JP2005309046A - Photoinitiator composition, photosensitive lithographic printing plate material, and method for manufacturing lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a good photosensitive lithographic printing plate material having excellent sensitivity and printing durability, a method for manufacturing a photosensitive lithographic printing plate, and a photoinitiator composition for manufacturing the photosensitive lithographic printing plate material. <P>SOLUTION: The photoinitiator composition contains a photoinitiator and at least one of the sensitizing dyes represented by formula (1) wherein R<SB>1</SB>-R<SB>4</SB>each represents H or a substituent; and Z represents a group of atoms forming a carbon ring or a heterocycle in combination with adjacent carbon atoms. The photosensitive lithographic printing plate material and the method for manufacturing a photosensitive lithographic printing plate are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photopolymerization initiator composition, a photosensitive lithographic printing plate material and a method for producing a lithographic printing plate, and more specifically, a photopolymerization initiator composition having high sensitivity and excellent printing durability, and photosensitivity. The present invention relates to a lithographic printing plate material and a method for producing a photosensitive lithographic printing plate.

  Conventionally, there has been known a photosensitive lithographic printing plate material in which a photopolymerizable layer and a protective layer are laminated on a support subjected to a hydrophilic surface treatment. In particular, in recent years, in order to quickly obtain a high-resolution lithographic printing plate material, and for the purpose of filmlessness, digital exposure based on image information using a laser is performed, and this is developed to produce a lithographic printing plate. The manufacturing method has been generalized.

  For example, a light source is modulated by an output signal from an electronic plate-making system or an image processing system or an image signal transmitted through a communication line, etc., and the photosensitive lithographic printing plate material is directly scanned and exposed to a lithographic plate. Systems for forming printing plates are known.

  The photopolymerizable layer generally contains an acrylic monomer, an alkali-soluble resin, a photopolymerizable initiator, and, if necessary (especially when laser writing), a sensitizing dye to match the wavelength. It is known.

  A long-wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) is used as a light source for exposing and making a photopolymerization type photosensitive lithographic printing material. Furthermore, in recent years, for example, semiconductor lasers that can continuously oscillate in the 350 to 450 nm region using InGaN-based or ZnSe-based materials have been put into practical use. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because a semiconductor laser can be manufactured at a low cost because of its structure. Furthermore, there is a possibility that a photosensitive lithographic printing plate material having a shorter photosensitive area capable of working under a brighter safe light can be used as compared with a system using a conventional FD-YAG or Ar laser. .

From these facts, it has been strongly desired in the present industrial field to obtain a photosensitive lithographic printing plate material that is exposed and subjected to plate making using a relatively short wave semiconductor laser of 350 nm to 450 nm. For example, a ketocoumarin-based compound has been described as a sensitizing dye added to a photopolymerizable composition having high photosensitivity to a short-wave semiconductor laser region of 350 nm to 450 nm (see, for example, Patent Document 1). However, there is a problem that it is difficult to obtain a high sensitivity, and the printing durability is not sufficient.
JP 2003-21901 A (Example)

  An object of the present invention is to provide a photosensitive lithographic printing plate material excellent in sensitivity and printing durability, a method for producing the photosensitive lithographic printing plate, and a photopolymerization initiator composition for producing the photosensitive lithographic printing plate material Is to provide.

  The above object of the present invention can be achieved by the following configuration.

(Claim 1)
A photopolymerization initiator composition comprising at least one of a photopolymerization initiator and a sensitizing dye represented by the following general formula (1).

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represents a hydrogen atom or a substituent, and Z represents an atomic group which forms a carbocycle or a heterocycle with an adjacent carbon atom. ]
(Claim 2)
The photopolymerization initiator composition according to claim 1, wherein the substituent represented by R ₃ in the general formula (1) is a substituted amino group.

(Claim 3)
The photopolymerization initiator composition according to claim 1 or 2, wherein the photopolymerization initiator is an iron arene complex compound or a titanocene compound.

(Claim 4)
The photopolymerization initiator composition according to any one of claims 1 to 3, wherein an addition-polymerizable ethylenic double bond-containing monomer, a polymer binder having an acryloyl group or a methacryloyl group, and a support are provided. A photosensitive lithographic printing plate material comprising a photopolymerizable photosensitive layer containing a product.

(Claim 5)
A method for producing a lithographic printing plate, comprising producing the photosensitive lithographic printing plate material according to claim 4 by scanning and recording imagewise with a laser light source having a wavelength of 350 to 450 nm.

  According to the present invention, a photosensitive lithographic printing plate material having improved sensitivity and printing durability was obtained.

The present invention will be described in more detail. First, the dye represented by the general formula (1) will be described. In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and the substituent includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, Allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heteroaryl group (eg, furyl group, thienyl group, pyridyl group, pyridadyl group, pyrimidyl group) Group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazole Group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy) Group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.) , Alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, , Phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyl) Oxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, Dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl) , Ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, Acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group) Propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonyl Amino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexyl) Aminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido) Group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridyl Aminoureido groups, etc.), sulfinyl groups (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2 -Pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethyl Silamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trimethyl group) Fluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group) Etc.). These substituents may be further substituted with the above substituents. Further, a plurality of adjacent groups out of R ₁ , R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring.

Of these, the group represented by R ₃ is preferably a substituted amino group. Examples of the group that substitutes the amino group include a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, and heterocyclic group. These substituents may be combined with the adjacent groups represented by R ₂ and / or R ₄ to form a ring.

Z represents a group that forms a carbocycle or a heterocycle with adjacent carbon atoms, specifically a methylene group, a methine group, a carbonyl group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, a substituted or unsubstituted imino group. A group in which a plurality of arbitrary divalent groups such as a group are bonded to form a ring structure. Examples of the substituent of the substituted imino group include the same groups as the substituents represented by R _{1 to} R ₄ described above. These divalent groups may have a substituent, and examples of the substituent include the same groups as those described above.

  The carbocyclic or heterocyclic ring formed by Z and the adjacent carbon atom is preferably a 5-membered ring or a 6-membered ring.

  Hereinafter, although the specific example of a compound represented by General formula (1) is given, this invention is not limited to these.

  These compounds represented by the general formula (1) can be easily synthesized by a conventionally known method. For example, for Compound D04, Journal of Heterocyclic Chemistry; vol. 37 (2), 2000, 395-399.

  The content of the sensitizing dye represented by the general formula (1) of the present invention is usually 0.05 to 30 parts by mass, preferably 0 with respect to 100 parts by mass of the compound having at least one ethylenically unsaturated bond. .1 to 20 parts by mass. Furthermore, the sensitizing dye of the present invention can be suitably used alone or in combination of two or more.

  As photopolymerization initiators, preferably halides (α-haloacetophenones, trichloromethyltriazines, etc.), azo compounds, aromatic carbonyl compounds (benzoin esters, ketals, acetophenones, o-acyloxyiminoketones, acyls) Phosphine oxides), hexaarylbisimidazole compounds, peroxides, iron arene complexes, titanocene compounds, and the like.

  As the peroxide, organic peroxides described in JP-A-59-1504 and JP-A-61-240807 can be used.

  Specific compounds include ketones such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and acetyl peroxide. , Propionyl peroxide, isobutyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl, decanoyl peroxide, uraroyl peroxide, benzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2 , 4-Dichlorobenzoyl peroxide, diacetyl such as acetylcyclohexanesulfonyl peroxide -Oxides, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3 -Hydroperoxides such as tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl- Peroxyketals such as 2,5-di (tert-butyl) peroxy-3,3,5-trimethylcyclohexane and n-butyl-4,4′-bis (tert-butylperoxy) butane, tert-butylper Oxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxyoctoate, tert-butylperoxypivalate, tert-butylperoxyneodecanate, tert-butylperoxy-3,5,5-trimethylhexanoate , Alkyl such as tert-butyl peroxybenzoate di-tert-butyl peroxyphthalate, tert-butyl peroxyisophthalate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane Peresters, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxycarbonate, di-n-propyl peroxydicarbonate, dimethoxyisopro Peroxycarbonates such as pyrperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, Water-soluble peroxides typified by acid peroxide are listed.

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

  Examples of the iron arene complex that can be preferably used in the present invention include the following structures.

The titanocene compound that can be preferably used in the present invention is not particularly limited, and is appropriately selected from various titanocene compounds described in, for example, JP-A Nos. 59-152396 and 61-151197. be able to. More specifically, dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis- (2,3,4,5,6-penta Fluoro-phenyl), dicyclopentadienyl-Ti-bis- (2,3,5,6-tetrafluoro-phenyl), dicyclopentadienyl-Ti-bis- (2,4,6-trifluoro- Phenyl), dicyclopentadienyl-Ti-bis- (2,6-difluoro-phenyl), dicyclopentadienyl-Ti-bis- (2,4-difluoro-phenyl), dimethylpentadienyl-Ti- Bis- (2,3,4,5,6-pentafluoro-phenyl), dimethylpentadienyl-Ti-bis- (2,3,5,6-tetrafluoro-phenyl), dimethyl Pentadienyl -Ti- bis - (2,6-difluoro-phenyl) -, dicyclopentadienyl -Ti- bis - (2,6-difluoro-3-pyrryl-phenyl) - (hereinafter, referred to as Ti-1)
Among these, Ti-1 having the following structure is particularly preferable.

  In the present invention, the following onium salts can be preferably used.

  Examples of onium salts include iodonium salts, sulfonium salts, phosphonium salts, stannonium salts, and the like.

  Various onium compounds described in JP-B-55-39162, JP-A-59-14023 and “Macromolecules, Vol. 10, page 1307 (1977)” can be used. As the iodonium salt, a diaryl iodonium salt can be preferably used.

  Examples of the onium salt include diphenyliodonium salt, ditolyliodonium salt, phenyl (p-methoxyphenyl) iodonium salt, bis (m-nitrophenyl) iodonium salt, bis (p-tert-butylphenyl) iodonium salt, bis ( p-cyanophenyl) iodonium salts and other chlorides, bromides, boron tetrafluoride salts, boron hexafluoride salts, phosphorus hexafluoride salts, arsenic hexafluoride salts, anthromonic hexamonide salts, perchlorates, benzenesulfones Acid salts, p-toluenesulfonic acid salts, p-trifluoromethylbenzenesulfonic acid salts, n-butyltriphenylboron salts, and the like are also included.

  In the present invention, 2,4,5-triarylimidazole dimer can be preferably used.

  The following structures described in JP-A Nos. 55-127550 and 60-202437 are preferably used.

  Although the compounding quantity of these photoinitiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 polymerization parts of compound which can be addition-polymerized or bridge | crosslinked. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.

  The compound containing an ethylenic double bond capable of addition polymerization according to the present invention includes an ethylenic double bond capable of addition polymerization in a molecule generally used for general radical polymerizable monomers and UV curable resins. Polyfunctional monomers having a plurality of bonds and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate , Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypentylate neopentyl glycol, Diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1, Ε-caprolactone adduct of 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Difunctional acrylic acid esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of hexaacrylate, pyrogallol triacrylate Polyfunctional acrylic acid esters such as propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester polymers obtained by introducing (meth) acrylic acid into polyesters obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol and 1,2,6-hexanetriol. Relates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylate in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resin Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  The photosensitive composition of the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoate. Addition-polymerizable oligomers and prepolymers having monomers such as acid esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.

  Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl 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, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, the present invention uses a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule. Is preferred.

  Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'- Tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol N, N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) ) -1,2-propanediol and the like, but not limited thereto.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto. Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, and the like.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

Specific examples of reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. Shown in
M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-1-methylethyl ) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanate) Natomethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) An acrylate or an alkyl acrylate described in JP-A-1-105238 and JP-A-2-127404 can be used.

  The photosensitive lithographic printing plate material used in the present invention contains a polymer binder in the photopolymerizable photosensitive layer.

  Examples of the polymer binder of the present invention include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, and other natural materials. Resin etc. can be used. Two or more of these may be used in combination.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Furthermore, in the polymer binder of the present invention, monomers described in the following (1) to (14) can be used as other copolymerization monomers.

  (1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, and the like.

  (2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl Methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  (3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl) acrylamide and the like.

  (4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  (5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N -Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  (6) Monomers containing alkyl fluoride groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  (7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  (9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  (11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  (13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  (14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

  Further, other monomers that can be copolymerized with these monomers may be copolymerized.

  Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder. Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  These copolymers preferably have a mass average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

The content of the high molecular polymer in the photosensitive layer composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and the sensitivity to use in the range of 20 to 50% by mass. Particularly preferred from the viewpoint.
Furthermore, the acid value of the resin is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 from the viewpoint of balancing the polarity of the entire photosensitive layer. Particularly preferred, this can prevent pigment aggregation in the photosensitive layer coating solution.

  Although a synthesis example, a support preparation example, and an example are specifically shown below, embodiments of the present invention are not limited thereto. In the examples, “parts” represents “parts by mass” unless otherwise specified.

(Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The mass average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The desmutted roughened aluminum plate was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute, and further with 1% polyvinylphosphonic acid. Hydrophilic treatment was performed at 75 ° C. to prepare a support.

  At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of lithographic printing plate materials)
On the support, a photopolymerizable photosensitive layer coating solution 1 having the following composition was applied with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. A coated sample was obtained.

(Photopolymerizable photosensitive layer coating solution 1)
Addition-polymerizable ethylenic double bond-containing monomer described in Table 1 Amount described in Table Amount of polymerization initiator described in Table 1 Amount described in Table 1 Spectral sensitizing dye described in Table 1 Amount described in Table Acrylic copolymer 1 40.0 parts N-phenylglycine benzyl ester 4.0 parts phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co.) 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methyl) Benzyl)-
4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluorosurfactant (F-178K; manufactured by Dainippon Ink & Co.) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts Application of the above photopolymerized photosensitive layer An oxygen barrier layer coating solution having the following composition is applied on the sample with an applicator so as to be 1.8 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes, and the oxygen barrier layer on the photosensitive layer. A photosensitive lithographic printing plate material having a layer was prepared.

(Oxygen barrier layer coating solution 1)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: Toray Industries, Inc.) 10 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 (Evaluation of planographic printing plate)
(sensitivity)
Using a plate setter (Tiger Cat: ECRM modified product) equipped with a laser light source of 408 nm and 30 mV output on a photosensitive lithographic printing plate material, 2400 dpi (1 dpi means 2.5 dots per inch) Exposure).

  The exposure pattern used was a 100% image area and 175 LPI 50% square dots. Next, a preheating part that heat-treats the plate material at 105 degrees for 10 seconds, a pre-washing part that removes the overcoat layer before development, a developing part that is filled with a developer having the following composition, and a washing part that removes the developer attached to the plate surface , Development processing is performed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with a processing unit for gum solution for protecting the image area (GW-3: manufactured by Mitsubishi Chemical Corporation). A lithographic printing plate was obtained. In the 100% image portion recorded on the planographic printing plate, the minimum exposure energy amount at which no film reduction was observed was defined as the recording energy, and was used as an index of sensitivity. The smaller the recording energy, the higher the sensitivity. The results are shown in Table 1.

(Developer composition (aqueous solution containing the following additives))
A Potassium silicate 8.0% by mass
New Coal B-13SN: Nippon Emulsifier Co., Ltd. 3.0% by mass
Caustic potash pH = 12.3 (printing durability)
A lithographic printing plate produced by exposing and developing an image of 175 lines at 200 μJ / cm ² , coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, Inc.) with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) Printing using soybean oil ink “Naturalis 100”) and dampening water (Tokyo liquid ink H liquid SG-51 concentration 1.5%) The number of sheets was used as an index of printing durability.

NK Ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
From Table 1, it can be seen that the sample according to the present invention is excellent in sensitivity and printing durability.

Claims (5)

A photopolymerization initiator composition comprising at least one of a photopolymerization initiator and a sensitizing dye represented by the following general formula (1).

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represents a hydrogen atom or a substituent, and Z represents an atomic group which forms a carbocycle or a heterocycle with an adjacent carbon atom. ] The photopolymerization initiator composition according to claim 1, wherein the substituent represented by R ₃ in the general formula (1) is a substituted amino group. The photopolymerization initiator composition according to claim 1 or 2, wherein the photopolymerization initiator is an iron arene complex compound or a titanocene compound. The photopolymerization initiator composition according to any one of claims 1 to 3, wherein an addition-polymerizable ethylenic double bond-containing monomer, a polymer binder having an acryloyl group or a methacryloyl group, and a support are provided. A photosensitive lithographic printing plate material comprising a photopolymerizable photosensitive layer containing a product. A method for producing a lithographic printing plate, comprising producing the photosensitive lithographic printing plate material according to claim 4 by scanning and recording imagewise with a laser light source having a wavelength of 350 to 450 nm.