JPS63153542A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having high sensitivity and contg. a free radical producing agent having high sensitivity to photolysis by incorporating a specified s-triazine compd. and a compd. having at least one addition- polymerizable ethylenic unsatd. double bond. CONSTITUTION:This photosensitive compsn. contains a photosensitive s-triazine compd. represented by formula I and a compd. having at least one addition- polymerizable ethylenic unsatd. double bond. In the formula I, each of R1 and R2 is H atom, alkyl, substd. alkyl group or the like, R1 and R2 may form a hetero ring consisting of nonmetallic atoms together with N bonding to R1 and R2, each of R3 and R4 is H, halogen atom, alkyl group or the like, each of X and Y is Cl or Br atom and each of (m) and (n) is 0, 1 or 2. The photosensitive compsn. has high sensitivity and can be advantageously used to produce a photosensitive lithographic printing plate, a proofreading plate for printing or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition containing a novel compound that generates free radicals when exposed to light. More specifically, the present invention relates to a photosensitive composition containing a novel photosensitive 5-)IJ azine compound.

[Conventional technology]

Compounds that decompose to produce free radicals on exposure to light (
free radical generators) are well known in the field of graphic arts. They are photopolymerization initiators in photopolymerizable compositions,
Photoactive agents and photogenerated acids in free radical photographic compositions; widely used as photoinitiators for reactions catalyzed thereby. Such free radical generators are used to make a variety of photosensitive materials that are useful in printing, duplication, copying, and other imaging systems.

Organic halogen compounds photolyze to give halokene radicals such as chlorine radicals and bromine radicals. These halogen radicals are good hydrogen abstractors and in the presence of hydrogen donors, acids are produced. For their application to photopolymerization processes and free radical photography processes, see J.
Sensitive Systems JJ, Willie & Sons (2 Knee York l 965) CJ, K
Written by osarrLightSensitive Syst
ems J J] 1ley & 5oz (Ne%v
York 1965) pp. 3180-181 and 361-
It is described on page 370.

Conventionally, carbon tetrabromide, iodoform, tribromoacetophenone, and the like are representative compounds that generate halogen free radicals by the action of light, and have been widely used. However, these free radical generators have the disadvantage that they are only decomposed by light in a very limited wavelength range.

In other words, it was sensitive to the ultraviolet region, which is shorter than the dominant wavelength of commonly used light sources. Therefore, these compounds lack the ability to effectively utilize light in the near-ultraviolet to visible range emitted by a light source, and therefore have poor free radical-generating ability.

In order to improve this drawback, it has been proposed to widen the sensitive wavelength range by mixing a certain kind of sensitizer. For example, U.S. Pat. No. 3.106.466 and U.S. Pat.
．． 633, sensitizers such as merocyanine dyes, styryl bases and cyanine bases. It is true that the addition of these sensitizers has expanded the sensitivity wavelength range of carbon tetrabromide and iodoform to visible light, but this is still not satisfactory. This is because it is necessary to select a sensitizer that has good compatibility with the free radical generator or other elements in the photosensitive composition. This is because it was difficult to choose.

In order to improve this drawback, a halogen free radical generating agent has been proposed whose sensitivity wavelength range is from near ultraviolet to visible light. For example, U.S. Pat. No. 3,954,475, U.S. Pat.
．． No. 037 and No. 4. There is a group of halomethyl-5-) riazine compounds described in ig9.323. These compound groups range from near ultraviolet to visible light! : Although there is a sensitive wavelength range, the irradiated light is not used effectively and the sensitivity of photolysis is relatively low. Furthermore, photosensitive compositions using these triazine compounds have the disadvantage that the triazine compounds crystallize during long-term storage, resulting in a decrease in sensitivity.

[Problem that the invention seeks to solve]

Therefore, it is an object of the present invention to provide a highly sensitive photosensitive composition containing a free radical generating agent that is highly sensitive to photolysis.

Another object of the present invention is to provide a photosensitive composition with good storage stability.

[Means for solving problems]

As a result of various studies, the present inventors have found that the above problem can be solved by using a novel s'-) riazine compound represented by the following general formula (I) and a compound having at least one ethylenically unsaturated double bond capable of addition polymerization. It has been found that the problem can be solved by a photosensitive composition containing.

The compound represented by the general formula (I) also has good compatibility with other components in the composition.

R3 In the general formula [I], R3 and R2 may be the same or different, and are a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a formula [■], a formula 2■] The group represented by Rs CL II :i or R, , R2 may form a heterocyclic ring consisting of a nonmetallic atom together with the nitrogen atom to which it is bonded.

In formula CII), R6 represents an alkyl group, substituted alkyl group, aryl group, or substituted aryl group, and in formula [1] IE, R6 and R may be the same or different from each other and are hydrogen atoms. , an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.

R3 and R1 represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.

X and Y may be the same or different and represent a chlorine atom or a bromine atom. m1η represents 0.1 or 2.

The present invention will be explained in more detail below.

In general formula (I), (I[>, (I[I)), R3-
The alkyl group for R7 is one having 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group, and the aryl group is one having 6 to 1 carbon atoms such as phenyl group or naphthyl group.
It is preferable to use up to 4.

Examples of substituents for the substituted alkyl groups and substituted aryl groups of R1, R2, R5, R6, and R1 include aryl groups such as phenyl groups, halogen atoms such as chlorine atoms, methoxy groups, and methoxy groups. alkoxy group; carboxyl group; carboalkoxy group such as carbomethoxy group or carboethoxy group; carboaryloxy group; cyano group; acyl group such as acetyl group or benzoyl group; nitro group; dialkylamino group; or general formula % formula Examples include sulfonyl derivatives represented by %( ) (where Z represents a hydrogen atom, an alkyl group, or an aryl group).

Further, the substituents of the substituted aryl groups of R1, R2, R5, R6, and R1 include alkyl groups in addition to the above-mentioned substituents.

When R2 and R2 together with the nitrogen atoms packed therein form a heteroarticulated ring consisting of a nonmetallic atom, the heteroarticulated ring is as follows (
Examples include those shown in D) to (H).

Among the substituents of the substituted alkyl group or substituted aryl group of R1 and R2, particularly preferred are electron-withdrawing groups such as a halogen atom, a carboxyl group, a carbalkoxy group, a cyano group, an acyl group, and a sulfonyl derivative. Particularly preferred among the substituents of the substituted alkyl group and substituted aryl group are electron-donating groups such as dialkylamide 7 groups and alkoxy.

Among the compounds represented by the above-mentioned general formula (I), particularly preferred are those in which R7 and R
2 is a hydrogen atom, a carbalkoxymethyl group, a chloromethyl group, a chloroethyl group, a cyanomethyl group, or a cyanethyl group, and at least one of R1 and R2 is a group other than a hydrogen atom, or a group consisting of R3 and R2 and R3 and R1 are a hydrogen atom, a halogen atom, or an alkyl group.

The compound represented by the general formula (I) used in the photosensitive composition of the present invention is an aromatic nitrile compound represented by the general formula (■) and R.

Using haloacetonitrile, K. Wakabayashi et al., Bulletin of the Chemical Society of Japan
alSociety of Japan), 42.
It can be synthesized by cyclization according to the method described in 2924-2930 (I960).

Examples of compounds useful as free radical generating agents for use in the present invention are shown below. However, it goes without saying that the present invention is not limited to the following compounds.

The free radical generating agent represented by the general formula (I) is particularly useful when used as a photoinitiator in a photopolymerizable composition.

When the free radical generating agent represented by general formula (I) is used in a photopolymerizable composition, the photopolymerizable composition contains a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and the necessary components. If so, it is composed of a binder and, if necessary, a sensitizer, especially the photosensitive layer of a photosensitive printing plate, photoresist, etc.! This is helpful.

The polymerizable compound having an ethylenically unsaturated bond in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, and is a monomer, a prepolymer, i.e. It has chemical forms such as dimers, trimers and other oligomers, mixtures thereof and copolymers thereof. Examples of these include unsaturated carboxylic acids and their salts, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds,
Examples include amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid,
These include maleic acid.

Salts of unsaturated carboxylic acids include alkali metal salts of the aforementioned acids, such as sodium and potassium salts.

Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol cyacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
Examples include dipentaerythritol triacrylate, dipentaerythritol triacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomers. Examples of meccrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol diconate, and pentaerythritol. diacrylate, penquerythritol trimecacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p
-(3-methacryloxy-2-hydroxypropoxy)phenylcdimethylmethane, bis-[p-(methacryloxyethoxy)phenylnidimethylmethanelene glycol cyitaconate, brobylene glycol diitacone), l,3-butane Diolsheitaconate, 1.
Examples thereof include 4-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate, and sorbitol tetratrataconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. ink) 7E2-[-
Steltocytes include ethylene glycol diisocrotonate, pentaerythritol diincrotonate, sorbitol tetraisocrotonate, and the like. Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.

Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis-methacryl. amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

As another example, the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by V) is added.

CH2=C(R)COOCH2C)I(R' )0)!
(V) (However, R and R' represent H or CH3.) When the free radical generating agent represented by general formula (I) is used as a photopolymerization initiator in a photopolymerizable composition, the photopolymerizable composition The composition can contain a binder if necessary.

As the binder in the photopolymerizable composition of the present invention, the compatibility with the polymerizable ethylenically unsaturated compound and the photopolymerization initiator is determined in the manufacturing process of the photosensitive material including preparation of the coating solution, coating, and drying of the composition. The photosensitive layer or resist layer should be of good quality to the extent that no demixing occurs, and the photosensitive layer or resist layer should be able to be developed after 0 light, whether it is by solution development or peeling development. It should be strong as a photosensitive layer or resist layer. Although it is required to have characteristics such as being able to form a film, it is usually appropriately selected from linear organic polymers. Specific examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-butyl group, 1sO-butyl group, n-hexyl group, - ethylhexyl group, etc.), copolymers of acrylic acid alkyl esters (alkyl groups are the same as above) and at least one of monomers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, etc. Copolymers, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, polymeth Acrylic acid alkyl ester (alkyl group includes methyl group, ethyl group, n-
Propyl group, n-butyl group, iso-butyl group, n-
hexyl group, cyclohexyl group, 2-ethylhexyl group, etc.), copolymer of mecacrylic acid alkyl ester (alkyl group is same as above) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polystyrene , poly-α-methylstyrene, polyamide (6-nylon, 6.6-nylon nato), methylcellulose, ethylcellulose, acetylcellulose, polyvinyl formal, polyvinyl butyral, and the like.

Furthermore, if a water or alkaline water soluble organic polymer is used, water or alkaline water development becomes possible. Examples of such high molecular weight polymers include addition polymers having carboxylic acid in their side chains, such as methacrylic acid copolymers (for example, copolymers of methyl methacrylate and methacrylic acid,
Copolymer of ethyl methacrylate and methacrylic acid, copolymer of butyl methacrylate and methacrylic acid, copolymer of allyl methacrylate and methacrylic acid, copolymer of ethyl acrylate and methacrylic acid, methacrylic acid copolymers of ethyl styrene and methacrylic acid), acrylic acid copolymers (copolymers of ethyl acrylate and acrylic acid, copolymers of butyl acrylate and acrylic acid, copolymers of ethyl acrylate and acrylic acid, etc.) copolymers with styrene and acrylic acid), as well as itaconic acid copolymers, crotonic acid copolymers, partially esterified maleic acid copolymers, and similar acidic celluloses with carboxylic acids in their side chains. There are derivatives.

These high molecular weight polymers may be used alone as a binder, but two or more types must be compatible with each other to the extent that demixing does not occur during the manufacturing process from preparation of the coating solution to application and drying. High molecular weight polymers can be mixed in appropriate ratios and used as a binder.

The molecular weight of the high molecular weight polymer used as a binder can take a wide range of values depending on the type of polymer, but -IIE) has a molecular weight in the range of 5,000 to 2 million, more preferably in the range of 10,000 to 1 million. is suitable.

When the photopolymerizable composition of the present invention further contains a sensitizer, a sensitizer that increases the photopolymerization rate is used in combination with a free radical generator represented by the general formula (I), that is, a photopolymerization initiator. agent is selected. Specific examples of such sensitizers include benzoin, benzoin methyl ether, benzoin ethyl nityl, 9-fluorenone, 2-chloro-9
-fluorenone, 2-methyl-9-fluorenone, 9-
Anthrone, 2-bromo-9-anthrone, 2-ethyl-9-antrone, 9.10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9
, 10-anthraquinone, 2,6-dichloro-9,10
-Anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p-(dimethylamino)phenylstyryl ketone, p-(dimethylamino)phenyl p
-Methylstyryl ketone, benzophenone, p-(dimethylamino)benzophenone (or Michler's ketone)
, p-(diethylamino)benzophenone, benzanthrone, and the like. Among these compounds, it is particularly preferable to use Michler's ketone.

Furthermore, as a preferable sensitizer in the present invention, the general formula (
Examples include compounds represented by Vl).

, Pa-“,.

R6 In the formula, R1 is an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (e.g.,
2-hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2-carboxyethyl group, etc.).

R2 is an alkyl group (for example, methyl group, ethyl group, etc.)
, or an aryl group (eg, phenyl group, p-hydroxyphenyl group, naphthyl group, chenyl group, etc.).

Z is a nonmetallic atomic group necessary to form the nitrogen-containing heterocyclic nucleus usually used in cyanine dyes, such as benzothiazoles (benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, etc.), naphthothiazole. (alpha-naphthothiazole, β-naphthothiazole, etc.), benzoselenazole (benzoselenazole, 5-chlorpenzoselenazole, 6-medoxybenzoselenazole, etc.), naphthoselenazole (α-naphthothiazole, etc.) Naphthoselenazole, β-naphthoselenazole, etc.), benzoxazole (benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, etc.), naphthoxazole (α-naphthoxazole, β-naphthoxazole, etc.) represent.

Specific examples of compounds represented by the general formula (\l) include:
It has a chemical structure that is a combination of these Z, R, and R2, and many of them exist as known substances. Therefore, it is possible to appropriately select and use these known materials.

Furthermore, this invention! =O: preferably ',) As the sensitizer, Japanese Patent Application No. 60-44021, Japanese Patent Application No. 60-4402
No. 9: The merocyanine dye described herein, and the following general formula [■
Ketocoumarin compounds represented by `` and 1 can also be mentioned.

Here, R represents an alkyl group such as a methyl group or an ethyl group.

Furthermore, during the production or storage of the composition of the present invention, it is desirable to add a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, aethylcatechol, benz'quino:/, salts (IJ-copper, phenothiazine, floranil, naphthylamine, β - Naphthol, nitrobenzene, dinitrobenzene, etc.

In some cases, dyes or pigments such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon black, iron oxide, phthalocyanine pigments, azo pigments, etc. are used for coloring purposes. May be added.

After anodizing (sulfuric or phosphoric acid), a negative-working diazo resin, such as a PFs salt of a condensate of p-diazodiphenylamine and formaldehyde, may be added to improve adhesion to the silicate aluminum support.

Furthermore, a plasticizer can be added to the photopolymerizable composition of the present invention, if necessary. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diethyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, dimethyl glycol phthalate, ethyl fucryl ethyl glycolate, butyl phthalyl butyl glycolate. Glycol esters such as chloride, phosphate esters such as tricresyl phosphate, triphenyl phosphate,
Examples include aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dibutyl sebacate, and dibutyl maleate.

The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various components in a solvent and coating it on a suitable support by a known method. Next, preferred ratios of the various constituent components in this case are expressed in parts by weight based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

/-death = 0 00 L+) OO -1% e+ 0 NNL"') xii':! Jujube ζ Dye Dye Dye r+ C:) C'1-1j') 0 j 20+ CN Photosensitivity of the present invention Solvents used when applying the composition include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosolve acetate, methyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methanol, monochlorobenzene, toluene, and ethyl acetate. These solvents may be used alone or in combination.

The photosensitive composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. When producing a photosensitive lithographic printing plate, the coating amount is generally 0.1 to 10.0 g/m'' in terms of solid content, particularly preferably 0.5 to 5.0 g/m''. Suitable supports for photosensitive lithographic printing plates include hydrophilized aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, grained aluminum plates, silicate electrodeposited aluminum plates, and other surface-leaded plates. Examples include stainless steel plates, chromium-treated copper plates, and hydrophilized plastic films and paper.

In addition, when the photosensitive composition of the present invention is used to produce printing proof plates, films for overhead projectors, and films for second original drawings, suitable supports include transparent films such as polyethylene terephthalate film and cellulose triacetate film. The surface of these plastic films may be chemically or materially matted.

When the photosensitive composition of the present invention is used in the production of a photomask film, suitable supports include polyethylene terephthalate films deposited with aluminum, aluminum alloys, and chromium, and polyethylene terephthalate films with colored layers. can be mentioned.

Furthermore, when the composition of the present invention is used as a photoresist, various materials such as a copper 5 or copper plated plate, a stainless steel plate, a glass plate, etc. can be used as a support.

, 39 [Example] Synthesis examples of the free radical generating agent used in the present invention and Examples of the present invention will be described below, but the present invention is not limited thereto.

Synthesis example>4-CP-N,N'-di(ethoxycarbonylmethyl)aminophenyl)-2,6-di(trichloromethyl)
-3-) Synthesis of riazine [exemplified compound (I)] 4-[:P-N,N'-di(ethoxycarbonylmethyl)aminocobenzonitrile 4.35 g,)lichloroacetonitrile 13 g and aluminum triAide 0 .4
g were mixed and stirred, and hydrogen chloride gas was introduced for 1 hour at an internal temperature of 5°C. The internal temperature was returned to room temperature and stirring was continued for 20 hours. The reaction solution was extracted with methylene chloride, washed with water, and the treated methylene solution was distilled off under reduced pressure. The residue is acetonitic) and crystallized from IJ.
3.5 g of yellow crystals with a melting point of 109-111°C were obtained.

Uv spectrum (in tetrahydrofuran) λ+aax
386nm (log ε4.57>IR spectrum 1735cm-', 1545cm-', 1410c
m-', 1200 cm-', Example 1 After graining with a nylon brush, the following photosensitive solution was applied to a silicate-treated aluminum plate using a rotary coating machine.
It was dried at 00° C. for 3 minutes to form a photosensitive layer, thereby producing a photosensitive plate.

Photosensitive plates were prepared using the compound represented by the general formula (I) of the present invention, and for comparison, using a known compound. The compounds are shown in Table 1.

Photosensitive liquid Methyl methacrylate-methacrylic acid (molar scale 8/'15) copolymer (in methyl ethyl ketone, intrinsic viscosity 0.166 at 30°C) 62 g Dibenquelinuritol hexaacrylate 38 g Free radical generator (Table 1) i) 5g ethyl cellosolve 650d methylene chloride
3507 Exposure is performed using a vacuum printing frame device, and a step wedge (density step 0.15°, density step number 0) is placed on the photosensitive plate.
~15 stages) and a metal halide lamp (0.5kW).
), and after exposure, it was developed using a developer having the following formulation.

Developer solution Trisodium phosphate 25g Sodium phosphate 5g Butyl cellosolve
70g activator
2mf! water 1
Steps in the image obtained by 0100O development
Table 1) shows the exposure time when exposure was performed so that the number of solid wedges was the same. The shorter the exposure time, the higher the sensitivity.

As shown in Table 1, the compound represented by the general formula (I) according to the present invention has an existing trichloromethyl group-containing S
) IJ azine compound (experiment No., S, C compound)
It showed higher sensitivity compared to the above, and the intended effect of the present invention was fully recognized.

Example 2 The following photosensitive [I] was applied to the aluminum plate obtained in Example 1 to obtain a photosensitive printing plate I.

Dipentaerythritol hexaacrylate 30g Allyl methacrylate-methacrylic acid (molar ratio 85/15) copolymer 50g Free radical generator [Exemplary compound (3) E 2g Oil Blue #6
03 (Orient Chemical Industry Cleavage> 1.0g ethylene glycol monomethyl ether 500g methyl alcohol 150g methyl ethyl ketone
300gAs a comparative example, a photosensitive solution (I) was prepared by replacing only the free radical generating agent in the photosensitive solution I with the following compound, and the aluminum plate obtained in Example 1 was obtained! Coat this and make a photosensitive printing plate■
I got it.

A forced aging test (60° C., 5 days) was conducted on some of these photosensitive printing plates (1) and (2).

In order to see the decrease in sensitivity due to forced aging, samples subjected to forced aging and samples that were not subjected to forced aging were developed using α light for a certain period of time in the same manner as in Example 1, and the number of step wedges that appeared was compared. The results are shown in Table 2.

Example 3 The surface of an aluminum plate having a thickness of 0.301 m was grained using a nylon brush and a water suspension of 400 mesh bumiston, and then thoroughly washed with water. After etching by immersing in 10% sodium hydroxide at 70° C. for 60 seconds, washing with running water, neutralization washing with 20% HN◯3, and then washing with water. This was electrolytically blocked in a 1% nitric acid aqueous solution under the condition of Va=12.7V using a sinusoidal alternating waveform current at an anode specific electricity amount of 60 chrome/dm'. When the surface roughness was measured, it was 0.6 μ (indicated by JLA). Subsequently, 20%
One pole oxidation treatment was carried out for 2 minutes in H, SO, aqueous solution at a current density of 2 A/d m' so that the thickness became 2.7 g/m'. Thereafter, it was immersed in a 70°C sodium silicate 2.596 aqueous solution for 1 minute, washed with water, and dried.

A photosensitive solution having the composition shown below was coated on the aluminum plate thus treated so that the dry coating weight was 2 g/m' and dried at 100° C. for 2 minutes to obtain a photosensitive 10G plate. The photopolymerization initiators used and their amounts used in the photosensitive solution are shown in Table 3.

[Composition of photosensitive liquid]

・Photopolymerization initiator (shown in Table 3) 0.1 g
・Behenic acid 0.05 g
・Behenic acid amide 0. ．． 05g
- 7.5 g of methanol - 15 g of methyl ethyl ketone The obtained photosensitive lithographic printing plate was left at 60° C. for 5 days. The surface of the photosensitive lithographic printing plate thus obtained was observed using a microscope 1; the surface of the plate was rubbed with a filter paper, extracted with methanol, and UV measured.
Face+=f After hooking up and putting out the pestle, IR meeting 1, Yofute l
The presence/absence of j + false nails was checked to see if the presence or absence of ``Wayurot≦Kidashi9-'' is shown in Table 3.

When the swollen parts of the sample of Comparative Example J-1vJ-17 were analyzed, they were identified as each photopolymerization initiator.

Further, the photosensitive lithographic printing plates obtained in Examples 3-/~J-/& were left at temperatures of 25°C (in the laboratory) and 60°C for 5 days, respectively.

A Fuji PS step guide (ΔD=0.
15 (gray scale in which the transmission density changes discontinuously) was placed in close contact with the film, and exposure was performed from a distance of 10 cm using a 10 ampere high pressure mercury lamp.

Development was carried out using a developer described in Japanese Patent Publication No. 56-42860 to remove unexposed areas. 25℃ (in the laboratory) and 6
Each sample was exposed to a temperature condition of 0° C. for 5 days, and the exposure time at which the third row became completely solid on a gray scale was compared.

Examples in Table 8 where there was no crystal precipitation of the photopolymerization initiator &-
/ % J-/d samples had no difference in exposure time at which the third stage was completely exposed in the step guide. However, all of the samples of Comparative Example j-tJ-% required longer exposure times when left at 60°C. [Effects of the Invention] The photosensitive composition of the present invention has high sensitivity to photolysis. Contains a free radical generator, has high sensitivity, and is advantageous for producing photosensitive lithographic printing plates, printing proof plates, films for overhead projectors, films for second original drawings, films for photomasks, photoresists, etc. used. Furthermore, when the photosensitive composition of the present invention is used, a photosensitive lithographic printing plate with high sensitivity can be obtained even after storage under high temperature conditions.

Claims (1)

[Scope of Claims] A photosensitive composition containing a photosensitive s-triazine compound represented by the following general formula (I) and a compound having at least one ethylenically unsaturated double bond capable of addition polymerization. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] In the general formula [I], R_1 and R_2 may be the same or different, and are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, or a group represented by formula [II] or [III], ▲ there is a mathematical formula, chemical formula, table, etc. ▼ [II] ▲ there is a mathematical formula, chemical formula, table, etc. ▼ [III] or R_1, R_2 is the bond that it A heteroartic ring consisting of a nonmetallic atom may be formed together with the nitrogen atom. In formula [II], R_5 represents an alkyl group, substituted alkyl group, aryl group, or substituted aryl group, and in formula [III]
R_6 and R_7 may be the same or different and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R_3 and R_4 represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X and Y may be the same or different and represent a chlorine atom or a bromine atom. m and n represent 0, 1 or 2.