formulas III] to [Vll, respectively. Examples of mer units include ethylene, propylene,
Ethylenically unsaturated olefins such as isobutylene, butadiene and isoprene, styrenes such as styone, α-methylstyrene, p-methylstyrene, p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, e.g. Unsaturated aliphatic dicarboxylic acids such as itaconic acid, malic acid, and maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, and 2-chloroethyl acrylate. , phenyl acrylate, α-
Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide; e.g. acrylanilide; ,
Anilides such as p-chloro γ-acrylanilide, m-nitroacrylanilide, +Tl-methoxyacrylanilide, vinyl nitrides such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, such as methyl vinyl ether, Vinyl ethers such as vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride+r, t-”nylidene 1-ide, such as 1-methyl-1-methoxyj, ditone, 1.]- Dimethoxylene, 1,2 dimeth4-thione, 1,1-dimethoxymethylsulfonylethylene, ]-]methyl-1-disil+
Examples include N-vinyl monomers such as ethylene, ethylene derivatives, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N=vinylpyrrolidene, and N-vinylpyrrolidone. These vinyl m-isomers exist in polymer compounds with a structure in which an unsaturated double bond is cleaved.

Among the above-mentioned monomers, aliphatic monocarboxylic acids such as Nisdels and nitriles exhibit excellent performance for the purpose of the present invention and are preferred (7).

These alkali-soluble resins preferably have a molecular weight of 1-500 or more, more preferably 1. ＜Ha.

Any molecular weight between 2,000 and 10 is fine.

These alkali-soluble resins are preferably contained in the photosensitive composition of the present invention in an amount of 50 to 90% by weight based on the nonvolatile components of the photosensitive composition.

The triazine compound used in the present invention has the following general formula [
1].

General Formula IIF In the general formula [1], A is a homocyclic group or a heterocyclic group having aromaticity. These homocyclic groups or heterocyclic groups include those having substituents.

The aromatic homocyclic group or heterocyclic group represented by A is preferably monocyclic or bicyclic.

A homocyclic group or a helicyclic group having %'N group character represented by A
m/ring group and "C" is, for example, phenyl group, naphthyl group,
Examples thereof include oxazole group, benzofuryl group, benzongizazole group, benzimidazole group, and quinolyl group, but from the viewpoint of synthesis yield and solubility in a developer, ]J, 1-ring phenyl group is preferred.

These substituents which may have 5 or more combined rings and E2 are preferably electron-loving groups. Electrician (Rr-i group refers to a group whose Hammett elongation value is negative, such as phenyl group, l
・Alkyl groups such as lymethylsilicate group, methyl group, yutyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group, butoxy group, n-propoxy group, isopropoxy group , n-butoxy group, alkoxy group such as t-butoxy group, )Jnoxy group, amino group,
Examples include substituted amino groups. Particularly preferred among these substituents are alkyl groups and alkoxy groups.

In the above general formula [1], mSn is preferably O.

Specific examples of triazine compounds represented by the general formula [1] are shown below, but the present invention is not limited to these compounds.

Ch The proportion of these triazine compounds in the photosensitive composition is preferably 0.1 to 5% by weight based on the nonvolatile components of the photosensitive composition, and a particularly preferable usage amount is 0.5% of the nonvolatile components of the photosensitive composition. ~3% by weight.

The oxadiazole compound used in the present invention is a compound represented by the following general formula [II].

General Formula [■] In the general formula [11], B represents an aromatic homocyclic group or a heterocyclic group.

The aromatic ring of these aromatic homocyclic groups or heterocyclic groups may be monocyclic or bicyclic, or may have a substituent.

Examples of the aromatic homocyclic group or heterocyclic group represented by B include a phenyl group, an oxazole group, a benzofuryl group, a benzoxazole group, a benzimidazole group, and a quinolyl group.

In addition, substituents include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups such as methyl and ethyl groups, alkenyl groups such as vinyl groups and β-phenylvinyl groups, alkoxy groups such as methoxy groups and ethoxy groups, Examples include aryl groups such as phenyl group and naphthyl group, and cyano group.

As the oxadiazole compound used in the present invention,
Japanese Patent Publication No. 57-6098, Fit-51788, Special Publication No. 1-28389, Japanese Unexamined Patent Publication No. 1988-13
No. 8589, No. 80-177340, No. 60
Examples include those described in Publication No.-241049, etc.
More specifically, the following compounds can be mentioned.

However, the compounds that can be used in the present invention are not limited to these.

The proportion of these oxadiazole compounds in the photosensitive composition is 0.01 to 10% of the nonvolatile components of the photosensitive composition.
% by weight is preferred, and a particularly preferred amount used is 0.1 to 5% by weight of the non-volatile components of the photosensitive composition.

Further, 5 to 200% by weight of the triazine compound of the present invention,
In particular, 20 to 100% by weight is preferred.

Next, a dye that changes its color tone by interaction with a photodecomposition product of a triazine compound represented by the general formula [1F] or an oxadiazole compound represented by the general formula [n] will be described.

The dyes in the present invention include pigments as well as dyes, and inorganic pigments can also be used, but it is preferable to use organic dyes whose color tone changes with acid.

Examples of organic dyes that can be used include diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminonaphthoquinone, and azomethine dyes.

Examples of these organic dyes include Eisen Brilliant Basic Cyanine 6GH [manufactured by Odogaya Chemical Industry ■],
Astra New Fuchsin, Alizarin Red S, Eosin, Ethyl Violet, Erythrosin B1 Auramine, Oil Green #502 [Manufactured by Orient Chemical Industry ■]
, Oil Blue Let #308 (manufactured by Orient Chemical Industry ■), Oil Pink #31.2 (manufactured by Orient Chemical Industry ■), Oil Blue #603 (manufactured by Orient Chemical Industry ■), Oil Red 5B (manufactured by Orient Chemical Industry ■)
, Oil Red OGC (manufactured by Orient Chemical Industry ■), Oil Red: RR (manufactured by Orient Chemical Industry ■), Orange ■, 2-carboxyanilino-4,-p-diethylaminophenylimino naphthoquinone, 2-carbostearylamino-4- p-dihydroxyethylaminophenylimino naphthoquinone, xylenol blue, quinaldine red, crystal violet, crystal violet F], OB, m-cresol purple, cresol red, Congo red, cyano-p-diethylaminophenyliminoacetanilide, 4-p diethylaminophenyl Iminonaphthoquinone, 2,7-dichlorofluorescein, diphenylthiocarbazone, 1,3-diphenyltriazine, Spin Red BEH Special [manufactured by Odugaya Chemical Industry Co., Ltd.], sulforhodamine B1 thymol sulfophthalein, thymol phthalein, thymol pur, Nile Blue 2B, Nile Blue A, 1-β naphthyl-4-
p-diethylaminophenylimino-5-pyrazolone,
α-Naphthyl Red, Parafuthacine, Rose Methyl Red, Victoria Pure Blue BOH, First and Violet R1 Phenacetaline, 1-Phenyl-3-
Methyl-4-p-diethylaminophenylimino-5-
Pyrazolone, phenolphthalein, phenol red,
Tsuksin, Brilliant Green, Bromocresol Purple, Bromophenol Pur, Peisic Tsuksin,
Benzopurpurin 4B.

Magenta, malachite green, methanyl yellow, methyl orange, methyl green, methyl bioresotho 2B
, methylviolet, l)-meth↑-dibenzoyl-p
Specific examples include '-diethylamino-0'-methylphenyliminoacetanilide, rose bengal, rhodamine 6G, and rhodamine B.

Among these compounds, triphenylmethyl-based compounds are preferred from the viewpoint of degree of discoloration and storage stability.

Dye particularly preferably used in the present invention is Malachi Green (CI A2000) 1.
7' Chill Violet (CI 42535), Methyl Green (CI 42585), Crystal Violet (C142555), Brilliant Green (
CI 4204.0), ethyl violet cc I
4.2600), phenol'tutarein, phenol red, promophenol blue, thymol blue, bromocresol purple, Victoria Pure Blue BOH (C142595), Eisen Brilliant Basic Cyanine 6GH [manufactured by Odugaya Chemical Co., Ltd.]
(C142025), Astranewfuchsin (CI
4.2520), 7 Zenta (CI 42510)
, Crystal Bai 1st knot F1.0B (manufactured by BASF) (Ci 4255'i"), Tsukushin (C14
2500).

The proportion of these dyes in the photosensitive composition is preferably 0.1 to 10% by weight of the nonvolatile components of the photosensitive composition.
Particularly preferred is 0.3 to 5% by weight.

In addition to the materials described below, the photosensitive ill composition of the present invention may contain other additives as necessary.

Plasticizers include various low-molecular compounds such as phthalate esters, triphenyl phosphates, maleic acid esters, coating properties improvers, and surfactants such as fluorosurfactants, ethyl cellulose polyal 4. Examples include nonionic surfactants represented by -1 nonether and the like.

Further, a sensitizer for improving sensitivity may also be added to the photosensitive composition of the present invention. As the sensitizer, gallic acid derivatives described in JP-A No. 57-118237, 5-membered cyclic acid anhydrides such as those described in JP-A-52-80022, such as phthalic anhydride; , tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Examples include maleic anhydride, succinic anhydride, virometic acid, itaconic acid, etc., and 6-membered cyclic acid anhydrides such as those described in JP-A-58-11932, such as glutaric anhydride and its derivatives. . Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

A positive-working photosensitive lithographic printing plate can be formed by dissolving the photosensitive composition of the present invention in a solvent that dissolves each of the above-mentioned components, and applying and drying the solution on the surface of a suitable support. Solvents that can be used include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, t-
Alcohols such as butatane, 1-pentanol, 2-pentanol, 1-hexanol, acetone, methyl ethyl ketone, methyl-〇-propyl ketone, methyl isopropyl ketone, methyl-〇-butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. ketones, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate], ethylene glycols such as ethylene glycol isopropyl ether acetate, diethylene glycol monomethyl Ether, diethylene glycols such as diethylene glycol monoethyl ether, diethylene glycol isopropyl ether, diethylene glycol phenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene Propylene glycols such as glycol isopropyl ether, acetate esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, pond water, methyl lactate, ethyl lactate, diethyl ether, dioxane, dimethylformamide, dimethyl sulfoxide , γ-butyrolactone, 3-methoxy-1-butanol, 3-methyl-
3-methoxy-1-butanol, tetrahydrofuran,
Examples include methylene chloride.

In the present invention, preferred organic solvents are solvents whose main component is a compound belonging to diethylene glycols or propylene glycols. These have become problems in recent years. It is preferably used as a compound that improves the toxicity of compounds such as ethylene glycols and also has good solubility in the composition.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, etc. can be used.

Examples of the support on which the photosensitive layer using the photosensitive composition of the present invention is provided include metal plates such as aluminum, zinc, copper, and steel, and metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, and the like. Examples include metal plates, paper, plastic films, paper coated with resin, paper covered with metal foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, aluminum plates are preferred. When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing.

The various methods described above can be used alone or in combination depending on the composition of the aluminum material. Preferred is electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, desmut treatment is performed with an aqueous alkali or acid solution, neutralized, and washed with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of anodic oxide film formed is 1 to 50 mg/dr
rr is appropriate, preferably 1O~40mg/dr+
It is f. The amount of anodized film can be determined, for example, by immersing an aluminum plate in a phosphoric acid chromic acid solution (85% phosphoric acid solution + 35 ml of chromium oxide (Vl): prepared by dissolving 20 g in 1 g of water) and dissolving the oxide film. It is determined by measuring changes in weight before and after dissolving the film on the plate.

Specific examples of the sealing treatment include hot water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, in general, when contact baking a film original onto a photosensitive lithographic printing plate, the printing frame is vacuumed, and a method for improving this vacuum adhesion is also a positive-working photosensitive lithographic printing plate using the photosensitive composition of the present invention. Can be applied to printing plates. Methods for improving vacuum adhesion include mechanically creating unevenness on the surface of the photosensitive layer, scattering solid powder on the surface of the photosensitive layer,
A method of providing a matte layer on the surface of a photosensitive layer as described in JP-A-50-125805, and JP-A-55
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer, as described in Japanese Patent No. 1.2974.

A positive-working photosensitive lithographic printing plate to which the photosensitive composition of the present invention is applied can be used in the same manner as those conventionally used. For example, an ultra-high pressure mercury lamp is passed through a transparent film,
It is exposed to light using a light source such as a metal halide lamp, a xenon lamp, or a tungsten lamp, and then developed with an alkaline developer, leaving only the unexposed portions on the surface of the support, creating a positive relief image.

Examples of alkaline developers include sodium hydroxide,
Examples include aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.

The concentration of the alkali metal salt is preferably 0.1 to 10% by weight. In addition, an anionic surfactant, if necessary, is added to the developer.
Amphoteric surfactants and organic solvents such as alcohols can be added.

[Examples] The present invention will be explained below using Examples, but the present invention is not limited thereto.

Example 1 (Preparation of photosensitive lithographic printing plate sample) An aluminum plate with a thickness of 0.24 mm was degreased in a 5% by weight aqueous sodium hydroxide solution at 60°C for 1 minute, and then treated with 1 g of 0.5 mol hydrochloric acid. Temperature 25 in aqueous solution
The electrolytic etching treatment was performed under the following conditions: °C, current density: 60 A/dL, 112 seconds, and treatment time: 30 seconds. Then, after desmutting in a 5% by weight aqueous sodium hydroxide solution at 60°C for 10 seconds, desmutting was performed in a 20% by weight sulfuric acid solution at a temperature of 20°C.
The anodization treatment was performed under the conditions of a current density of 3 A, /d rrr, and a treatment time of 1 minute. Furthermore, 20℃ with hot water of 30℃
A hot water sealing treatment was performed for 2 seconds to produce an aluminum plate to be used as a support for lithographic printing plate material.

A photosensitive composition coating solution having the following composition was applied to the aluminum plate prepared as above using a spin coater, and dried at 90°C for 4 minutes to obtain positive photosensitive lithographic printing plate sample No. 1.
I got it. The coating amount of the photosensitive composition is 24mg/dr
It was d.

(Coating liquid composition) Binder resin (BD-1) 7.0g Quinonediazide compound (photoreceptor) (QI)-1,) 1.6
g Triazine compound (No. 1) 0.0
4g xadiazole compound (No. 1) 0.
02 g Victoria Pure Blue Gray H (manufactured by Odugaya Kagaku ■) 0.06 g Methyl Cellosolve 100 ml In the coating liquid composition of the above photosensitive composition, as shown in Table 1,
Photosensitive lithographic printing plate samples Nos. 2 to 12 were obtained by changing the binder resin, quinonediazide compound, triazine compound, and oxadiazole compound.

Photosensitive planographic printing plate sample No. obtained in this way,
1 to 12, a step tablet for sensitivity measurement (No. manufactured by Eastman Kodak Co., 2 gray scale of 21 steps with a density difference of 0.5) was placed in close contact with
) was used as a light source and exposed from a distance of 90c+n. Next, this sample was developed at 27° C. for 20 seconds using a developer prepared by diluting Konica's 5DR-1 developer 6 times with water.

Next, in order to examine the visible image quality after exposure, the difference in density between the exposed and unexposed areas of the sample before development, which was exposed under the above conditions, was measured using a density system (Sakura Densitometer PUMA-65 manufactured by Konica ■). It was measured. It means that the larger the density difference ΔD, the better the exposure visible image quality.

In addition, in order to examine the shelf life of the product, we
Samples 1 to 12 left under the condition of %RH for 5 days were also evaluated for exposure visibility in the same manner as described above, and compared with ΔD of the sample before storage.

In addition, in order to evaluate under-developability, the developability was evaluated using a developer whose alkali concentration was further diluted, that is, a developer whose developing ability was reduced. The above developability is determined by diluting the 5DR-1 developer at a dilution rate of 9.10.11.
A printing test was conducted on the lithographic printing plate samples obtained by developing each sample at 27° C. for 20 seconds and visually evaluating the extent of halftone dots in some shadows.

The method for evaluating safelight properties is as follows.

Unexposed samples 1 to 12 were placed under a white fluorescent light (40W).
, 5 m, and left for a predetermined period of time. after that,
The sample was developed at 27 DEG C. for 20 seconds using a developer prepared by diluting 5DR-1 (manufactured by Konica ■) six times with water. After development,
The sample was visually observed, and the safelight property was evaluated based on the time at which it was recognized that the photosensitive layer began to be removed by the developer.

The results are shown in Table 1.

The following margins are oxadiazole compound N011 No, 2 No, 3 ] Quinonediazide compound (photoreceptor) D x:y-2:1 Mw of resin before reacting Q -900D-2 Triazine compound D Reacting Q. Mw of previous resin Mw - 1,500D Mw of resin before reacting Q2 - 1,500D Binder resin BD-1 A combination of phenol, m-cresol and p-cresol (molar ratio 48:32:20) and formaldehyde Polymer resin D-2 From the results in Table 1, sample N using the photosensitive composition of the present invention
It can be seen that Samples Nos. 1 to 9 are superior in sensitivity, under-developability, exposed visible image quality, and exposed visible image quality after storage, compared to comparative samples Nos. 10 to 12.

[Effects of the Invention] According to the present invention, it is possible to provide a photosensitive composition that has high development tolerance, excellent exposed visible image properties, and does not deteriorate in exposed visible image properties even after storage.

(k II : m: n-25:20:50: 2Mw-60
000) Below blank space Applicant Konica Co., Ltd.

Claims (1)

[Scope of Claims] At least (a) a triazine compound represented by the following general formula [I], (b) an oxadiazole compound represented by the following general formula [II], and (c) the above general formula [I] A photosensitive composition characterized by containing a dye that changes its color tone by interaction with a photodecomposition product of a triazine compound represented by the above general formula [II] or an oxadiazole compound represented by the above general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, A represents a homocyclic group or a heterocyclic group having aromaticity, and m and n represent integers of 0 to 2. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an integer from 1 to 3. ]