JPH10101719A - Photoinitiator, photopolymerizable composition, free radical generating method, photosensitive material for preparation of lithographic printing plate, and method for preparing lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide photopolymerizable compsn. which has improved resolution and sensitivity by incorporating a compd. having an ethylenically unsatd. bond, a specified photoinitiator, and a polymn. accelerator. SOLUTION: This photopolymerizable compsn. comprises: 100 pts.wt. compd. having at least one ethylenically unsatd. bond; 0.01 to 10 pts.wt. free radical generator, as a photoinitiator, selected from among organic peroxides, onium salts, triazine halides, iron-arene complex, bisimidazole, and titanocene compds.; dyes represented by formulae I to IV (wherein L1 to L5 represent methine; B1 to B4 represent a five-membered or six-membered arom. ring or hetero ring; X and Z represent O or S; W and Y represent O, S, or -N(R)-, provided that Y or W is -N(R)-; and R represents H or a monovalent substituent); and an amine compd. or a sulfur compd. as a polymerization accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photoinitiator using a novel sensitizing dye and a radical generator, a photopolymerizable composition, a radical generating method, a photosensitive material for preparing a lithographic printing plate, and preparation of a lithographic printing plate. For the method, more specifically, for example, ink,
Photosensitive printing plate, photoresist, direct plate material,
The present invention relates to a photoinitiator, a photopolymerizable composition, and a radical generation method for obtaining a cured product having good physical properties in fields such as a proof material for plate making, a hologram material, a sealant, an adhesive, and an optical molding material.

[0002]

2. Description of the Related Art In recent years, semiconductor lasers and YAG lasers have been
From the viewpoints of stability, small size, ease of maintenance, and the like, they are increasingly used as lasers for image recording. These lasers have been reduced in wavelength, and in particular, lasers (532 nm) using YAG (1064 nm) SHG have been put to practical use.

There is known a method of forming an image by performing imagewise exposure using a laser such as a semiconductor laser or a YAG laser to cause radical polymerization to cure an exposed portion, change physical properties with an unexposed portion, and develop to develop an image. ing.

In order to form an image, it is necessary to select a photosensitive material suitable for the wavelength of a laser light source, and a large number of radical generators have been studied as initiators for radical polymerization. Many of them have absorption only to the outside, and are usually used in combination with a sensitizing dye corresponding to the wavelength of the light source.

[0005] 488 nm argon laser or 532 nm
Various combinations of sensitizing dyes and radical generators (hereinafter, initiator systems) corresponding to the light source of the W-YAG laser described above are also known. For example, U.S. Pat. No. 2,850,
No. 445 describes certain photoreducing dyes as effective sensitizing dyes. In addition, Japanese Patent Publication No. 44-20189
No. 3 is a compound initiation system of a dye and an amine.
No. 77 discloses a system of biimidazole, a radical generator and a dye, JP-B-47-2528, and JP-A-54-15529.
No. 2 discloses a system of biimidazole and dialkylaminobenzylidene ketone, and JP-A-58-15503 discloses a system of a keto-substituted coumarin compound and an active halide.
No. 15102 proposes a system of a substituted triazine and a merocyanine dye, but all have problems such as low sensitivity and poor storage stability.

[0006]

SUMMARY OF THE INVENTION In order to solve the above problems, a first object of the present invention is to provide 488 nm or 532 nm.
An object of the present invention is to provide a photopolymerizable composition which can be written in the vicinity of m and can form an image having good resolution and sensitivity. A second object is to provide a photopolymerizable composition having good storage stability. A third object is to provide a radical generation method for generating radicals with high sensitivity by light near 488 nm or 532 nm. A fourth object is to provide a photosensitive material for preparing a lithographic printing plate having high photosensitivity in a wavelength region near 488 nm or 532 nm and having excellent storage stability, and a method for preparing a lithographic printing plate using the same. Is to do. A fifth object is to provide a highly sensitive photoinitiator.

[0007]

The above object of the present invention is achieved by the following means.

(1) A photoinitiator comprising a radical generator and a dye represented by the following general formula [1], [2], [3] or [4].

[0009]

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Wherein L ₁ , L ₂ , L ₃ , L ₄ , L ₅ represent a methine group, and B ₁ , B ₂ , B ₃ , B ₄ are a 5- or 6-membered aromatic ring or heterocyclic ring. Represents a ring. n represents 0 or 1. X, Z
Represents an oxygen atom or a sulfur atom, W and Y represent an oxygen atom or a sulfur atom or -N (R)-, and one of W and Y represents -N (R)-, and R represents H to 1 Represents a valent substituent. (2) The photoinitiator according to the above (1), which contains an amine compound or a sulfur compound as a polymerization accelerator.

(3) A photopolymer composition comprising a compound having an ethylenically unsaturated bond and the photoinitiator according to the above item (1) or (2).

(4) The radical generator is an organic peroxide,
Onium salts, halogenated triazines, iron arene complexes,
The photoinitiator according to the above (1) or (2), wherein the photoinitiator is selected from bisimidazole, titanocene compounds and organic peroxides.

(5) The radical generator is an organic peroxide,
Onium salts, halogenated triazines, iron arene complexes,
The photopolymerizable composition according to the above (3), which is selected from bisimidazole, titanocene compounds and organic peroxides.

(6) The photoinitiator according to the above (1) or (2), comprising a titanocene compound and a dye represented by the above general formula [2].

(7) The photopolymerizable composition according to the above (3), comprising a titanocene compound and a dye represented by the general formula [2].

(8) The photoinitiator according to the above (6), wherein the dye represented by the general formula [2] is the following general formula [2-1].

[0017]

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[Wherein L ₄ and L ₅ represent a methine group, m represents an integer of 1 to 4, and EDG represents an electron donating group. m
Is equal to or greater than 2, the EDGs may be the same or different, and may form a ring. X and Z each represent an oxygen atom or a sulfur atom; y, W and Y each represent an oxygen atom or a sulfur atom or -N (R)-; and one of W and Y represents -N (R)-; R represents H or a monovalent substituent. (9) The photopolymerizable composition according to the above (7), wherein the dye represented by the general formula [2] is the general formula [2-1].

(10) Any one of the above items (1) to (9)
Item 488 nm or 5
A radical generating method, which comprises exposing to a laser beam having a wavelength of 32 nm.

(11) In a photosensitive material for preparing a lithographic printing plate comprising a hydrophilic support and at least a photosensitive layer and a protective layer provided in this order, the photosensitive layer has at least one ethylenically unsaturated bond. A photosensitive material for preparing a lithographic printing plate, comprising a compound having the compound, a binder component, a photoinitiator or a photopolymerizable composition according to the above item (3) or (4).

(12) A lithographic printing plate-forming photosensitive material comprising a hydrophilic support and at least a photosensitive layer and a protective layer provided in this order, wherein the photosensitive layer has at least one ethylenically unsaturated bond. A method for preparing a lithographic printing plate using a photosensitive material for preparing a lithographic printing plate, characterized by containing a compound, a binder component, a photoinitiator or a photopolymerizable composition according to claim 3 or 4, wherein 4 in layer
A method for preparing a lithographic printing plate, comprising performing imagewise scanning exposure with a laser beam having a wavelength of 88 nm or 532 nm, and then eluting and removing unexposed portions of a protective layer and a photosensitive layer.

Hereinafter, the present invention will be described specifically.

First, the general formulas [1], [2], [3],
The sensitizing dyes represented by [4] and [2-1] will be described in detail. In the formula, B ₁ , B ₂ , B ₃ and B ₄ represent a 5- or 6-membered aromatic or hetero ring, and are represented by the following general formula [5].

[0024]

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[Wherein R ₁₇ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ₁₈ , —SR ₁₈ ,
NR ₁₉ R ₂₀ , R ₆ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an alkyl group or an aryl group, Y represents an oxygen atom or a sulfur atom, p represents 0 to 4, q Represents 0 to 3, and r represents 0 to 2. When each of p, q, and r is 2 or more, a plurality of R ₁₇ may be the same or different, and may form a ring.

The general formulas [1], [2], [3], [4],
In [2-1] and [5], R, R ₆ , R ₁₇ , R ₁₈ , R ₁₉ ,
The alkyl group represented by R ₂₀ is a chain or cyclic alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, cyclopropyl ,
Cyclopentyl and cyclohexyl) are preferable, and may have a substituent.

The aryl group represented by R, R ₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ is preferably an aryl group having 6 to 12 carbon atoms (eg, phenyl, naphthyl) and has a substituent. May be. The heterocyclic group represented by R is a 5- or 6-membered heterocyclic ring (for example, oxazolyl ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, thiophene ring, sulfolane ring, virazole ring, pyrrole ring , A chroman ring, and a coumarin ring), and may have a substituent.

L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group, which may be unsubstituted or substituted. When there are a plurality of substituents, they may be the same or different. And a ring may be formed.

Examples of the substituent which each of the above groups may have include, for example, a carboxylic acid group and a sulfonamide group having 1 to 12 carbon atoms (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide, n- Octanesulfonamide), a sulfamoyl group having 0 to 12 carbon atoms (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group having 2 to 12 carbon atoms (eg, methane Sulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group having 1 to 12 carbon atoms (eg, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), carbon number 1-12 Jo or cyclic alkyl group (e.g., methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl,
2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl), alkenyl having 2 to 12 carbon atoms (eg, vinyl, acryl),
An alkoxy group having 1 to 12 carbon atoms (for example, methoxy, ethoxy, butoxy), a halogen atom (for example, F, C
l, Br), an amino group having 0 to 12 carbon atoms (eg, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), an ester group having 2 to 12 carbon atoms (eg, methoxycarbonyl), 12 amide groups (eg, acetylamino, penzamide), a carbamoyl group having 1 to 12 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), and an aryl group having 6 to 12 carbon atoms (eg, phenyl, naphthyl) , 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), aryloxy groups having 6 to 10 carbon atoms (for example, phenoxy, 4- Carboxyphenoxy, 4-methylphenoxy, naphthoxy) Alkylthio group having 1 to 8 carbon atoms (e.g., methylthio, ethylthio, octylthio),
An arylthio group having 6 to 10 carbon atoms (eg, phenylthio, naphthylthio), an acyl group having 1 to 10 carbon atoms (eg, acetyl, benzoyl, propanoyl), and 1 carbon atom
To 10 sulfonyl groups (eg, methanesulfonyl, benzenesulfonyl), ureido groups having 1 to 10 carbon atoms (eg, ureido, methylureide), and urethane groups having 2 to 10 carbon atoms (eg, methoxycarbonylamino, ethoxycarbonylamino) ), Cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring) and the like. be able to.

Next, examples of the compound of the sensitizing dye of the present invention will be described.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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The sensitizing dye of the present invention can be synthesized according to a conventionally known method.

Synthesis Example 1 (Synthesis of Exemplified Dye D-3)

[0042]

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Compound (1) in 30 ml of ethanol
5 g and 4.0 g of the compound (2) were added and dissolved by heating, and then 0.5 g of triethylamine was added dropwise over 30 seconds. The mixture was stirred for 1 hour while heating under reflux. After cooling at room temperature, the precipitate was collected by filtration, washed with methanol, and dried to obtain 3.5 g of Exemplified Dye D-3. N. M. R. And the mass spectrum confirmed that it was the desired product.

Synthesis Example 2 (Synthesis of Exemplified Dye D-31)

[0045]

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7. Compound (1) in 30 ml of ethanol
24 g and 4.35 g of the compound (2) were added and dissolved by heating, and then 4.92 g of triethylamine was added dropwise in 30 seconds. The mixture was stirred for 1 hour while heating under reflux. After allowing to cool at room temperature, the precipitate is collected by filtration, washed with ethanol, and dried to give Exemplified Dye D.
4.8 g of -31 was obtained. N. M. R. And the mass spectrum confirmed that it was the desired product.

Next, the radical generator will be described. Specific examples of the radical generator include halides (α-haloacetophenones, trichloromethyltriazines, etc.), azo compounds, aromatic carbonyl compounds (benzoin esters, ketals, acetophenones, o-acyloxy imino ketones, Acylphosphine oxides), hexaarylbisimidazole compounds, peroxides and the like. As the peroxide, JP-A-5
Organic peroxides described in JP-A-9-1504 and JP-A-61-240807 can be used. Specific compounds include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, ketone peroxides such as 3,3,5-trimethylcyclohexanone peroxide, acetyl peroxide, propionyl peroxide, Isobutyl peroxide, octanoyl peroxide, 3,5,5
-Trimethylhexanoyl, decanoyl peroxide, uraroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-
Diacyl peroxides such as dichlorobenzoyl peroxide and acetylcyclohexanesulfonyl peroxide, tert-butyl hydroperoxide,
Hydrogen such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide Peroxides, di-
tert-butyl peroxide, tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy-3,3,3)
5-trimethylcyclohexane, n-butyl-4,4 '
Peroxy ketals such as -bis (tert-butylperoxy) butane, tert-butylperoxyacetate, tert-butylperoxyisobutyrate,
tert-butyl peroxyoctoate, tert-
Butylperoxypivalate, tert-butylperoxyneodecanate, tert-butylperoxy-
3,5,5-trimethylhexanoate, tert-butylperoxybenzoate, di-tert-butylperoxyphthalate, tert-butylperoxyisophthalate, tert-butylperoxylaurate,
Alkyl peresters such as 2,5-dimethyl-2,5-dibenzoylperoxyhexane, di-2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxycarbonate, di- n-propylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis- (4-tert-butylcyclohexyl)
Examples include peroxycarbonates such as peroxydicarbonate and water-soluble peroxides represented by peroxysuccinate.

Preferably, an organic peroxide having the following structure can be used.

[0049]

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As the metal arene complex which can be used in the present invention, the following titanocene compounds and iron arene complexes can be used. Examples of the iron arene complex include those having the following structures.

[0051]

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Preferably,

[0053]

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Is used.

The titanocene compound that can be preferably used in the present invention is not particularly limited, but is appropriately selected from various titanocene compounds described in, for example, JP-A-59-152396 and JP-A-61-151197. Can be used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclopentadienyl-Ti-bis-2,3,
5,6-tetrafluorophenyl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, di-cyclopentadienyl-Ti-bis-2,6-
Di-fluorophenyl, di-cyclopentadienyl-T
i-bis-2,4-di-fluorophenyl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,
6-pentafluorophenyl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, di-methylcyclopentadienyl-Ti-
Bis-2,6-difluorophenyl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyrrol-1-yl) -phenyl (hereinafter abbreviated as Ti-1) and the like can be mentioned. Can be. Particularly preferably, Ti-1
It is.

In the present invention, the following onium salts can be used. Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, a stannonium salt and the like. JP-B-55-39162, JP-A-5
No. 9-14023 and "Macromoleculars (Ma
Chromolecules), vol. 10, p. 1307 (1977). As the iodonium salt, a diaryliodonium salt can be preferably used. For example,
Diphenyliodonium salt, ditolyliodonium salt,
Phenyl (p-methoxyphenyl) iodonium salt, bis (m-nitrophenyl) iodonium salt, bis (p-
tert-butylphenyl) iodonium salt, bis (p
Chlorides such as -cyanophenyl) iodonium salt, bromide, boron tetrafluoride, boron hexafluoride, phosphorus hexafluoride, arsenic hexafluoride, anthmon hexafluoride, perchlorate, benzenesulfonic acid Salts, p-toluenesulfonate, p-trifluoromethylbenzenesulfonate,
n-butyltriphenyl boron salt and the like.

In the present invention, a 2,4,5-triarylimidazole dimer can be used. JP-A-55-1
It is preferable to use those having the following structure described in Japanese Patent No. 27550 and Japanese Patent Application Laid-Open No. 60-202037.

[0059]

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The amount of the radical generator of the present invention varies depending on the type and the use form of the radical generator, but is 0.01 to 10 parts by weight based on 100 parts by weight of the compound having at least one ethylenically unsaturated bond. Is preferred. As the support, paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component), resin film or sheet, plastic film or sheet formed by laminating two or more layers of resin, various polymer materials, metal Examples thereof include a film or sheet obtained by laminating a resin layer on paper or the like made of ceramic, wood pulp, cellulose pulp, sulfite pulp, or the like. Examples of the resin constituting such a resin film or sheet include acrylic resins such as acrylates and methacrylates, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate and polyarylate, and polychlorinated resins. Polyolefin resins such as vinyl, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polypropylene, and polystyrene; polyamide resins such as nylon and aromatic polyamide; polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and polyparaban Examples include acids, phenoxy resins, epoxy resins, urethane resins, melamine resins, alkyd resins, phenolic resins, fluororesins, and silicone resins. It is.

When the present invention is used for preparing a lithographic printing plate, the support on which the photosensitive layer is provided may be aluminum,
Zinc, copper, steel and other metal plates, as well as chromium, zinc, copper, nickel, aluminum, iron and other metal plates, paper, plastic films and glass plates, resin-coated paper, aluminum, etc. Paper with metal foil,
Examples include a plastic film subjected to a hydrophilic treatment.
Of these, an aluminum plate is preferred. As the support of the present invention, it is more preferable to use an aluminum plate that has been subjected to a surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment. Known methods can be used for these treatments.

Examples of the graining method include a mechanical method and a method of etching by electrolysis.

Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material and the like. Preferred is a method by electrolytic etching.

The electrolytic etching is performed in a bath of an acid such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid or a mixture of two or more kinds.
After the graining treatment, if necessary, a desmut treatment is performed with an aqueous solution of an alkali or an acid to neutralize and wash with water.

In the anodic oxidation treatment, sulfuric acid,
Electrolysis is performed using a solution containing one or more of chromic acid, oxalic acid, phosphoric acid, malonic acid, and the like, using an aluminum plate as an anode. The amount of anodic oxide film formed is 1-50mg
/ Dm ² is suitable, and preferably 10 to 40 mg / d
m ² . The amount of the anodic oxide film can be determined by, for example, immersing an aluminum plate in a chromic phosphate solution to dissolve the oxide film, and measuring the change in weight before and after the film is dissolved.

Examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment and the like. In addition, the aluminum plate support may be subjected to an undercoating treatment with a water-soluble polymer compound or an aqueous solution of a metal salt such as zircon fluoride.

The thickness of the support is usually preferably from 3 to 1000 μm, more preferably from 8 to 300 μm.

As the binder resin used for the photosensitive layer, various known polymers can be used. Details of specific binders are described in U.S. Pat. No. 4,072,52.
No. 7, and more preferably described in JP-A-54-9.
No. 8613, monomers having an aromatic hydroxyl group, such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p- Copolymers of hydroxystyrene, o-, m- or p-hydroxyphenyl methacrylate with other monomers, U.S. Pat.
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate as described in U.S. Pat. No. 23,276; natural resins such as shellac, rosin; polyvinyl alcohol;
No. 57, a linear polyurethane resin as described in U.S. Pat. No. 3,660,097, a phthalated resin of polyvinyl alcohol, condensed from bisphenol A and epichlorohydrin. Cellulose resins such as epoxy resin, cellulose acetate, and cellulose acetate phthalate are exemplified.

As the binder resin, one or more of the above resins can be used in combination. Among them, vinyl chloride, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, styrene-acrylonitrile, polyvinyl acetal, nitrocellulose,
Solvent-soluble polymers such as ethyl cellulose are preferred.

These binders may be used not only by dissolving one kind or two or more kinds in an organic solvent, but also in the form of a latex dispersion. The amount of the binder used varies depending on the purpose of the image forming material of the present invention and depends on whether it has a single-layer structure or a multi-layer structure.
1.0 to ²⁰ g per m ² is preferred.

Next, the compound having an ethylenically unsaturated bond will be described in detail. The compound having an ethylenically unsaturated double bond of the present invention is defined as an ethylenically unsaturated double bond that undergoes addition polymerization and cures by the action of a photoinitiator when the photopolymerizable composition is irradiated with actinic rays. A compound having a heavy bond, for example, a monomer having the double bond, or
It is a polymer having an ethylenically unsaturated double bond in the side chain or main chain. In the present invention, the meaning of the monomer is a concept corresponding to a so-called polymer substance, and therefore includes not only monomers in a narrow sense but also dimers, trimers, and oligomers. is there.

As the polymerizable compound, known monomers can be used without any particular limitation. Specific monomers include, for example, 2-ethylhexyl acrylate,
Monofunctional acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate and derivatives thereof or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc., polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A
Diacrylates, bifunctional acrylates such as diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate and derivatives thereof, or acrylates of these methacrylates, itaconates,
Compounds substituted with crotonate, maleate, etc., or polyfunctional acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pyrogallol triacrylate and derivatives thereof, or methacrylates of these acrylates , Itaconate, crotonate, maleate and the like.

A so-called prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerizability can also be suitably used. In addition, JP-A-58-212994, 61
No.-6649, No.62-46888, No.62-485
No. 89, No. 62-173295, No. 62-18709
No. 2, 63-67189, JP-A-1-2444891
And the like.
1290 Chemical Products ", Chemical Daily, p. 286 ~
p. 294, “UV / EB curing handbook (raw material)”, Polymer Publishing Association, p. The compounds described in 11 to 65 and the like can also be suitably used in the present invention.

Of these, compounds having two or more acrylic or methacrylic groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred. In the present invention, one or more of these monomers or prepolymers can be used as a mixture. In the present invention, the compound having an ethylenically unsaturated group is preferably 20 to 80 parts by weight, more preferably 30 to 7 parts by weight in the photosensitive layer.
0 parts by weight are contained.

In the photosensitive layer of the present invention, other components such as a sensitizer, a polymerization accelerator, a thermal polymerization inhibitor, a hot-melt compound, an oxygen scavenger, and a plasticizer are used as long as the purpose is not impaired. Inclusion is optional.

Examples of sensitizers include triazine compounds described in JP-A-64-13140 and JP-A-64-13141.
Onium salts, aromatic halonium salts, organic peroxides described in JP-A-64-13143, and bisimidazoles described in JP-B-45-37377 and U.S. Pat. No. 3,652,275. And thiols. The sensitizer is added in an amount of 10 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder.
About part by weight is added.

As the polymerization accelerator, a polymerization accelerator represented by an amine compound or a sulfur compound (thiol, disulfide, etc.), a chain transfer catalyst, or the like can be added.

Specific examples of the polymerization accelerator and the chain transfer catalyst that can be added to the photopolymerizable composition of the present invention include, for example, N-
Amines such as phenylglycine, triethanolamine, N, N-diethylaniline and the like, U.S. Pat.
Thiols described in No. 312 and JP-A-64-13144, disulfides described in JP-A-2-29161, U.S. Pat. No. 3,558,322 and JP-A-64-1704.
And thiones described in JP-A-2-291560 and N-alkoxypyridinethiones. Particularly preferably, the amine compound is N, N-diethylaniline, and the sulfur compound is 2-mercaptobenzothiazole.

As the thermal polymerization inhibitor, quinone compounds, phenol compounds and the like are preferably used. For example, hydroquinone, pyrogallol, p-methoxyphenol,
Catechol, β-naphthol, 2,6-di-t-butyl-p-cresol and the like.

With respect to 100 parts by weight of the total amount of the polymerizable compound having an ethylenically unsaturated bond and the binder, 1
0 parts by weight or less, preferably about 0.01 to 5 parts by weight is added.

The oxygen quencher is preferably an N, N dialkylaniline derivative. For example, US Pat.
Compounds described in column 2, line 58 to column 12, line 35 of No. 2,541 can be mentioned.

Examples of the plasticizer include phthalates, trimellites, adipic esters, other saturated or unsaturated carboxylic esters, citrates, epoxidized soybean oil, epoxidized linseed oil, epoxy Epoxy stearates, orthophosphates,
Examples include phosphites and glycol esters. As the heat-fusible compound, a compound that is solid at room temperature and reversibly liquid when heated is used.

Examples of the heat-fusible substance include alcohols such as terpineol, menthol, 1,4-cyclohexanediol and phenol, amides such as acetamide and benzamide, esters such as coumarin and benzyl cinnamate, diphenyl ether and crown. Ethers such as ethers, ketones such as camphor and p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, and palmitic acid Monomolecular compounds represented by higher fatty acid esters such as cetyl, higher fatty acid amides such as stearamide, higher amines such as behenylamine, beeswax, candelilla wax, paraffin wax, ester wax Wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax, etc., ester gum, rosin maleic acid resin, rosin derivative such as rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, Terpene hydrocarbon resin, cyclopentadiene resin, polyolefin resin,
Polycaprolactone resin, polyethylene glycol,
Examples thereof include high molecular compounds represented by polyolefin oxides such as polypropylene glycol.

If necessary, an antioxidant may be added to the photosensitive layer.
A filler, an antistatic agent and the like may be added. Examples of the antioxidant include chroman compounds, Claman compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds, and the like.
No. 82785, No. 60-130735, No. 61-15
No. 9644, JP-A-1-127387, "11290
Chemical Products ", Chemical Daily, p. Compounds described in JP-A Nos. 862 to 868 and known compounds which improve durability of photographs and other image recording materials can be given. Examples of the filler include inorganic fine particles and organic resin particles.

Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, zinc oxide, barium sulfate, talc, clay, kaolin, acid clay, activated clay, and alumina. Resin particles such as guanamine resin particles, acrylic resin particles, and silicone resin particles; as antistatic agents, cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, conductive fine particles "11290 Chemical Products", Chemical Daily, p. 87
5-p. 876 and the like can also be suitably used.

In the present invention, the photosensitive layer may be formed as a single layer, or may be formed as two or more layers.
In the case of comprising a plurality of layers, the layers may be composed of photosensitive layers having different compositions, and in this case, a photosensitive layer containing no colorant may be included. In the present invention, the thickness of the photosensitive layer is preferably 0.2 to 10 μm, more preferably 0.5 to 10 μm.
５5 μm. The photosensitive layer is formed by dispersing or dissolving the constituents in a solvent to prepare a coating solution, and directly applying the coating solution on the intermediate layer and drying or coating or drying the coating solution on a cover sheet. You.

Solvents used in the above coating method include water, alcohols (eg, ethanol, propanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, For example, acetone, methyl ethyl ketone), ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane), chlorine solvents (eg, chloroform, trichloroethylene), amide solvents (eg, dimethylformamide, N-methyl) Pyrrolidone), dimethyl sulfoxide and the like. For the coating, a conventionally known gravure roll can be employed such as a face-to-face coating method, an extrusion coating method, a wire bar coating method, a roll coating method, or the like.

[0088]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 [Preparation of Support] 5% of a 0.24 mm thick aluminum plate (material: 1050, tempered H16) kept at 65 ° C.
It was immersed in an aqueous solution of sodium hydroxide, degreased for 1 minute, and then washed with water. This degreased aluminum plate is
It was immersed in a 10% hydrochloric acid aqueous solution maintained at 5 ° C. for 1 minute to neutralize, and then washed with water. Then, this aluminum plate was placed on 1.
In an aqueous solution of 0 parts by weight of hydrochloric acid, electrolytic surface roughening was performed for 60 seconds with an alternating current at a temperature of 25 ° C. and a current density of 100 A / dm ² , and then 10% in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. A second desmutting process was performed. The surface-roughened aluminum plate subjected to desmut treatment is placed in a 40% phosphoric acid solution at a temperature of 30 ° C. and a current density of 4 A / dm.
Anodizing treatment was performed for 6 minutes under the conditions of ² and sealing treatment was performed with sodium silicate to prepare a support.

[Preparation of Photosensitive Layer] A photosensitive layer having the following formulation was coated on the above support so as to have a coating weight of about 1.3 g / m ² . After coating, the photosensitive layer was dried at 80 ° C. for 3 minutes.

Dye (D-1) 0.20 parts by weight Radical generator (BTTB) 0.40 parts by weight M450 (pentaerythritol tetraacrylate: manufactured by Toagosei Co., Ltd.) 4.47 parts by weight Fluorinated surfactant (MegaFac F179: manufactured by Dainippon Ink) 0.10 parts by weight Polymerization inhibitor (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.) 0.02 parts by weight Methyl ethyl ketone 45 parts by weight Propylene glycol monomethyl ether 45 parts by weight Copper phthalocyanine pigment (0 0.58 parts by weight [Formulation of protective layer] Approximately 1.3 g of a protective layer having the following formulation.
/ M ² . After the application, it was dried at 80 ° C. for 3 minutes.

Polyvinyl alcohol (Gohsenol GL-05) 9.9 parts by weight Fluorinated surfactant (MegaFac F120, manufactured by Dainippon Ink) 0.1 part by weight Water 90.0 parts by weight Examples 2 to 20 Examples Examples 2 to 20 were prepared by changing the dye 1 as shown in Table 1. The amount of addition in Table 1 is a value obtained by converting the amount of addition to the weight of the entire photosensitive material after drying into weight%. The titanocene compound Ti-1 used was CGI784 manufactured by Ciba-Geigy Japan.

Example 21 A photosensitive layer was prepared in the same manner as in Example 1, except that the following formulation was used.

Dye (D-31) 0.20 parts by weight Radical generator (BTTB) 0.40 parts by weight M450 (pentaerythritol tetraacrylate: manufactured by Toagosei Co., Ltd.) 4.47 parts by weight Polymerization accelerator 1 ( Iron arene complex) 0.45 parts by weight Polymerization accelerator 2 (1,3,5-pentamethylaniline) 0.083 parts by weight Fluorinated surfactant (MegaFac F179: manufactured by Dainippon Ink Co., Ltd.) 0.10 parts by weight Polymerization inhibitor (SUMILIZER GS: manufactured by Sumitomo Chemical Co., Ltd.) 0.02 parts by weight Methyl ethyl ketone 45 parts by weight Propylene glycol monomethyl ether 45 parts by weight Copper phthalocyanine pigment (0.3 μm) 0.58 parts by weight Examples 22 to 34 Example 21 The same as Example 21 except that the dye, radical generator, polymerization accelerator 1 and polymerization accelerator 2 were changed as shown in the following table To, the photosensitive resin composition was prepared as shown in Tables 1 and 2.

[0095]

[Table 1]

[0096]

Embedded image

[0097]

[Table 2]

The light-cured lithographic printing plate thus prepared was subjected to a light room printer [Dainippon Screen Co., Ltd.]
After exposure using P-627-HA], the photosensitive layer in the unexposed area was eluted by immersion in the following developer at 30 ° C. for 30 seconds, washed with water and dried to form an image. .

(Developer Solution Formulation) Potassium A silicate (manufactured by Nippon Chemical Industries: (SiO ₂ = 26%, K ₂ O = 13.5%)) 400 parts by weight Potassium hydroxide (50% aqueous solution) 195 parts by weight N-phenylethanol Amine 6 parts by weight Propylene glycol 50 parts by weight pt-butylbenzoic acid 150 parts by weight Potassium sulfite 300 parts by weight Nonionic surfactant (Emulgen 147: manufactured by Kao Corporation) 5 parts by weight Gluconic acid (50% aqueous solution) 100 parts by weight Tri Ethanolamine 25 parts by weight Water 11500 parts by weight Adjusted to pH = 12.5 The obtained lithographic printing plate was evaluated for the following properties.

(Evaluation method) [Evaluation of dirt] An image was formed by an Ugra plate control wedge PCW82 (manufactured by Mika Denshi) at an exposure amount such that the continuous tone wedge had three steps, and was printed by a printing machine (Heidel GTO). , Coated paper, printing ink (manufactured by Toyo Ink Mfg. Co., Ltd .: Hiplus M Red) and fountain solution (manufactured by Konica Co., Ltd .: 2.5% aqueous solution of SEU-3), and the initial printing stage (1000 sheets) (At about the time), the stain on the non-image area of the printed matter was visually evaluated on a four-point scale. ：: There was no stain ○: There was slight stain △: There was no stain on the entire surface as much as ×, but there was a stain that was practically problematic X: Dirt was found on the entire surface. ◎ and ○ are practically usable.

[Sensitivity evaluation] The prepared lithographic printing original plate was
Wrap around the drum so that the protective layer side is the light source side, and rotate the drum to make a 100 mW harmonic YAG laser (DP
Y315M, LD pumped SHG, YAG laser (532
nm): manufactured by ADLAS). The laser light intensity is considered to have a Gaussian distribution, and the light intensity (μW) where the line width corresponding to 1 / e 2 of the laser light intensity is equal to the line width of the formed image is set at a constant rotation speed of the drum. /
cm ² ), and the energy value was determined from the product of the irradiation time and the product. 488 nm was exposed using an argon laser.

[Evaluation of storage stability] The plate prepared from each sample before the exposure and development treatment was subjected to forced deterioration at 55 ° C./20% RH for 3 days, and then exposed and developed in the same manner as described above.
The developability after storage was evaluated based on the removability of the non-image area.
Printing evaluation was also performed in the same manner as described above.

Table 3 summarizes the obtained results.

[0104]

[Table 3]

From the results shown in Table 3, the sample of the present invention was 488 n
It can be seen that the optical writing at a wavelength of about m or 532 nm has high sensitivity, is less contaminated, and has good storage stability.

[0106]

According to the present invention, 488 nm or 532
It is possible to provide a photopolymerizable composition that can be written with light in the vicinity of nm, and that can form an image with good resolution and sensitivity. The material was made.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // G03F 7/028 G03F 7/028

Claims (12)

[Claims] 1. A radical generator and the following general formula [1]:
A photoinitiator comprising a dye represented by [2], [3] or [4]. Embedded image [Wherein L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group,
B ₁ , B ₂ , B ₃ and B ₄ represent a 5- or 6-membered aromatic ring or hetero ring. n represents 0 or 1. X and Z each represent an oxygen atom or a sulfur atom; W and Y each represent an oxygen atom or a sulfur atom or -N (R)-; and one of W and Y is-
N (R)-, wherein R represents an H to monovalent substituent. ] 2. The photoinitiator according to claim 1, wherein the photoinitiator contains an amine compound or a sulfur compound as a polymerization accelerator. 3. A photopolymer composition comprising a compound having an ethylenically unsaturated bond and the photoinitiator according to claim 1. 4. The method according to claim 1, wherein the radical generator is selected from organic peroxides, onium salts, halogenated triazines, iron arene complexes, bisimidazoles, titanocene compounds, and organic peroxides. Photoinitiator. 5. The photopolymerization according to claim 3, wherein the radical generator is selected from organic peroxides, onium salts, triazine halides, iron arene complexes, bisimidazoles, titanocene compounds, and organic peroxides. Composition. 6. A titanocene compound and the above general formula [2]
The photoinitiator according to claim 1, further comprising a dye represented by the following formula: 7. The photopolymerizable composition according to claim 3, comprising a titanocene compound and a dye represented by the general formula [2]. 8. The photoinitiator according to claim 6, wherein the dye represented by the general formula [2] is the following general formula [2-1]. Embedded image [Wherein L ₄ and L ₅ represent a methine group, m represents an integer of 1 to 4, and EDG represents an electron donating group. When m is 2 or more, the EDGs may be the same or different, and may form a ring. X and Z each represent an oxygen atom or a sulfur atom; y, W and Y represent an oxygen atom or a sulfur atom or -N
(R)-, and one of W and Y is -N (R)
And R represents H or a monovalent substituent. ] 9. The photopolymerizable composition according to claim 7, wherein the dye represented by the general formula [2] is the general formula [2-1]. 10. A radical generation method, comprising exposing the photoinitiator or the photopolymerizable composition according to claim 1 to laser light having a wavelength of 488 nm or 532 nm. 11. A lithographic printing plate-forming photosensitive material comprising at least a photosensitive layer and a protective layer provided in this order on a hydrophilic support, wherein the photosensitive layer has at least one ethylenically unsaturated bond. A photosensitive material for preparing a lithographic printing plate, comprising a compound, a binder component, a photoinitiator or a photopolymerizable composition according to claim 3. 12. A lithographic printing plate-forming photosensitive material comprising at least a photosensitive layer and a protective layer provided in this order on a hydrophilic support, wherein the photosensitive layer has at least one ethylenically unsaturated bond. A method for preparing a lithographic printing plate using a photosensitive material for preparing a lithographic printing plate, characterized by containing a binder component, a photoinitiator or a photopolymerizable composition according to claim 3. 488n
A method for preparing a lithographic printing plate, comprising performing imagewise scanning exposure with a laser beam having a wavelength of m or 532 nm, and then eluting and removing unexposed portions of a protective layer and a photosensitive layer.