JP2006308879A - Photosensitive composition, photosensitive lithographic printing forme material, and recording method for lithographic printing forme material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing forme material suitable for exposure with laser light whose emission wavelength is in a range of 350-450 nm, having good safelight aptitude, and excellent in printing durability, sensitivity and linearity, a photosensitive composition giving the photosensitive lithographic printing forme material, and a recording method for a lithographic printing forme material. <P>SOLUTION: The photosensitive composition contains (A) a compound containing an addition polymerizable ethylenic double bond, (B) a photopolymerization initiator, (C) a polymeric binder and (D) a dye having an absorption maximum wavelength of 350-450 nm, wherein the photosensitive composition further contains a charge transport material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate material used in a computer-to-plate system (hereinafter referred to as CTP), a photosensitive composition used therein, and a recording method of a lithographic printing plate material using this photosensitive lithographic printing plate, The present invention relates to a photosensitive composition suitable for exposure with a laser beam having a wavelength of 350 to 450 nm, a photosensitive lithographic printing plate material, and a method for recording a lithographic printing plate material using the photosensitive lithographic printing plate.

  In recent years, CTP recording digital image data directly on a photosensitive lithographic printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Among these, in the field of printing that requires a relatively high printing durability, it is known to use a negative photosensitive lithographic printing plate material having a polymerization type photosensitive layer containing a polymerizable compound. (For example, refer to Patent Documents 1 and 2.)

  Furthermore, there is known a printing plate material capable of image exposure with a laser having a wavelength of 390 nm to 430 nm, which has improved safe light properties from the viewpoint of handleability of the printing plate.

  And, a high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm can be easily obtained, and by developing a photosensitive lithographic printing plate suitable for this laser wavelength, a bright room has been developed. (For example, refer to Patent Documents 3, 4 and 5.)

  Also known is a printing plate material containing biimidazole in the photosensitive layer, which has improved safelight properties under yellow light (see, for example, Patent Document 6).

However, these printing plate materials may still have insufficient printing durability and sensitivity, and the size of dots (halftone dots) based on image output data and the size of dots (halftone dots) on the printing plate. However, there is a problem that so-called linearity may be insufficient.
JP-A-1-105238 JP-A-2-127404 JP 2000-35673 A JP 2000-98605 A JP 2001-264978 A JP 2001-194882 A

  An object of the present invention is a photosensitive lithographic printing plate material suitable for exposure with a laser beam having an emission wavelength in the range of 350 nm to 450 nm, having good safe light properties, and excellent printing durability, sensitivity and linearity. It is an object of the present invention to provide a photosensitive composition that gives a photosensitive lithographic printing plate material, and a method for recording a lithographic printing plate material.

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

(Claim 1)
(A) Addition-polymerizable compound containing an ethylenic double bond, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a photosensitivity containing a dye having an absorption maximum wavelength of 350 to 450 nm. In the photosensitive composition, the photosensitive composition further contains a charge transport material.

(Claim 2)
2. The photosensitive composition according to claim 1, comprising a biimidazole compound or an iron arene complex compound as the photopolymerization initiator (B).

(Claim 3)
The photosensitive composition according to claim 2, further comprising a polyhalogen compound as the photopolymerization initiator (B).

(Claim 4)
The (A) addition-polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (1) or general formula (2). 2. The photosensitive composition according to item 1.

[Where Q ¹ is

Or -S-, R ⁴ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ³ represents a hydrogen atom, a methyl group or Represents an ethyl group, X ¹ represents a divalent group having 2 to 12 carbon atoms, and X ² represents a ² to 4 valent group, or

Z represents an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group, or a heterocyclic group, p represents an integer of 1 to 4, q represents an integer of 1 to 3, and p + q ≦ 5. . D ¹ and D ² each represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and E is a saturated hydrocarbon group having 2 to 12 carbon atoms, having 5 to 7 ring members. And a cycloaliphatic group containing up to two N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic fragrance having a 5-membered or 6-membered ring Represents a group, a represents 0 or an integer of 1 to 4, b represents 0 or 1, c represents an integer of 1 to 3, m represents an integer of 2 to 4 depending on the valence of Q ^1. , N represents an integer of 1 to m, and all groups having the same definition can be the same or different from each other. ]

[Where Q ² is

R ⁸ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. , D ³ and D ⁴ each represent a saturated hydrocarbon group having 1 to 5 carbon atoms, G is a saturated hydrocarbon group having 2 to 12 carbon atoms, and has 5 to 7 ring members And a cyclic aliphatic group containing up to 2 N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic aromatic group having 5 to 6 ring members D and e represent an integer of 1 to 4, g represents an integer of 2 to 4 depending on the valence of Q ² , f represents an integer of 1 to g, and all groups having the same definition are mutually It can be the same or different. ]
(Claim 5)
A photosensitive lithographic printing plate material comprising a photosensitive layer comprising the photosensitive composition according to any one of claims 1 to 4 on an aluminum support.

(Claim 6)
A method for recording a lithographic printing plate material, comprising performing image recording on the photosensitive lithographic printing plate material according to claim 5 using a laser beam having an emission wavelength in a range of 350 nm to 450 nm as a recording light source.

  According to the present invention, a photosensitive lithographic printing plate material and photosensitivity suitable for exposure with a laser beam having an emission wavelength in the range of 350 nm to 450 nm, having good safe light properties, and excellent printing durability, sensitivity and linearity. A photosensitive composition that provides a lithographic printing plate material and a method for recording a lithographic printing plate material can be provided.

  Next, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

  The present invention provides (A) an addition-polymerizable ethylenic double bond-containing compound, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a dye having an absorption maximum wavelength of 350 to 450 nm. The photosensitive composition to be contained is characterized in that the photosensitive composition further contains a charge transport material.

  In particular, a photosensitive lithographic printing plate material excellent in printing durability, sensitivity and linearity can be provided by incorporating a charge transport material into the photosensitive composition.

  Each component contained in the photosensitive composition used for the photosensitive layer of the photosensitive lithographic printing plate material of the present invention will be described.

  The charge transport material according to the present invention is a compound having the property of drift mobility of electrons or holes, and is caused by charge transport by a known method capable of detecting charge transport ability such as Time-Of-Flight method. A compound that provides a detected current.

  Charge transport materials include hole transport materials and electron transport materials.

  Examples of hole transport materials include 9-ethylcarbazole-3-aldehyde 1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde 1,1-diphenylhydrazone, 4-diethylaminostyrene-β-aldehyde 1-methyl. -1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone, 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-benzyl-1 -Phenylhydrazone, 4-diethylaminobenzaldehyde 1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1-benzyl-1- (4-methoxyphenyl) hydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-fur Hydrazone compounds such as nilhydrazone, 4-dibenzylaminobenzaldehyde 1,1-diphenylhydrazone, 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 2,2′-dimethyl Triphenylmethane compounds such as -4,4'-bis (diethylamino) -triphenylmethane, or diphenylmethane compounds, 9- (4-diethylaminostyryl) anthracene, 9-bromo-10- (4-diethylaminostyryl) anthracene, 9 -(4-Dimethylaminostyryl) fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole, 1,2-bis (2,4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl) ) Benzene, 3-styryl-9- Ethylcarbazole, 3- (4-methoxystyryl) -9-ethylcarbazole, 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4-diethylaminostyryl) naphthalene, 4′-diphenylamino-α-phenylstilbene, stilbene compounds such as 4′-methylphenylamino-α-phenylstilbene, or arylvinyl compounds, 1-phenyl-3- (4-diethylamino) Pyrazoline compounds such as styryl) -5- (4-diethylaminophenyl) pyrazoline, 1-phenyl-3- (4-dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazoline, 2,5-bis (4- Diethylaminophenyl) -1 , 3,4-oxadiazole, 2,5-bis {4- (4-diethylaminostyryl) phenyl} -1,3,4-oxadiazole, 2- (9-ethylcarbazolyl-3-)- 5- (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-vinyl-4- (2-chlorophenyl) -5- (4-diethylaminophenyl) oxazole, 2- (4-diethylaminophenyl)- Heterocyclic compounds such as 4-phenyloxazole, triphenylamine, tri-p-tolylamine, 4,4′-dimethoxytriphenylamine, N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine 1,1-bis (4-di-p-triphenylaminophenyl) cyclohexane, N, N, N ′, N′-tetra (p-tolyl) benzidine, N Triphenylamine compounds such as N, N ′, N′-tetra (p-tolyl) -o-phenylenediamine, N, N′-bis (4-methoxyphenyl) -1-aminopyrene, or triarylamine compounds, etc. There are low molecular weight compounds.

  In addition, polymer compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, pyreneformaldehyde resin, and ethylcarbazole formaldehyde resin can also be used.

  Examples of the electron transport material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, diphenoquinone, 2 , 4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno {1,2-b} thiophen-4-one, 1,3,7 -Trinitrodibenzothiophene-5,5-dioxide, succinic anhydride, maleic anhydride, phthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 4-nitrophthalic anhydride, 3-nitrophthalic anhydride, pyro anhydride Merit acid, picric acid, o-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, dichlorodicyano-p-benzoquinone, anthraquinone, Examples include chloroanthraquinone, dichloroanthraquinone, dinitroanthraquinone, 9-fluorenylidene {dicyanomethylenemalonodinitrile} and the like having a high electron affinity. These charge transport materials may be used alone or in combination of two or more.

  Of these, carbazole compounds, stilbene compounds, amine compounds, oxadiazole compounds, quinodimethane compounds, benzoic acid compounds, and quinone compounds are preferred, and stilbene compounds, amine compounds, oxadiazole compounds, nodimethane compounds, and benzoic acid compounds are particularly preferred. It is done.

  The content of the charge transport material in the photosensitive composition is preferably 0.01% by mass to 30.0% by mass and more preferably 0.1% by mass with respect to the solid content of the photosensitive composition in terms of printing durability. % To 10.0 mass% is preferable, and 0.5 mass% to 8.0 mass% is particularly preferable.

  Moreover, 0.01 mass%-25.0 mass% are preferable with respect to a photoinitiator from the surface of a sensitivity, and it is preferable to contain especially in 0.05 mass%-15.0 mass%.

((A) Addition-polymerizable ethylenic double bond-containing compound)
The (A) addition polymerizable ethylenic double bond-containing compound according to the present invention is a compound having an ethylenic double bond that can be polymerized by image exposure.

  Addition-polymerizable ethylenic double bond-containing compounds include general radical-polymerizable monomers and polyfunctional compounds having a plurality of addition-polymerizable ethylenic double bonds commonly used in UV curable resins. Monomers 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 singly 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 obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates 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 acrylates 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 resins 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 photosensitive composition of the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing compound containing a tertiary amino group in the molecule, which is a tertiary amine monomer. 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, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, in the present invention, a tertiary amine monomer, 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 are used. It is preferred to use a reaction product.

  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, Although 2-propanediol etc. are mentioned, it is not limited to this.

  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 the following compounds MH-1 to MH-13, but are not limited thereto.

  Preferably, 2-hydroxyethyl methacrylate (MH-1), 2-hydroxyethyl acrylate (MH-2), 4-hydroxybutyl acrylate (MH-4), 2-hydroxypropylene-1,3-dimethacrylate (MH-) 7), 2-hydroxypropylene-1-methacrylate-3-acrylate (MH-8) 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-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) 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.

  In the present invention, the addition-polymerizable ethylenic double bond-containing compound is particularly preferably a compound represented by the general formula (1) or the general formula (2).

  The compound represented by the general formula (1) will be described below.

In the general formula (1), examples of the alkyl group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. N-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-docosadecyl group and the like. Examples of the hydroxyalkyl group represented by R ⁴ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxypentyl group. Examples of the aryl group represented by R ⁴ include a phenyl group and a naphthyl group.

In General formula (1), the alkyl group represented by R < ¹ > and R < ² > is synonymous with the alkyl group represented by said R < ⁴ >. Examples of the alkoxyalkyl group represented by R ¹ and R ² include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and a propoxyethyl group.

In the general formula (1), examples of the divalent group having 2 to 12 carbon atoms represented by X ¹ include a group having a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group. A group having a divalent aromatic group, a group having a divalent heterocyclic group, etc., among which a group having a divalent unsaturated hydrocarbon group is preferred. A group having a group and a group having a divalent heterocyclic group.

  In the general formula (1), examples of the group having a divalent saturated hydrocarbon group include an ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2 , 4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), cyclopentylene Group (for example, 1,5-cyclopentanediyl group and the like) and the like.

  In the general formula (1), as the group having a divalent unsaturated hydrocarbon group, one of the bonds connecting at least two carbon atoms constituting the above group having a divalent saturated hydrocarbon group is a double bond. A group formed by being replaced with an unsaturated bond such as a bond or a triple bond. For example, a propenylene group, a vinylene group (also referred to as an ethynylene group), a 4-propyl-2-pentenylene group, and the like can be given.

In the general formula (1), examples of the group having a divalent heterocyclic group represented by X ¹ include an oxazolediyl group, a pyrimidinediyl group, a pyridazinediyl group, a pyrandiyl group, a pyrrolinediyl group, an imidazolinediyl group, Examples include imidazolidinediyl group, pyrazolidinediyl group, pyrazolinediyl group, piperidinediyl group, piperazinediyl group, morpholinediyl group, quinuclidinediyl group and the like.

In the general formula (1), examples of the group having a divalent aromatic group represented by X ¹ include a phenylene group, a naphthylene group, a pyridinediyl group, a pyrrolediyl group, a thiophenediyl group, and a frangylyl group. It is done. X ¹ is preferably an aromatic group, and examples thereof include a phenylene group and a naphthylene group, and particularly preferably a phenylene group.

In the general formula (1), a trivalent group represented by X ² include those divalent group (saturated hydrocarbon group, an arylene group) represented by the above X ² is further one linking group attached For example, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, undecantriyl group, dodecantriyl group , Cyclohexanetriyl group, cyclopentanetriyl group, benzenetriyl group, naphthalenetriyl group and the like.

In the general formula (1), tetravalent groups represented by X ^2, which has with a further one linking group to a trivalent group represented by the aforementioned X ^2, for example, pro Panjii alkylidene group, 1,3-propanediyl-2-ylidene group, butanediylidene group, pentanediylidene group, hexanediylidene group, heptanediylidene group, octanediylidene group, nonanediylidene group, decandiylidene group, undecandiylidene group, dodecandiylidene group , Cyclohexanediylidene group, cyclopentanediylidene group, benzenetetrayl group, naphthalenetetrayl group and the like.

In X ² of the general formula (1), Z represents an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group, or a heterocyclic group. Examples of the alkyl group represented by Z include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Examples of the alkenyl group represented by Z include a 2-propenyl group, a 3-butenyl group, a 1-methyl-3-propenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group, and a 4-hexenyl group. Is mentioned. Examples of the aryl group represented by Z include a phenyl group, an m-chlorophenyl group, a p-tolyl group, and a naphthyl group. Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxyl group represented by Z include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the heterocyclic group represented by Z include a pyridyl group, a pyrrolyl group, a 2-methylpyrrolyl group, an indolyl group, an imidazolyl group, a furyl group, a thiazolyl group, and a pyrimidinyl group.

In the general formula (1), the saturated hydrocarbon group having 1 to 5 carbon atoms represented by D ¹ and D ² includes a methylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, Examples include a pentamethylene group and a cyclopentylene group.

In the general formula (1), the saturated hydrocarbon group having 2 to 12 carbon atoms represented by E is synonymous with the divalent group having 2 to 12 carbon atoms represented by X ^1. is there.

  In the general formula (1), as the cyclic aliphatic group represented by E having 5 to 7 ring members and containing up to 2 N, O or S atoms as ring members, for example, tetrahydrofuran Ring, pyrrolidine ring, pyrazoline ring, imidazoline ring, oxazoline ring, thiazoline ring, pyridazine ring, pyran ring, thiophene ring, isoxazoline ring, pyrroline ring, imidazoline ring, imidazolidine ring, pyrazolidine ring, pyrazoline ring, piperidine ring, piperazine A ring, a morpholine ring, and the like.

  In the general formula (1), examples of the aromatic group having 6 to 12 carbon atoms represented by E include a phenylene group and a naphthylene group.

  In the general formula (1), the heterocyclic ring of the heterocyclic aromatic group having a 5-membered or 6-membered ring represented by E includes a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, 1,2,3-oxadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples thereof include s-triazine ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, purine ring, quinoline ring and isoquinoline ring.

  Here, each substituent represented by the general formula (1) described above may further have a substituent.

In the general formula (1), Q ¹ is preferably> N—, X ¹ has an aromatic ring, and more preferably X ¹ is derived from tolylene diisocyanate in specific examples of the following compounds 1-12 1-15, and more preferably X ¹ has a structure such as 1-16 to 1-20 derived from tetramethylxylene diisocyanate.

  The compound represented by the general formula (1) can be synthesized with reference to a method well known to those skilled in the art, for example, a method described in Japanese Patent No. 2509288.

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

  Next, the compound represented by the general formula (2) will be described.

In the general formula (2), R ⁸ may be different from each other when (g−f) is 2 or more. Compounds in which g and f are the same value are preferred. When R ⁸ is an alkyl group or a hydroxyalkyl group, the number of carbon atoms is preferably 2 to 8, and more preferably 2 to 4. When R ⁸ is an aryl group, it is preferably a single ring or two rings, more preferably a single ring, and may be substituted with an alkyl group, alkoxyalkyl group or halogen atom having up to 5 carbon atoms. If R ⁵ and R ⁶ is an alkyl group or an alkoxyalkyl group, the carbon number 1 to 5 are preferred. R ⁷ is preferably a methyl group.

D ³ and D ⁴ may be the same or different, and preferably form a 6-membered saturated heterocyclic ring with two nitrogen atoms.

  When G is a saturated hydrocarbon group, it preferably has 2 to 6 carbon atoms. When G is an aromatic group, a phenylene group is preferred. When G is a cyclic aliphatic group, a cyclohexylene group is preferred. In the case of an aromatic group, a 5- to 6-membered ring containing a nitrogen atom or a sulfur atom is preferable.

In order to obtain the compound represented by the general formula (2), when Q ² is> N- and f and g have the same value, glycidyl acrylate or alkyl acrylate is reacted with hydroxyalkylamine. Other compounds can be obtained in the same manner.

  Specific examples of the compound represented by the general formula (2) according to the present invention are shown below.

  30-70 mass% of the non-volatile component of a photopolymerizable photosensitive layer is preferable, and, as for the addition amount of the ethylenic double bond containing compound which can perform addition polymerization based on this invention, 40-60 mass% is more preferable.

((B) Photopolymerization initiator)
The photopolymerization initiator according to the present invention is a compound capable of initiating polymerization of an (A) polymerizable, ethylenically unsaturated bond-containing compound by image exposure, such as a biimidazole compound, an iron arene complex compound, a titanocene compound. , Polyhalogen compounds, monoalkyltriaryl borate compounds and the like are preferably used. Among these, a biimidazole compound and an iron arene complex compound are particularly preferable, and in addition to this, it is particularly preferable that a polyhalogen compound is further included.

(Biimidazole compound)
The biimidazole compound according to the present invention is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.

  In the present invention, it is preferable to contain a hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compound as the biimidazole compound.

  Processes for the production of HABIs are described in DE 1,470,154 and their use in photopolymerizable compositions is described in EP 24,629, EP 107,792, US 4,410,621, EP 215,453 and DE 3, 211 and 312.

  Preferred derivatives are, for example, 2,4,5,2 ′, 4 ′, 5′-hexaphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole. Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-dimethyl) Xylphenyl) biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,5 , 4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole.

  The amount of HABI is typically in the range of 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the non-volatile components of the photosensitive composition.

<Iron arene complex compound>
The iron arene complex compound according to the present invention is a compound represented by the following general formula (a).

Formula (a) [A-Fe-B] ⁺ X ⁻
In the formula, A represents a substituted or unsubstituted cyclopentadienyl group or a cyclohexadienyl group. In the formula, B represents a compound having an aromatic ring. In the formula, X ⁻ represents an anion.

Specific examples of the compound having an aromatic ring include benzene, toluene, xylene, cumene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, fluorene, anthracene, and pyrene. Examples of X ⁻ include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , AlF ₄ ⁻ , CF ₃ SO ₃ ^{− and the} like. Examples of the substituent of the substituted cyclopentadienyl group or cyclohexadienyl group include alkyl groups such as methyl and ethyl groups, cyano groups, acetyl groups, and halogen atoms.

  It is preferable to contain an iron arene complex compound in the ratio of 0.1-20 mass% with respect to the compound which has a group which can superpose | polymerize, More preferably, it is 0.1-10 mass%.

Specific examples of the iron arene complex compound are shown below.
Fe-1: (η6-benzene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-2: (η6-toluene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe— 3: (η6-cumene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-4: (η6-benzene) (η5-cyclopentadienyl) iron (2) hexafluoroarsenate Fe-5 : (Η6-benzene) (η5-cyclopentadienyl) iron (2) tetrafluoroporate Fe-6: (η6-naphthalene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-7: ( η6-anthracene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-8: (η6-pyrene) Lopentagenyl) iron (2) hexafluorophosphate Fe-9: (η6-benzene) (η5-cyanocyclopentadienyl) iron (2) hexafluorophosphate Fe-10: (η6-toluene) (η5-acetylcyclopentazinini ) Iron (2) Hexafluorophosphate Fe-11: (η6-cumene) (η5-cyclopentadienyl) Iron (2) Tetrafluoroborate Fe-12: (η6-benzene) (η5-carboethoxycyclohexadienyl) ) Iron (2) hexafluorophosphate Fe-13: (η6-benzene) (η5-1,3-dichlorocyclohexadienyl) iron (2) hexafluorophosphate Fe-14: (η6-cyanobenzene) (η5- Cyclohexadienyl) iron (2) hexafluorophosphate Fe-15: (η6 Acetophenone) (η5-cyclohexadienyl) iron (2) hexafluorophosphate Fe-16: (η6-methylbenzoate) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-17: (η6-benzene Sulfonamide) (η5-cyclopentadienyl) iron (2) tetrafluoroborate Fe-18: (η6-benzamide) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-19: (η6-cyano Benzene) (η5-cyanocyclopentadienyl) iron (2) hexafluorophosphate FE-20: (η6-chloronaphthalene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-21: (η6- Anthracene) (η5-cyanocyclopentadienyl) iron (2) Xafluorophosphate Fe-22: (η6-chlorobenzene) (η5-cyclopentadienyl) iron (2) Hexafluorophosphate Fe-23: (η6-chlorobenzene) (η5-cyclopentadienyl) iron (2) Tetrafluoroborate These compounds are described in Dokl. Akd. It can be synthesized by the method described in Nauk SSSR 149 615 (1963).

  Examples of titanocene compounds include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride, bis (Cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6 -Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis- , 3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis -2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE 784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2, 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like It is below.

  The photosensitive composition of the present invention preferably further contains a polyhalogen compound as a photopolymerization initiator. As the polyhalogen compound, for example, compounds represented by the following general formulas (3) to (5) are preferable.

In the formula, Z ₁ and Z ₂ each independently represent a halogen atom, X represents a hydrogen atom or an electron-withdrawing group, Y ₁ represents a —CO— group or a —SO ₂ — group, and Q ₃ represents an arylene group. Or a divalent heterocyclic group, L represents a linking group, W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphoric acid group or a salt thereof, a hydroxyl group, a quaternary ammonium group, or a polyethyleneoxy group. . r represents 0 or 1;

In the formula, Q ₄ represents an alkyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ each represent a halogen atom. Z represents a hydrogen atom or an electron-withdrawing group. Y represents —C (═O) —, —SO— or —SO ₂ —. s represents 0 or 1.

In the formula, Q ₅ represents an alkyl group, an aryl group or a heterocyclic group, and X ₄ , X ₅ and X ₆ each represent a hydrogen atom or a halogen atom, but at least one of X ₄ , X ₅ and X ₆ is Represents a halogen atom. t represents an integer of 0 to 4, and u represents an integer of 1 to 5.

  Typical specific examples of the compounds represented by the general formulas (3) to (5) are listed below, but the present invention is not limited thereto.

  The polyhalogen compound according to the present invention is preferably a polyhaloacetyl compound, and more preferably a trihaloacetylamide compound. Examples of the polyhaloacetyl compound include a compound represented by the following general formula (6) or more preferably a compound represented by the following general formula (7).

Formula ^{(6) R 11 -C (X} 10) 2 - (C = O) -R 12
In the formula, X ¹⁰ represents a chlorine atom or a bromine atom. R ¹¹ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group. R ¹² represents a monovalent substituent. R ¹¹ and R ¹² may be bonded to form a ring.

Formula ^{(7) C (X 11)} 3 - (C = O) -Y 10 -R 13
In the formula, X ¹¹ represents a chlorine atom or a bromine atom. R ¹³ represents a monovalent substituent. Y ¹⁰ represents —O— or —NR ¹⁴ —. R ¹⁴ represents a hydrogen atom or an alkyl group. R ¹³ and R ¹⁴ may combine to form a ring.

  Typical specific examples (BR1 to BR76) of the compound represented by the general formula (6) are listed below, but the present invention is not limited thereto.

  Among the compounds represented by the general formula (6), preferred specific examples of the compound represented by the general formula (7) are the compounds of BR2 to BR47 and BR67 to BR76.

  In the polyhalogen compounds represented by the general formulas (3) to (7), polybromine compounds are more preferable.

  The polyhalogen compound preferably used in the present invention further includes a trihalomethyltriazine compound. For example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4, 6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4, - bis (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine , 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc., compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-tria 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl)- Examples include 4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis-trichloromethyl-S-triazine, and the compounds described in German Patent 3337024. be able to. F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium / n-butyrate. Linaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n -Butylammonium n-hexyl rootri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium n-hexyl rootri- (3-fluorophenyl) -borate and the like.

  In the present invention, other known photopolymerization initiators may be used in combination as the photopolymerization initiator.

((C) polymer binder)
Next, the polymer binder will be described.

  Examples of the polymer binder used in 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 others. Natural resins 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 preferred.

  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 fluorinated alkyl 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, the polymer binder of the present invention is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, 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. In addition, an unsaturated bond-containing vinyl copolymer obtained by adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl. Isocyanates are preferred, and (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate and the like can be mentioned.

  A known method can be used for the addition reaction of 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. For example, the reaction temperature is 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is 2 to 10 hours, preferably 3 to 6 hours. Can do. Examples of the solvent to be used include those used in the polymerization reaction of the vinyl copolymer. In addition, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the alicyclic epoxy group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary.

  Here, the catalyst is preferably an amine-based or ammonium chloride-based material, and specifically, the amine-based material is triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine. , Isopropylamine, 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, benzylamine, and the like, and ammonium chloride-based substances include triethylbenzylammonium chloride and the like.

  When using these as a catalyst, what is necessary is just to add in 0.01-20.0 mass% with respect to the alicyclic epoxy group containing unsaturated compound to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is 0.01 to 5.0% by mass with respect to the alicyclic epoxy group-containing unsaturated compound to be used. The progress of the reaction may be determined by measuring the acid value of the reaction system and stopping the reaction when the acid value becomes zero.

  A known method can be used for the addition reaction of a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer. For example, the reaction temperature is usually 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is usually 2 to 10 hours, preferably 3 to 6 hours. It can be carried out. Examples of the solvent to be used include solvents used in the polymerization reaction of the polymer copolymer. Further, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the isocyanate group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary. Here, the catalyst is preferably a tin-based or amine-based substance, and specific examples include dibutyltin laurate and triethylamine.

  The catalyst is preferably added in the range of 0.01 to 20.0 mass% with respect to the compound having a double bond to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is usually 0.01 to 5.0% by mass with respect to the isocyanate group-containing unsaturated compound to be used. The progress of the reaction may be determined by determining the presence or absence of an isocyanato group in the reaction system using an infrared absorption spectrum (IR), and stopping the reaction when the absorption disappears.

  The above-mentioned vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain used in the present invention is preferably 50 to 100% by mass and 100% by mass in the total polymer binder. More preferred.

  The content of the polymer binder in the photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and use in the range of 20 to 50% by mass from the viewpoint of sensitivity. Particularly preferred.

(Dye having an absorption maximum wavelength of 350 to 450 nm)
The photosensitive composition of the present invention contains a sensitizing dye having an absorption maximum in a wavelength range of 350 to 450 nm.

  Examples of these dyes include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, azo compound, diphenylmethane, triphenylmethane, triphenylamine, coumarin derivative, quinacridone, Examples include indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.

  Of these sensitizing dyes, a coumarin dye represented by the following general formula (8) is preferably used.

Wherein, R ³¹ to R ³⁶ represents a hydrogen atom, a substituent group. Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aryl group (eg, phenyl group, naphthyl group). Etc.), heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group , Phthalazyl groups, etc.), heterocyclic groups (eg , Pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, 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 (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) Group, dodecylthio group etc.), cycloalkylthio group (eg cyclopentylthio group, cyclohexylthio group etc.), arylthio group (eg phenylthio group, naphthylthio group etc.), alkoxycarbonyl group (eg methyl Xycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, 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 group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexane) A silcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group, etc.), an acyloxy group (for example, an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group) Octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonyl) Amino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylca Carbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl 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-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethyls) Finyl 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, ethyl group) Amino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridyl Amino group etc.), a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a cyano group, a nitro group, hydroxy group, and the like. These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

Among these, particularly preferred is a coumarin having an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group as R ³⁵ . In this case, an alkyl group substituted with an amino group that forms a ring with the substituents of R ³⁴ and R ³⁶ can also be preferably used.

Further, either or both of R ³¹ and R ³² are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), Heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group Etc.), heterocyclic groups (eg, pyrrolidyl group, imida Zolidyl group, morpholyl group, oxazolidyl group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group etc.), aryloxycarbonyl group (eg , Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), acyl group (for example, acetyl group, 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, butylcarbonyl) Xy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy 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.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group) Group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group Group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), aryl Sulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group, halogenated alkyl group (trifluoromethyl group) , Tribromomethyl group, trichloromethyl group, etc.).

  Preferable specific examples include, but are not limited to, the following compounds.

  In addition to the above specific examples, coumarin derivatives of B-1 to B-22 in JP-A-8-129258, coumarin derivatives of D-1 to D-32 in JP-A-2003-21901, JP-A-2002-363206 No. 1 to 21 Coumarin Derivatives, JP-A No. 2002-363207 No. 1 to 40 Coumarin Derivatives, JP-A No. 2002-363208 No. 1 to 34 Coumarin Derivatives, JP-A No. 2002-363209 No. 1 56 coumarin derivatives and the like can also be preferably used.

  Hereinafter, various additives that can be added to the photosensitive composition in the present invention, a support as a photosensitive lithographic printing plate, a protective layer, application of the photosensitive composition to the support, an image of the photosensitive lithographic printing plate The recording method and the like will be described sequentially.

(Various additives)
In the photosensitive composition of the present invention, in addition to the above-described components, in order to prevent unnecessary polymerization of an ethylenic double bond monomer that can be polymerized during production or storage of a photosensitive lithographic printing plate, It is desirable to add a polymerization inhibitor. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.

  The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the total solid content of the composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, or it may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

  Moreover, a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

  Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.

  From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, violet pigments and blue pigments are preferably used. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.

  Moreover, the said composition can contain surfactant as a coating property improving agent in the range which does not impair the performance of this invention. Of these, fluorine-based surfactants are preferred.

  In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solid content.

  The solvent used in the photosensitive layer coating solution prepared for providing the photosensitive layer according to the present invention includes, for example, alcohol: polyhydric alcohol derivatives such as sec-butanol, isobutanol, and n-hexanol. , Benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: di Preferred examples include acetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

  Although the photosensitive composition according to the present invention has been described above, the photosensitive lithographic printing plate material according to the present invention is prepared by mixing and preparing the above-mentioned compositions so as to have the above ratios, and coating this on an aluminum support. It is constituted by doing.

(Protective layer: oxygen barrier layer)
If necessary, a protective layer can be provided on the upper side of the photosensitive layer according to the present invention.

  This protective layer (oxygen barrier layer) is preferably highly soluble in a developer (described below, generally an aqueous alkali solution) described below, and specific examples include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  When a protective layer is provided on the photosensitive lithographic printing plate material of the present invention, the peeling force between the photosensitive layer and the protective layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and even more preferably 75 mN / mm or more. It is. Preferred examples of the protective layer composition include those described in Japanese Patent Application No. 8-161645.

  Peeling force is measured by applying a predetermined width of adhesive tape with a sufficiently large adhesive force on the protective layer and peeling it with the protective layer at an angle of 90 degrees with respect to the plane of the photosensitive lithographic printing plate material. Can be obtained.

  The protective layer can further contain a surfactant, a matting agent and the like as required. The protective layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a protective layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol.

  When providing a protective layer, the thickness is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

(Support)
The photosensitive composition of the present invention is coated on a support to constitute a photosensitive lithographic printing plate material.In the present invention, as the support, an aluminum support having a hydrophilic surface is used. Pure aluminum or aluminum alloy may be used.

  Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. .

  Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. It is preferable to perform the treatment.

  As a roughening method used in the present invention, roughening is performed by electrolysis, but before that, roughening can be performed by, for example, a mechanical method.

The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to neutralize by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

In the present invention, as a roughening method, roughening by electrolysis is performed. In this method, the surface is electrochemically roughened in an acidic electrolytic solution, and the acidic electrolytic solution has an effective value of 30 A in a hydrochloric acid or nitric acid solution having a concentration of 0.4% by mass to 2.8% by mass. / dm ² or more 100A / dm ² or less at a current density of 10 seconds to 120 seconds, performing electrolytic graining. The concentration of hydrochloric acid or nitric acid is more preferably 1% by mass or more and 2.3% by mass or less. Current density is more preferably 30A / dm ² or more 80A / dm ² or less, further preferably 40A / dm ² or more 75A / dm ² or less.

The temperature at which the electrolytic surface-roughening method is performed is not particularly limited, but is preferably in the range of 5 ° C. to 80 ° C., more preferably in the range of 10 ° C. to 60 ° C. The applied voltage is not particularly limited, but is preferably performed by applying a voltage in the range of 1 to 50 volts, and more preferably in the range of 10 to 30 volts. Quantity of electricity is not particularly limited, it is preferable to use a range of 5000 C / dm ^2, still preferably selected from the range of 100~2000c / dm ^2.

  If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

After the surface is roughened by the electrolytic surface roughening method, it is preferably immersed in an acid or alkaline aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

Following the electrolytic surface roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. A method of electrolysis at a high current density in sulfuric acid described in Japanese Patent No. 1,412,768, a method of electrolysis using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more oxalic acid, malonic acid and the like. The formed anodic oxidation coating amount is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is determined from the measurement of mass change before and after dissolution of the coating on the plate.

  In the present invention, the support is preferably treated with a sodium silicate solution having a temperature of 20 ° C. or more and 50 ° C. or less after the anodizing treatment. The temperature is preferably 20 ° C. or higher and 50 ° C. or lower, and more preferably 20 ° C. or higher and 45 ° C. or lower. If it is less than 20 ° C., it may become dirty and recovery may be worsened. Further, if it is higher than 50 ° C., the printing durability may be deteriorated. The concentration of sodium silicate is not particularly limited, but is preferably 0.01% or more and 35% or less, and more preferably 0.1% or more and 5% or less.

  In the present invention, the support is preferably treated with a polyvinylphosphonic acid solution having a temperature of 20 ° C. or more and 70 ° C. or less after the anodizing treatment. The temperature is preferably 20 ° C. or higher and 70 ° C. or lower, and more preferably 30 ° C. or higher and 65 ° C. or lower. If it is less than 20 ° C., it may become dirty and recovery may be worsened. On the other hand, if it is higher than 70 ° C., the printing durability may be deteriorated. The concentration of the polyvinylphosphonic acid solution is not particularly limited, but is preferably 0.01% or more and 35% or less, and more preferably 0.1% or more and 5% or less.

(Application)
The prepared photosensitive composition (coating solution for photopolymerizable photosensitive layer) can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. I can list them.

  If the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained. If the drying temperature is too high, not only marangoni is produced but also fogging of non-image areas occurs. The preferable drying temperature range is preferably 60 to 160 ° C., more preferably 80 to 140 ° C., and particularly preferably 90 to 120 ° C.

(Image recording method)
As a light source for recording an image on the photosensitive lithographic printing plate material according to the present invention, laser light having an emission wavelength of 350 to 450 nm is preferably used.

  As a light source for exposing the photosensitive lithographic printing plate material of the present invention, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO 3 as a semiconductor laser system, a ring A resonator (430 nm), AlGaInN (350 nm to 450 nm), an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 nm) and the like can be mentioned.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data.

  When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

  Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the planographic printing plate material is wound, and the rotation of the drum is the main scanning, and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a lithographic printing plate material is fixed to the inner surface of a drum, a laser beam is irradiated from the inner side, and part or all of the optical system is rotated to perform main scanning in the circumferential direction. Sub scanning is performed in the axial direction by linearly moving a part or all of the part in parallel with the axis of the drum. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

In the present invention, image recording is preferably performed with a plate surface energy (energy on the plate material) of 10 mJ / cm ² or more, and the upper limit is 500 mJ / cm ² . More preferably, it is 10-300 mJ / cm < ² >. For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by OphirOptics can be used.

(Developer)
The exposed portion of the photosensitive layer on which the image has been recorded is cured. By developing this with an alkaline developer, the unexposed areas are removed and image formation becomes possible. As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium An alkali developer using an inorganic alkaline agent such as sodium borate, potassium, ammonium; sodium hydroxide, potassium, ammonium and lithium;

  Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.

  These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.

(Developer concentrate)
In the present invention, the developer is preferably prepared using a well-known developer concentrate such as a granule or a tablet.

  In the present invention, it is advantageous to use these developer concentrates. The concentrated developer concentrate is diluted to a predetermined concentration with water before development and used for development or as a development replenisher. preferable.

  The developer concentrate may be evaporated to dryness once it is made into a developer, but preferably the materials are mixed by adding a small amount of water without adding water when mixing a plurality of materials. A method of concentrating with is preferable. The developer concentrates are disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266062, and JP-A-7. Granules and tablets can be obtained by a well-known method described in No. 13341 or the like. Further, the developer concentrate may be divided into a plurality of parts having different material types, material mixing ratios, and the like.

  These concentrated developer concentrates are preferably used for development after dilution to a predetermined concentration with water before development. Further, when this developer concentrate is used as a developer replenisher, it is most preferable to dilute with water to a predetermined concentration and then add it to the developer in use. It is also possible to put it into a developing solution as it is without diluting to a concentration. When adding the developer concentrate to the developer in use as it is, without diluting it to a concentration that is higher than the predetermined concentration or to the predetermined concentration, separately to the developer in use at the same timing or at another timing. Water may be added.

  The developer concentrate preferably has a water content of 10% by mass or less, more preferably 1% by mass or less. When the water content is high, the components of the developer are separated in water, causing problems such as loss of uniformity or liquefaction and difficulty in handling. As the material contained in the developer, the components used in the developer of a normal photosensitive lithographic printing plate can be used. However, when the water content is 10% by mass or less, even if it reacts and is diluted with water, It is preferable not to include materials that do not return, materials that contain a large amount of water, and materials that are liquid at room temperature. For example, since silicate is converted into stone when it becomes low in moisture, it becomes difficult to dissolve in water. Therefore, it is preferable to contain carbonates, phosphates, organic acid salts and the like described later instead of silicates. Particularly preferred is carbonate.

  The components of the developer concentrate that are preferably used will be described below. Unless otherwise noted, the description means both developer concentrate and developer replenisher concentrate. The term “developer” means a developer or developer replenisher after dilution with water to a predetermined amount.

(Alkaline agent)
Examples of the inorganic alkaline agent include tribasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, The same potassium, the same ammonium, the same lithium, etc. are mentioned. Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, Examples include diethanolamine, triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, pyridine, and tetramethylammonium hydroxide.

  These alkali agents are used alone or in combination of two or more. As the amount of the alkali agent, it is preferable that the pH when used as a developer is in the range of 9 to 13.5, and the conductivity is in the range of 2 to 40 mS / cm, and a more preferable range is pH 10.0 to 12.5, conductivity 3-30 mS / cm, more preferably 5-20 mS / cm. When the pH of the developer is lower than the above range, image formation cannot be performed, and when the pH is higher, over-development occurs, or damage caused by development in the exposed portion becomes strong. When the electrical conductivity is below the above range, it is usually difficult to elute the photosensitive composition on the aluminum plate support, resulting in smudges in printing. On the other hand, if it exceeds the above range, the elution rate of the photosensitive layer becomes extremely slow due to the high salt concentration, and a residual film is formed in the unexposed area.

  It is particularly preferable that the developer concentrate contains a nonionic surfactant having a polyoxyalkylene ether group. By this addition, the dissolution of the photosensitive layer in the unexposed area is promoted, and the permeability of the developer to the exposed area is increased. Reduction is possible. As the surfactant containing a polyoxyalkylene ether group, a compound represented by the following general formula (AO) is suitable.

Formula (AO) R ₁ —O (R ₂ —O) _n H
In the formula, each R ₁ represents an optionally substituted alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or a heteroaromatic ring group having 4 to 15 carbon atoms. . Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a halogen atom such as bromine, chlorine and iodine, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and 1 to 1 carbon atoms. Examples include 20 alkoxy groups, C2-C20 alkoxy-carbonyl groups, and C2-C15 acyl groups.

R ₂ represents an optionally substituted alkylene group having 1 to 100 carbon atoms, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms. It is done. n represents an integer of 1 to 100.

The part of (R ₂ —O) _{n in} the general formula (AO) may be two or three kinds of groups as long as it is in the above range. Specifically, a random or block combination of ethyleneoxy group and propyleneoxy group, ethyleneoxy group and i-propyleneoxy group, ethyleneoxy group and butyleneoxy group, ethyleneoxy group and i-butyleneoxy group, etc. Can be mentioned.

  The surfactant having a polyoxyalkylene ether group is used alone or in a composite system, and it is effective to add 1 to 30% by mass, preferably 2 to 20% by mass in the developer. If the addition amount is small, the developability is deteriorated. On the other hand, if the addition amount is too large, the development damage becomes strong and the printing durability of the printing plate is lowered.

  Further, other surfactants described below may be added. Examples of other surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate Monoglyceride alkyl esters such as sorbitan alkyl esters such as glycerol, glycerol monostearate and glycerol monooleate Nonionic surfactants such as alkylbenzenes; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylnaphthalene sulfonates such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, sodium octylnaphthalenesulfonate Anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinate ester salts such as sodium dilauryl sulfosuccinate; alkyl betaines such as lauryl betaine and stearyl betaine Although amphoteric surfactants such as amino acids can be used, anionic surfactants such as alkylnaphthalene sulfonates are particularly preferred.

  These surfactants can be used alone or in combination. Further, the content of the surfactant in the developer is preferably from 0.1 to 20% by mass in terms of active ingredient (in terms of solid content).

  In the developer concentrate, components such as organic solvents, chelating agents, reducing agents, dyes, pigments, hard water softeners, preservatives and antifoaming agents can be used in combination in addition to the above components. .

(Development stabilizer)
In the developer concentrate, various development stabilizers are preferably used. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride. Is a preferred example. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and water-soluble compounds described in JP-A-56-142528. There are amphoteric polymer electrolytes. Further, an organoboron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246, and JP-A-60 An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene of No. 129750, polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cationic group of JP-A-63-175858 Examples thereof include fluorine surfactants, water-soluble ethylene oxide addition compounds obtained by adding 4 mol or more of ethylene oxide to acids or alcohols disclosed in JP-A-2-39157, water-soluble polyalkylene compounds, and the like.

(Organic solvent)
If necessary, an organic solvent is added to the developer and the development replenisher. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 5% by mass or less. For example, 1- (or 2-) phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyl Examples include oxyethanol, benzyl alcohol, o- (or m-, p-) methoxybenzyl alcohol, cyclohexanol, 2- (or 3-, 4-) methylcyclohexanol, N-phenylethanolamine and N-phenyldiethanolamine. be able to.

  The content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the developer, but it is preferably substantially not contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.

(Reducing agent)
A reducing agent is added to the developer concentrate as necessary. This prevents stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include phenolic compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium salts, potassium salts and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. Can be mentioned. Of these reducing agents, sulfite is particularly excellent in the antifouling effect.

  These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.

(Organic carboxylic acid)
If necessary, an organic carboxylic acid can be further added to the developer concentrate. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,3- (or 2,4-, 2,5-, 2,6-) dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid There are acid, 1- (or 3-) hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like, and hydroxynaphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility.

  There is no particular restriction on the content of these organic carboxylic acids in the developer, but if the amount is less than 0.1% by mass, the effect is not sufficient, and if it is more than 10% by mass, the effect can be further improved. Not only that, it may interfere with dissolution when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

(Other additives)
In addition to the above, the following additives can be added to the developer concentrate in order to improve the developing performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, complexes such as [Co (NH ₃ )] ₆ Cl ₃ described in JP-A-59-121336, JP-A-56-142258 Amphoteric polymer electrolytes such as vinylbenzyltrimethylammonium chloride and sodium acrylate copolymers described in No. 59, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP-A-59-84241 And organic boron compounds described in the above-mentioned item.

  The developer and replenisher used for the plate making process of the printing plate material of the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softener, and the like as necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedioxalic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxy Aminopolycarboxylic acids such as ethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylene Phosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediamine Li (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

  The optimal value of such a hard water softener varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. More preferably, it is the range of 0.01-0.5 mass%. If the addition amount is less than this range, the intended purpose is not sufficiently achieved, and if the addition amount is more than this range, adverse effects on the image area such as color loss will occur.

(Automatic processor)
It is advantageous to use an automatic processor for developing the photosensitive lithographic printing plate material. The automatic developing machine is preferably provided with a mechanism for automatically replenishing the required amount of the developing replenisher to the developing bath, and preferably provided with a mechanism for discharging the developer exceeding a certain amount, preferably the developing bath. Is provided with a mechanism for automatically replenishing the required amount of water, preferably a mechanism for detecting plate passing is provided, preferably a mechanism for estimating the processing area of the plate based on detection of plate passing. Preferably, a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the detection of the printing plate and / or the estimation of the processing area is provided. Is provided with a mechanism for controlling the temperature of the developer, preferably a mechanism for detecting the pH and / or conductivity of the developer, preferably based on the pH and / or conductivity of the developer. Trying to replenish The amount of replenisher supplied and / or water and / or mechanism for controlling the replenishment timing is given that. The developer concentrate preferably has a function of once diluting and stirring with water. When there is a rinsing step after the development step, the rinsing water after use can be used as dilution water for the concentrate of the development concentrate.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid on the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 to 55 ° C. Is provided with a mechanism for rubbing the plate surface with a roller-like brush. Water or the like is used as the pretreatment liquid.

(Post-processing)
A lithographic printing plate developed with a developer having such a composition is subjected to a post-treatment with a washing water, a rinse solution containing a surfactant, a finisher or a protective gum solution mainly composed of gum arabic or starch derivatives. The These treatments can be used in various combinations. For example, the treatment with a rinsing solution containing development->washing-> surfactant or the development->washing-> finisher solution is preferable because of less fatigue of the rinse solution and the finisher solution. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment.

  These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. A method is also known in which a fixed amount of a small amount of washing water is supplied to the plate surface after the development, and the waste solution is reused as dilution water for the developing solution stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

(Gum solution)
It is preferable to add an acid or a buffer to the gum solution in order to remove alkali components from the developer. In addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizer, and the like can be added. . When the gum solution contains a hydrophilic polymer compound, a function as a protective agent for preventing scratches and stains on the developed plate is also added.

(Washing water before development)
A cleaning solution (pretreatment solution) used in a pretreatment part such as a washing step before development is usually water, but additives such as chelating agents, surfactants, and preservatives can be added as necessary.

  In the cleaning method, it is preferable to use the cleaning liquid used for pre-development cleaning by adjusting the temperature, and the temperature is preferably in the range of 10-60 ° C. As a cleaning method, known processing liquid supply techniques such as spraying, dipping, and coating can be used, and processing promoting means such as a brush, a drawing roll, and a submerged shower in the dip processing can be used as appropriate.

  The development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be carried out after drying before the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed. The pre-development rinse water that has been used once or more can be reused in post-development rinse water, rinse solution, or gum solution.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
<< Polymer binder: Synthesis of acrylic copolymer 1 >>
A three-necked flask under a nitrogen stream is charged with 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. The mixture was reacted for 6 hours in an oil bath at 0 ° C. 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 weight 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]
Using a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm, the treatment was continuously performed as follows.

(A) The aluminum plate was etched by spraying at a caustic soda concentration of 2.6 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C. to dissolve the aluminum plate by 0.3 g / m ² . Thereafter, washing with water was performed by spraying.

  (B) A desmut treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water by spraying.

(C) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time contains 1.1% by mass of hydrochloric acid, 0.5% by mass of aluminum ions, and 0.5% by mass of acetic acid. The temperature was 21 ° C. The AC power source was subjected to electrochemical surface roughening treatment using a sine wave alternating current having a time TP of 2 msec until the current value reached a peak from zero, using a carbon electrode as a counter electrode. The current density was an effective value of 50 A / dm ² and the energization amount was 900 C / dm ² . Then, water washing by spraying was performed.

  (D) A desmut treatment was performed for 10 seconds with a phosphoric acid concentration 20 mass% aqueous solution (containing 0.5 mass% of aluminum ions) at a temperature of 60 ° C., followed by washing with water by spraying.

  (E) An anodizing apparatus of an existing two-stage feed electrolytic treatment method (first and second electrolysis unit length 6 m, first feed unit length 3 m, second feed unit length 3 m, first and second feed electrode lengths 2.4 m each ) Was used to perform anodization at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) at a temperature of 38 ° C. Thereafter, washing with water was performed by spraying.

  At this time, in the anodizing device, the current from the power source flows to the first power supply electrode provided in the first power supply unit, flows to the plate-like aluminum via the electrolytic solution, An oxide film is formed on the surface, passes through the electrolytic electrode provided in the first power feeding portion, and returns to the power source.

On the other hand, the current from the power source flows to the second power feeding electrode provided in the second power feeding portion, similarly flows to the plate-like aluminum via the electrolytic solution, and an oxide film is formed on the surface of the plate-like aluminum by the second electrolysis portion. Although the amount of electricity fed from the power source to the first feeding unit and the amount of electricity fed from the power source to the second feeding unit are the same, the feeding current density on the oxide film surface in the second feeding unit is about It was 25 A / dm ² . In the 2nd electric power feeding part, it came to feed from the oxide film surface of 1.35 g / m < ² >. The final oxide film amount was 2.7 g / m ² . Furthermore, after spray water washing, it was immersed in 0.4 mass% polyvinylphosphonic acid solution for 30 seconds, and was hydrophilized. The temperature was 85 ° C. Thereafter, it was washed with spray water and dried with an infrared heater.
At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of photosensitive lithographic printing plate material)
On the above support, a photopolymerizable photosensitive layer coating solution having the following composition was coated with a wire bar so that the dried solution was 1.5 g / m ² and dried at 95 ° C. for 1.5 minutes. Got.

Further, on the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so as to be 1.8 g / m ² at the time of drying, and dried at 75 ° C. for 1.5 minutes. Photosensitive lithographic printing plate samples 1 to 10 having an oxygen blocking layer on the layer were prepared.

(Photopolymerizable photosensitive layer coating solution 1)
Ethylene double bond-containing monomer (1-17 (above)) 27.0 parts Ethylene double bond-containing monomer (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.)
14.0 parts Spectral sensitizing dye (dye-1) 3 parts Charge transport material (described in Table-1) 4 parts alone, 2 parts used together Photopolymerization initiator (Ti) 4.0 parts Acrylic copolymer Compound 1 45.0 parts Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluorosurfactant (FC-4430; manufactured by Sumitomo 3M) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts

(Oxygen barrier coating liquid)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 79 parts Polyvinylpyrrolidone (PVP K-30: manufactured by ASP Japan) 10 parts Polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts Cation-modified polyvinyl Alcohol (Kuraray C polymer: Kuraray Co., Ltd.) 5 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 parts <Developer composition>
A Potassium silicate 8.0 parts New Coal B-13SN (manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Pronon # 204 (Nippon Yushi Co., Ltd.) 1.0 part Caustic potash pH = 12.9 Additive amount << Photosensitive lithographic plate Evaluation of printing plate materials >>
(Evaluation of sensitivity)
Using a plate setter (manufactured by ECRM) equipped with a 405 nm light source, exposure was performed at 2400 dpi (dpi represents the number of dots per 2.54 cm). The exposure energy that reproduces 3% of the point corresponding to 3% of the output without linearity correction.

  The halftone dot output portion was photographed with a 1000 × optical microscope, and the area of the image portion was calculated to be halftone.

(Evaluation of printing durability)
Using a plate setter (manufactured by ECRM) equipped with a light source of 405 nm under the condition that the exposure energy on the printing plate is 50 μJ / cm ² , exposure is performed at 2400 dpi (dpi represents the number of dots per 2.54 cm). Went. After exposure, a preheating part for heat-treating the photosensitive lithographic printing plate at 105 ° C. for 10 seconds, a pre-water washing part for removing the oxygen blocking layer before development, a development part filled with a developer of the above composition, and a developer adhered to the plate surface Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with a washing section for removing water, and a gum solution for protecting the image area (GW-3: manufactured by Mitsubishi Chemical Corporation) Processing was carried out to obtain a lithographic printing plate.

  The prepared lithographic printing plate was coated with a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (Toyo King High Echo M Red manufactured by Toyo Ink Co., Ltd.) and dampening water (Tokyo Ink Co., Ltd.). ) Manufactured H liquid SG-51 density 1.5%), and after continuous printing 600 sheets, wipe the plate surface with a cleaner to reduce the number of prints where the highlight part is thin and the shadow part is entangled. It was used as an index of printing force.

  One printing durability refers to the operation of wiping with a cleaner after 600 continuous printings. The more it is, the better. The cleaner used was an Ultra Plate Cleaner (Distributor: Dainichi Seika Co., Ltd.).

(Evaluation of linearity)
A halftone dot image of 175 lines was drawn at an increment of 1% from 0% to 100% at 2400 dpi (dpi represents the number of dots per 2.54 cm). When exposed with Lake Biwa energy that reproduces 3%, a halftone dot output image that should be 70% was taken with a 1000 × optical microscope, and the area of the image area calculated was taken as linearity. The closer to 70%, the better.

  The results are shown in Table 1. From Table 1, it can be seen that the photosensitive lithographic printing plate material of the present invention is excellent in printing durability, sensitivity and linearity.

Example 2
Photosensitive lithographic printing as in Example 1 except that the photopolymerization initiator shown in Table 2 was used instead of the photopolymerization initiator in the photopolymerizable photosensitive layer coating solution 1 in Example 1. Plate samples 11 to 34 were prepared and evaluated.

  The results are shown in Table 2. From Table 2, it can be seen that the photosensitive lithographic printing plate material of the present invention is excellent in printing durability, sensitivity and linearity.

  Photosensitive lithographic printing in the same manner as in Example 1 except that the photopolymerization initiator shown in Table 3 was used instead of the photopolymerization initiator in the photopolymerizable photosensitive layer coating solution 1 in Example 1. Plate samples 35 to 46 were prepared and evaluated.

  The results are shown in Table 3. From Table 3, it can be seen that the photosensitive lithographic printing plate material of the present invention is excellent in printing durability, sensitivity and linearity.

Claims (6)

(A) Addition-polymerizable compound containing an ethylenic double bond, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a photosensitivity containing a dye having an absorption maximum wavelength of 350 to 450 nm. In the photosensitive composition, the photosensitive composition further contains a charge transport material. 2. The photosensitive composition according to claim 1, comprising a biimidazole compound or an iron arene complex compound as the photopolymerization initiator (B). The photosensitive composition according to claim 2, further comprising a polyhalogen compound as the photopolymerization initiator (B). The (A) addition-polymerizable ethylenic double bond-containing compound is a compound represented by the following general formula (1) or general formula (2). 2. The photosensitive composition according to item 1.

[Where Q ¹ is

Or -S-, R ⁴ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ³ represents a hydrogen atom, a methyl group or Represents an ethyl group, X ¹ represents a divalent group having 2 to 12 carbon atoms, and X ² represents a ² to 4 valent group, or

Z represents an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group, or a heterocyclic group, p represents an integer of 1 to 4, q represents an integer of 1 to 3, and p + q ≦ 5. . D ¹ and D ² each represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and E is a saturated hydrocarbon group having 2 to 12 carbon atoms, having 5 to 7 ring members. And a cycloaliphatic group containing up to two N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic fragrance having a 5-membered or 6-membered ring Represents a group, a represents 0 or an integer of 1 to 4, b represents 0 or 1, c represents an integer of 1 to 3, m represents an integer of 2 to 4 depending on the valence of Q ^1. , N represents an integer of 1 to m, and all groups having the same definition can be the same or different from each other. ]

[Where Q ² is

R ⁸ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. , D ³ and D ⁴ each represent a saturated hydrocarbon group having 1 to 5 carbon atoms, G is a saturated hydrocarbon group having 2 to 12 carbon atoms, and has 5 to 7 ring members And a cyclic aliphatic group containing up to 2 N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic aromatic group having 5 to 6 ring members D and e represent an integer of 1 to 4, g represents an integer of 2 to 4 depending on the valence of Q ² , f represents an integer of 1 to g, and all groups having the same definition are mutually It can be the same or different. ] A photosensitive lithographic printing plate material comprising a photosensitive layer made of the photosensitive composition according to claim 1 on an aluminum support. A method for recording a lithographic printing plate material, comprising performing image recording on the photosensitive lithographic printing plate material according to claim 5 using a laser beam having an emission wavelength in a range of 350 nm to 450 nm as a recording light source.