JP2004163918A - Photosensitive composition and photosensitive planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity and excellent printing durability and a photosensitive planographic printing plate. <P>SOLUTION: The photosensitive composition containing an addition polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymeric binder, in which the photopolymerization initiator composition contains a bromine compound expressed by the following general formula (1). The formula (1) is R<SP>1</SP>-CBr<SB>2</SB>-(C=O)-R<SP>2</SP>, where R<SP>1</SP>denotes a hydrogen atom, bromine atom, alkyl group, aryl group, acyl group, alkylsulfonyl group, arylsulfonyl group or cyano group. R<SP>2</SP>denotes a univalent substituent. Also, R<SP>1</SP>and R<SP>2</SP>may form a ring by bonding each other. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate, and more particularly to a photosensitive composition and a photosensitive lithographic printing plate having high sensitivity and excellent printing durability.

  In general, in a lithographic printing plate, after exposing an image, the exposed portion is cured, and the unexposed portion is dissolved and removed, followed by washing with water and finisher gum to obtain a lithographic printing plate. In recent years, in order to obtain high resolution and sharpness, a method of producing a lithographic printing plate by performing digital exposure with laser light based on image information and then performing development processing has been studied. For example, a system that modulates an exposure light source with an image signal transmitted by a communication line or an output signal from an electronic plate making system, an image processing system, etc., and directly scans and exposes a photosensitive material to produce a lithographic printing plate. It is.

  However, the conventional lithographic printing plate material using a diazo resin has a problem that it is difficult to increase the sensitivity and the spectral sensitization method in accordance with the oscillation wavelength of laser light by digital exposure. In recent years, lithographic printing plate materials having a photopolymerizable photosensitive layer containing a photopolymerization initiator have attracted attention for digital exposure with laser light because of its ability to achieve high sensitivity suitable for laser light. A CTP (Computer To Plate) plate material for recording digital data with the laser light source is required to have high sensitivity in order to shorten the recording time. In many printing fields, such as newspaper printing and commercial printing such as advertisements, plate materials having printing durability are required.

  Means utilizing photoradical polymerization have been studied for a long time to achieve high sensitivity, and use of an s-triazine compound having a trichloromethyl group as a photopolymerization initiator (for example, Patent Document 1, Patent Literature 2, Patent Literature 3.) Use of an iron arene complex compound and a peroxide as a photopolymerization initiator (for example, see Patent Literature 4). Use of a monoalkyltriaryl borate compound as a photopolymerization initiator. (For example, see Patent Literature 5, Patent Literature 6, and Patent Literature 7), and use of a titanocene compound as a photopolymerization initiator (for example, see Patent Literature 8 and Patent Literature 9). . However, these techniques have insufficient sensitivity.

On the other hand, for the purpose of improving sensitivity, a technique in which a tertiary amino group is introduced into a monomer (addition-polymerizable ethylenic double bond-containing monomer) structure and a trihalogenated methyl-s-triazine compound is used in combination ( For example, refer to Patent Document 10.), a tertiary amino group is introduced into a monomer (addition-polymerizable ethylenic double bond-containing monomer) structure, and in addition to a trihalogenated methyl-s-triazine compound, titanocene, etc. (For example, see Patent Literature 11) have been proposed, but with these techniques, although the sensitivity was improved, the printing durability was insufficient.
JP-A-48-36281 JP-A-54-74887 JP-A-64-35548 JP-A-59-219307 JP-A-62-150242 JP-A-62-143044 JP-A-64-35548 JP-A-63-41483 JP-A-2-291 JP-A-1-105238 JP-A-2-127404

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive composition and a photosensitive lithographic printing plate having high sensitivity and excellent printing durability.

The above object of the present invention is achieved by the following configurations.
(Claim 1) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition has at least the following general formula: A photosensitive composition comprising a bromine compound represented by the formula (1).

General formula (1) R ¹ —CBr ₂ — (C ＝ O) —R ²
In the formula, R ¹ represents a hydrogen atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group. R ² represents a monovalent substituent. Also, R ¹ and R ² may combine to form a ring.
(Claim 2) A photosensitive composition containing an addition-polymerizable monomer having an ethylenic double bond, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition has at least the following general formula: A photosensitive composition comprising a bromine compound represented by the formula (2).

General formula (2) CBr _3- (C = O) -XR ³
In the formula, R ³ represents a monovalent substituent. X is -O- or -NR ⁴ - represents a. R ⁴ represents a hydrogen atom or an alkyl group. Further, R ³ and R ⁴ may combine to form a ring.
(Claim 3) In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition may contain at least A photosensitive composition comprising a bromine compound represented by the formula (1) and a titanocene compound.
(Claim 4) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound described above. A photosensitive composition comprising a bromine compound represented by the formula (1) and a monoalkyltriaryl borate compound.
(Claim 5) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound described above. A photosensitive composition comprising a bromine compound represented by the formula (1) and an iron arene complex compound.
(Claim 6) In a photosensitive composition containing an addition-polymerizable monomer having an ethylenic double bond, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition may be at least one of A photosensitive composition comprising a bromine compound represented by the formula (2) and a titanocene compound.
(Claim 7) In a photosensitive composition containing an addition-polymerizable monomer having an ethylenic double bond, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least the general compound A photosensitive composition comprising a bromine compound represented by the formula (2) and a monoalkyltriaryl borate compound.
(Claim 8) In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition may contain at least A photosensitive composition comprising a bromine compound represented by the formula (2) and an iron arene complex compound.
(Claim 9) In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition may contain at least A photosensitive composition comprising a bromine compound represented by the formula (1) and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 10) In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is preferably at least A photosensitive composition comprising a bromine compound represented by the formula (1), a titanocene compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 11) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound A photosensitive composition comprising a bromine compound represented by the formula (1), a monoalkyltriarylborate compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 12) A photosensitive composition containing an addition-polymerizable monomer having an ethylenic double bond, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound A photosensitive composition comprising a bromine compound represented by the formula (1), an iron arene complex compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(13) A photosensitive composition comprising an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general A photosensitive composition comprising a bromine compound represented by the formula (2) and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 14) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound described above. A photosensitive composition comprising a bromine compound represented by the formula (2), a titanocene compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 15) In a photosensitive composition containing an addition-polymerizable monomer having an ethylenic double bond, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is preferably at least A photosensitive composition comprising a bromine compound represented by the formula (2), a monoalkyltriarylborate compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(Claim 16) A photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, wherein the photopolymerization initiator composition is at least the general compound described above. A photosensitive composition comprising a bromine compound represented by the formula (2), an iron arene complex compound, and a dye having an absorption maximum at 390 nm to 430 nm.
(17) The photosensitive composition according to any one of (1) to (16), wherein the addition-polymerizable ethylenic double bond-containing monomer has a tertiary amino group in the molecule. Composition.
(Claim 18) The addition-polymerizable ethylenic double bond-containing monomer is a polyhydric alcohol compound having a tertiary amino group in the molecule, a diisocyanate compound, and an addition-polymerizable ethylene having a hydroxyl group in the molecule. The photosensitive composition according to any one of claims 1 to 17, which is a reaction product with a compound containing an acidic double bond.
(19) A photosensitive lithographic printing plate comprising the support having a hydrophilic surface and the photosensitive composition according to any one of (1) to (18) coated thereon.

  According to the present invention, a photosensitive composition and a photosensitive lithographic printing plate having high sensitivity and excellent printing durability can be provided.

  As a result of intensive studies, the present inventors have found that the above composition can provide a photosensitive composition and a photosensitive lithographic printing plate having high sensitivity and excellent printing durability.

  Hereinafter, the details of the photosensitive composition of the present invention will be described.

  The photosensitive composition of the present invention is mainly composed of an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder.

  First, an addition-polymerizable ethylenic double bond-containing monomer will be described.

  Examples of the addition-polymerizable ethylenic double bond-containing monomer include general radically polymerizable monomers and a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for an ultraviolet curable resin. Polyfunctional monomers and polyfunctional oligomers can be used. These compounds are not limited, but preferred are, for example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, Monofunctional acrylates such as tetrahydrofurfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, and 1,3-dioxolane acrylate; or methacrylate, itaconate, crotonate, Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester substituted for maleate, such as ethylene glycol diester Acrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol dihydroxy hydroxypivalate diacrylate, neo Diacrylate of pentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3 -Dioxane diacrylate, tricyclodecane dimethylol acrylate, ε-caprolactone of tricyclodecane dimethylol acrylate Additives, bifunctional acrylates such as diacrylate of diglycidyl ether of 1,6-hexanediol; or methacrylic acid, itaconic acid, crotonic acid, maleic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, or maleate Acid esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, E-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol tria Polyacrylate acrylic acid such as acrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate; or methacrylate, itaconate, crotonate, or these acrylates. Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester and the like in place of maleate can be given.

  Further, a prepolymer can be used in the same manner as described above. Examples of the prepolymer include the compounds 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 also be suitably used. One or more of these prepolymers may be used in combination, or may be used as a mixture with the above-mentioned monomer and / or oligomer.

  As the prepolymer, for example, 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 and tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin and trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by bonding a polyhydric alcohol such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol. Acrylates, for example, epoxy acrylates obtained by introducing (meth) acrylic acid into an epoxy resin such as bisphenol A / epichlorohydrin / (meth) acrylic acid and phenol novolak / epichlorohydrin / (meth) acrylic acid; for example, ethylene glycol / adipin 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 Of trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate As described above, urethane acrylate in which (meth) acrylic acid is introduced into urethane resin, for example, polysiloxane acrylate, silicone resin acrylates such as polysiloxane / diisocyanate / 2-hydroxyethyl acrylate, and (meth) acryloyl in oil-modified alkyd resin Examples include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  In the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule as the addition-polymerizable ethylenic double bond-containing monomer. Although there is no particular limitation on the structure, a compound obtained by modifying a tertiary amine compound having a hydroxyl group with glycidyl methacrylate, methacrylic chloride, acrylic acid chloride or the like is preferably used. Specifically, those described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  In the present invention, the addition-polymerizable ethylenic double bond-containing monomer includes a polyhydric alcohol compound having a tertiary amino group in the molecule, a diisocyanate compound, and an addition-polymerizable ethylene having a hydroxyl group in the molecule. It is preferable to use a reaction product with a compound containing an acidic double bond.

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

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, and 1,3-diisocyanatomethyl-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. This But it is not limited to.

  Examples of the compound containing an addition-polymerizable ethylenic double bond having a hydroxyl group in the molecule include the following compounds such as MH-1 to MH-13, but are not limited thereto.

  Preferably, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate and the like are exemplified.

  The reaction with a polyhydric alcohol compound having a tertiary amino group in the molecule, a diisocyanate compound and a compound containing an addition-polymerizable ethylenic double bond having a hydroxyl group in the molecule is carried out by a usual diol compound, diisocyanate compound, The reaction can be performed in the same manner as in the method of synthesizing urethane acrylate by the reaction of the group-containing acrylate compound.

  In addition, specific examples of the reaction products with a polyhydric alcohol compound having a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an addition-polymerizable ethylenic double bond having a hydroxyl group in the molecule are described below. However, the present invention is not limited to these.

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), 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 (isocyanate) Natomethyl) 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) Acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.

  The photosensitive composition of the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, and trimethylolpropane acrylate benzoate. It may contain a monomer such as an acid ester, an alkylene glycol type acrylic acid-modified or a urethane-modified acrylate, and an addition-polymerizable oligomer or prepolymer having a structural unit formed from the monomer.

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

  In addition, JP-A-58-212994, JP-A-61-6649, JP-A-62-46688, JP-A-62-48589, JP-A-62-173295, JP-A-62-187092, and 63- Compounds described in JP-A-67189, JP-A-1-244891 and the like can be mentioned, and furthermore, "11290 Chemical Products", Chemical Daily, p. 286-p. 294, “UV / EB curing handbook (raw material edition)”, Polymer Publishing Association, p. The compounds described in 11 to 65 and the like can also be suitably used in the present invention. Of these, compounds having two or more acrylic or methacrylic groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In the photosensitive composition of the present invention, the proportion of the ethylenic double bond-containing monomer capable of addition polymerization is preferably contained in the range of 1 to 80% by mass, more preferably 3 to 70% by mass. Range.

  Next, the photopolymerization initiator composition will be described. The photopolymerization initiator composition according to the present invention is characterized by containing at least a bromine compound represented by the following general formula (1).

General formula (1) R ¹ —CBr ₂ — (C ＝ O) —R ²
In the formula, R ¹ represents a hydrogen atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group. R ² represents a monovalent substituent. Also, R ¹ and R ² may combine to form a ring. Examples of the monovalent substituent represented by R ² include a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an amino group, and an alicyclic amino group (cycloalkylamino group, adamantylamino group Etc.), arylamino group, alkylamino group (in the case of dialkyl substitution, alkyl may form a ring with each other), alkenylamino group, alkylsulfamoyl group, arylsulfamoyl group, arylsulfonyl group, alkyl Preferable examples include a sulfonyl group, an alkoxy group, an alicyclic oxy group (such as a cycloalkyloxy group and an adamantyloxy group), an aryloxy group, an amide group, and a cyano group. Further, these substituents may be further substituted with another substituent.

  Further, among the bromine compounds represented by the general formula (1), a bromine compound represented by the following general formula (2) is particularly preferable.

General formula (2) CBr _3- (C = O) -XR ³
In the formula, R ³ represents a monovalent substituent. X is -O- or -NR ⁴ - represents a. R ⁴ represents a hydrogen atom or an alkyl group. Further, R ³ and R ⁴ may combine to form a ring. Examples of the monovalent substituent represented by R ³ include a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group (such as a cycloalkyl group and an adamantyl group), an aryl group, and an alkenyl group. Further, these substituents may be further substituted with another substituent.

  Representative specific examples (BR1 to BR66) of the bromine compounds represented by the general formulas (1) and (2) are shown below, but the present invention is not limited thereto.

  BR2 to BR47 are compounds included in the general formula (2).

  The titanocene compound which is a photopolymerization initiator which can be preferably used in combination with the bromine compound according to the present invention will be described.

  Examples of the titanocene compound 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, and 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 (methylcyclopenta Dienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5 6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,6-difluorophenyl (IRUGACURE727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6- Difluoro-3- (pyrid-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyri-1) -Yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (2-5-dimethylpyr-1-yl) phenyl) titanium and the like.

  The monoalkyl triaryl borate compound which is a photopolymerization initiator which can be preferably used in combination with the bromine compound according to the present invention will be described.

  Examples of the monoalkyltriaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044. More preferred specific examples include tetra-n-butylammonium. n-butyl-trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-tert-butylphenyl) -borate And tetra-n-butylammonium / n-hexylrytoly (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium / n-hexyllytoly ((3-fluorophenyl) -borate, and the like.

  The iron arene complex compound which is a photopolymerization initiator which can be preferably used in combination with the bromine compound according to the present invention will be described.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred specific examples are η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron Hexafluorophosphate, η-xylene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron / tetrafluoroborate and the like can be mentioned.

  When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer. It is preferable to use a dye having an absorption maximum wavelength near the wavelength of the light source. Compounds that sensitize wavelength from visible light to near infrared include, for example, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenyl Keto alcohol borate complexes such as methane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, etc. And further, European Patent 568,993, U.S. Pat. Nos. 4,508,811 and 5,227,227, JP-A-2001-1252. 5 discloses, compounds described in JP-A 11-271969 Patent Publication also used. Further, specific examples of the combination of the photopolymerization initiator and the sensitizing dye include a combination described in JP-A-2001-125255 and JP-A-11-271969. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in molar ratio.

  Further, when recording is performed using a semiconductor laser having an emission wavelength in the range of 390 nm to 430 nm as a laser beam of a light source, that is, a violet laser, it is desirable to include a dye having an absorption maximum between 390 nm and 430 nm. The dye having an absorption maximum between 390 nm and 430 nm is not particularly limited in structure, but the above-mentioned cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, Polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbitur Any dye group such as an acid derivative and a keto alcohol borate complex can be used as long as the absorption maximum satisfies the requirement. Specifically, JP-A-2002-296564, JP-A-2002-268239, JP-A-2002-268238, JP-A-2002-268204, JP-A-2002-221790, JP-A-2002-202598 JP, JP-A-2001-42524, JP-A-2000-309724, JP-A-2000-258910, JP-A-2000-206690, JP-A-2000-147763, and JP-A-2000-98605 And the like, but are not limited thereto.

  The amount of the photopolymerization initiator composition according to the present invention is not particularly limited. Although it varies depending on the type and combination of the photopolymerization initiator used, it is generally 0.1 to 20 parts by mass relative to 100 parts by mass of the addition-polymerizable ethylenic double bond-containing monomer. When the photopolymerization initiator to be used is a bromine compound represented by the general formula (1) or a bromine compound represented by the general formula (2), 100 parts by mass of an addition-polymerizable ethylenic double bond-containing monomer 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, per part. When a titanocene compound, a monoalkyltriaryl borate compound, or an iron arene complex compound is used in combination, the amount of these compounds may be 0.1 to 100 parts by mass of the addition-polymerizable ethylenic double bond-containing monomer. -15 parts by mass is preferred. Further, when a dye having an absorption maximum at 390 nm to 430 nm is used in combination, an appropriate amount of the dye varies depending on the molar extinction coefficient of the dye, but generally, based on 100 parts by mass of an addition-polymerizable ethylenic double bond-containing monomer. 0.1 to 15 parts by mass.

  In addition, an arbitrary photopolymerization initiator can be used in combination. For example, J. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar. And the like. More specific compounds are disclosed in GB 1,459,563. That is, the following can be used as a photopolymerization initiator that can be used in combination. Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone and N-butylacridone Α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, as well as JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Described triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, and JP-A-44-6413. Diazonium compounds described in JP-A-47-1604 and U.S. Pat. No. 3,567,453; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853. Organic azide compounds described in JP-B-36-22062, JP-B-37-13109, JP-B-38-18015, and JP-B-45-9610; 39162, JP-A-59-14023, "Macromolecules", Vol. 10, p. 1307 (1977) Various onium compounds; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109,851 and 126,712, "Journal of Imaging" Science (J. Imag. Sci.), Vol. 30, p. 174 (1986); (oxo) sulfonium described in Japanese Patent Application Nos. 4-56831 and 4-89535. Organic boron complexes; Transition metal complexes containing transition metals such as ruthenium described in "Coordination Chemistry Review", vol. 84, pp. 85-277 (1988), and JP-A-2-182701; 2,4,5-tri as described in JP-A-3-209777 Reel imidazole dimer; carbon tetrabromide, organic halogen compounds described in JP-A-59-107344 and the like.

  Next, the polymer binder will be described.

  As the polymer binder according to the present invention, for example, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, Other natural resins and the like can be used. Further, two or more of these may be used in combination. In each of the above-mentioned polymer binders, it is preferably a vinyl copolymer obtained by copolymerization of an acrylic monomer, and further, the copolymer composition of the polymer binder includes (a) a carboxyl group-containing monomer, (b) It is preferably a copolymer of an alkyl methacrylate or an alkyl acrylate. 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, and itaconic anhydride. In addition, a carboxylic acid such as a half ester of phthalic acid and 2-hydroxymethacrylate is also preferable. Specific examples of alkyl methacrylate and alkyl acrylate include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacryl Nonyl acid, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate And unsubstituted alkyl esters such as decyl acrylate, undecyl acrylate, and dodecyl acrylate, and cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate. Ter, benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Substituted alkyl esters and the like can be mentioned.

  Furthermore, in the polymer binder according to the present invention, the following monomers (1) to (14) and the like can be used as other copolymerized monomers.

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

  (2) Monomers having an aliphatic hydroxyl group, for example, 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) Monomers having an aminosulfonyl group, for example, 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, for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  (5) acrylamide or methacrylamides, for example, 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 an alkyl fluoride group, for example, 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, for example, 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, and vinyl benzoate.

  (9) Styrenes, for example, styrene, methylstyrene, chloromethylstyrene and the like.

  (10) Vinyl ketones, for example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.

  (11) Olefins, for example, 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, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethylacrylate, o- (or m-, p-) cyanostyrene and the like.

  (14) Monomers having an amino group, for example, 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 copolymerizable with these monomers may be copolymerized.

  Further, a double bond-containing vinyl copolymer obtained by subjecting a carboxyl group present in the molecule of the vinyl copolymer to an addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule is also included. Preferred as a polymer binder. Specific examples of the compound containing both a double bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing double compound described in JP-A-11-271969. These copolymers preferably have a mass average molecular weight of from 10,000 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range. The polymer binder, if necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolak resin, natural resin, etc. You may use together with a copolymer. The content of the polymer binder in the composition for coating the photopolymerizable 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 in the range of 20 to 60% by mass. Is particularly preferable from the viewpoint of sensitivity. Furthermore, the vinyl-based copolymer obtained by copolymerization of an acrylic monomer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass in the polymer binder. The acid value of the polymer contained in the polymer binder according to the present invention is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and more preferably in the range of 50 to 90. It is particularly preferable from the viewpoint of balancing the polarities of the entire photosensitive layer, whereby the aggregation of the pigment in the coating solution for the photosensitive layer can be prevented.

  Hereinafter, various additives that can be added to the photosensitive composition according to the present invention, a support as a photosensitive lithographic printing plate, a protective layer, application of the photosensitive composition to the support, a photosensitive lithographic printing plate Will be sequentially described.

(Various additives)
The photopolymerizable photosensitive layer containing the photosensitive composition of the present invention, in addition to the components described above, an ethylenic double double bond monomer polymerizable during the production or storage of the photosensitive lithographic printing plate It is desirable to add a polymerization inhibitor in order to prevent unnecessary polymerization. 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), cerium N-nitrosophenylhydroxylamine, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like. The addition amount of the polymerization inhibitor is preferably from about 0.01% to about 5% based on the total solid content of the composition. Also, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Good. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition. A coloring agent can also be used, and conventionally known coloring agents including commercially available coloring agents can be suitably used. For example, those described in the revised new edition “Pigment Handbook”, edited by the Japan Pigment Technical Association (Seibundo Shinkosha), Color Index Handbook, and the like can be mentioned. Examples of the type of the pigment include a black pigment, a yellow pigment, a red pigment, a brown pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, and a metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium, and calcium, etc.) and organic pigments (azo, thioindigo) , Anthraquinone, anthranthrone, and triphenedioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, and quinacridone pigments. Among these, it is preferable to select and use a pigment that does not substantially absorb in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used, and in this case, an integrating sphere at the laser wavelength to be used is used. The reflection and absorption of the pigment used is preferably 0.05 or less. The amount of the pigment is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the solid content of the composition. When an argon laser (488 nm) or an SHG-YAG laser (532 nm) is used as an exposure light source, violet pigments and blue pigments are used from the viewpoints of pigment absorption in the above-described photosensitive wavelength region and visibility after development. Preferably, it is used. Such materials include, for example, cobalt blue, cerulean blue, alkali blue lake, Phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue fast sky blue, indanthrene blue, indico, dioxane violet, isohexane Biolanthrone violet, indanthrone blue, indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferred. Further, the above composition may contain a surfactant as a coatability improver as long as the performance of the present invention is not impaired. Among them, preferred are fluorine-based surfactants. Further, in order to improve the physical properties of the cured film, additives such as an inorganic filler and 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 solids. Further, as a solvent used when preparing the photosensitive composition of the photopolymerizable photosensitive layer according to the present invention, for example, alcohols: derivatives of polyhydric alcohols include sec-butanol, isobutanol, 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: diacetone Alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like are preferred.

(Protective layer: oxygen blocking layer)
It is preferable to provide a protective layer on the photopolymerizable photosensitive layer according to the invention. The protective layer (oxygen blocking layer) preferably has high solubility in a developing solution (generally an aqueous alkaline solution) described later, and specific examples thereof include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing oxygen permeation, and polyvinyl pyrrolidone has an effect of securing adhesiveness with an adjacent photosensitive layer. In addition to the above two polymers, if necessary, polysaccharide, polyethylene glycol, gelatin, glue, casein, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylstarch, gum arabic, saccharose octaacetate, ammonium alginate, sodium alginate And water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrenesulfonic acid, polyacrylic acid, and water-soluble polyamide.

  In the lithographic printing plate according to the present invention, the peeling force between the photosensitive layer and the protective layer is preferably at least 35 mN / mm, more preferably at least 50 mN / mm, even more preferably at least 75 mN / mm. Preferred protective layer compositions include those described in Japanese Patent Application No. 8-161645. The peeling force in the present invention is determined by applying an adhesive tape of a predetermined width having a sufficiently large adhesive force on the protective layer and peeling the adhesive tape together with the protective layer at an angle of 90 degrees with respect to the plane of the planographic printing plate material. It can be determined by measuring. The protective layer may further contain a surfactant, a matting agent, and the like, if necessary. The protective layer composition is dissolved in a suitable solvent, coated on 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 and the like. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

(Support)
The support according to the present invention has a hydrophilic surface, for example, a metal plate of aluminum, stainless steel, chromium, nickel, or the like, or a plastic film such as a polyester film, a polyethylene film, or a polypropylene film laminated or deposited with the above-described metal thin film. A polyester film, a vinyl chloride film, a nylon film, etc. whose surface has been subjected to a hydrophilization treatment can be used, but an aluminum support is preferably used. In this case, pure aluminum or aluminum It may be an alloy.

  As the aluminum alloy of the support, various materials can be used, for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, or iron is used. .

  The support according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). Examples of the degreasing treatment include a degreasing treatment using a solvent such as trichlene and thinner, and an emulsion degreasing treatment using an emulsion such as kesilon and triethanol. For the degreasing treatment, an aqueous solution of an alkali such as caustic soda can be used. 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 above degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support. In this case, the smut is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. Preferably, a treatment is applied. Examples of the method of surface roughening include a mechanical method and a method of etching by electrolysis.

The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The surface roughening by the brush polishing method is performed, for example, by rotating a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm, and applying, for example, particles of volcanic ash having a particle size of 10 to 100 μm to water on the support surface. It can be performed by pressing a brush while supplying a uniformly dispersed slurry. For surface roughening by honing polishing, for example, particles of volcanic ash having a particle size of 10 to 100 μm are uniformly dispersed in water, pressure is applied from a nozzle to be ejected, and the surface is made to impinge obliquely on the support surface to perform surface roughening. Can be. Further, for example, abrasive particles having a particle size of 10 to 100 μm are coated on the surface of the support at an interval of 100 to 200 μm at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ^2. The sheets can be roughened by laminating the sheets and transferring the rough surface pattern of the sheet by applying pressure.

After the surface is roughened by the above-mentioned mechanical surface roughening method, it is preferable to immerse the substrate in an aqueous solution of an acid or an alkali in order to remove the abrasive, the formed aluminum dust and the like that have penetrated the surface of the support. As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . After performing the immersion treatment with an alkali aqueous solution, it is preferable to immerse in an acid such as phosphoric acid, nitric acid, sulfuric acid, and chromic acid or a mixed acid thereof to perform a neutralization treatment.

Although the electrochemical surface roughening method is not particularly limited, a method of performing electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used for an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, the methods described in JP-B-48-28123, UK Patent 896,563, and JP-A-53-67507 can be used. This surface roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature for performing the surface roughening method can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

When performing electrochemical surface roughening using a nitric acid-based electrolyte as an electrolyte, it can be generally performed by applying a voltage in a range of 1 to 50 volts, but is selected from a range of 10 to 30 volts. Is preferred. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The nitric acid concentration in the electrolytic solution is preferably from 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of ^{100~5000c / dm 2, 100~2000c / dm} 2, and more preferably selected from the range of 200~1000c / dm ^2. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolyte is preferably 0.1 to 5% by mass.

After the surface is roughened by the above-mentioned electrochemical surface roughening method, it is preferable to immerse in an aqueous solution of an acid or alkali to remove aluminum dust and the like on the surface. As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . Further, it is preferable that after immersion treatment with an aqueous alkali solution, immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof to perform neutralization treatment.

  The mechanical surface roughening method and the electrochemical surface roughening method may be used alone for roughening, or the mechanical surface roughening method may be followed by the electrochemical surface roughening method. The surface may be roughened.

Subsequent to the roughening treatment, an anodic oxidation treatment can be performed. The method of the anodic oxidation treatment that can be used in the present invention is not particularly limited, and a known method can be used. By performing the anodic oxidation treatment, an oxide film is formed on the support. For the anodic oxidation treatment, a method of electrolyzing at an electric current density of 1 to 10 A / dm ² using an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is preferably used. Japanese Patent No. 1,412,768 discloses a method of electrolyzing at high current density in sulfuric acid, a method of electrolyzing using phosphoric acid described in 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more of oxalic acid and malonic acid. The formed anodized coating amount is suitably from 1 to 50 mg / dm ² , and preferably from 10 to 40 mg / dm ² . The anodic oxidation coating amount is obtained, for example, by immersing an aluminum plate in a chromic phosphate solution (prepared by dissolving 35 g of 85% phosphoric acid and 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It can be determined by measuring the change in mass before and after dissolving the coating on the plate.

  The support subjected to the anodizing treatment may be subjected to a sealing treatment as required. These sealing treatments can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

  Furthermore, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-5-304358 is preferably used.

(Application)
The prepared photosensitive composition (photosensitive layer coating solution) is applied on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of the application method of the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method, an extrusion coater method, and the like. Can be mentioned. If the drying temperature of the photosensitive layer is too low, sufficient printing durability cannot be obtained, and if it is too high, not only Marangoni occurs but also fogging of non-image areas occurs. The preferred drying temperature range is 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.

(Image recording method)
Examples of the light source for imagewise exposing the lithographic printing plate according to the present invention include a laser, a light-emitting diode, a xenon lamp, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high-pressure mercury lamp, and an electrodeless light source. Can be mentioned. In the case of collective exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be overlaid on the photopolymerizable photosensitive layer and exposed. When using an array type light source such as a light emitting diode array, or when controlling the exposure of a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp with an optical shutter material such as a liquid crystal or PLZT, a digital signal corresponding to an image signal is used. Exposure is possible and preferred. In this case, writing can be performed directly without using a mask material. In the case of laser exposure, light can be squeezed into a beam to perform scanning exposure in accordance with image data, so that it is suitable for directly writing without using a mask material. When a laser is used as a light source, the exposure area can be easily reduced to a very small size, and high-resolution image formation is possible. As a laser light source, any of an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, and the like can be suitably used. In the present invention, a laser light source having an emission wavelength in the visible region is preferably used. Specifically, there are a double high wavelength YAG laser emitting at around 532 nm, an Ar ion laser emitting at around 488 nm, and the like. In the present invention, a semiconductor laser that uses an InGaN-based or ZnSe-based material and that can continuously oscillate in the 380 to 430 nm region is also preferably used. Laser scanning methods include cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which a recording material is wound around the outer surface, and rotation of the drum is defined as main scanning and movement of laser light is defined as sub-scanning. In the cylindrical inner surface scanning, a recording material is fixed on the inner surface of the drum, a laser beam is irradiated from the inside, and a main scan is performed in the circumferential direction by rotating a part or all of the optical system, and a part of the optical system or Sub-scanning is performed in the axial direction by moving the whole linearly in parallel to the axis of the drum. In the planar scanning, the main scanning of the laser beam is performed by combining a polygon mirror or a galvanometer mirror with an fθ lens, and the sub-scanning is performed by moving the recording medium. The scanning of the outer surface of the cylinder and the scanning of the inner surface of the cylinder are easier to improve the precision of the optical system, and are suitable for high-density recording.

(Preheat)
In the present invention, it is preferable to heat-treat the photosensitive lithographic printing plate material after exposing the lithographic printing plate to an image and before or during the developing process. By performing the heat treatment in this manner, the adhesiveness between the photosensitive layer and the support is improved, and the effect of the invention according to the present invention can be improved. Preheating according to the present invention, for example, in an automatic developing device for developing a photosensitive lithographic printing plate material, by a preheat roller that heats the photosensitive lithographic printing plate carried during the developing process to a predetermined temperature range before development. A heating method can be given. For example, the pre-heat roller includes a pair of rollers including at least one roller having a heating unit therein, and the roller having the heating unit includes a hollow member made of a metal having a high thermal conductivity (eg, aluminum, iron, or the like). A pipe in which a nichrome wire or the like is embedded as a heating element inside the pipe and the outer surface of the metal pipe is covered with a plastic sheet such as polyethylene, polystyrene, or Teflon (R) can be used. For details of such a preheat roller, reference can be made to JP-A-64-80962. The preheating in the present invention is preferably performed at 70 to 180 ° C. for about 3 to 120 seconds.

(Developer)
The exposed portion of the photosensitive layer subjected to image exposure is cured. By developing this with an alkali developing solution, the unexposed portion is removed and an image can be formed. As such a developing solution, a conventionally known aqueous alkali solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium An alkali developer using an inorganic alkali agent such as 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 alkaline agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used. These alkaline agents are used alone or in combination of two or more. Further, an organic solvent such as an anionic surfactant, an amphoteric surfactant, or an alcohol can be added to the developer as needed. The aqueous solution according to the present invention is basically preferably an aqueous solution having a silicic acid concentration of 1.0% by mass in terms of SiO ₂ and a pH in a range of 8.5 to 12.5. May be contained. Further, an aqueous solution further containing a surfactant in the range of 0.1% by mass or more and 5.0% by mass or less is more preferable. Further, the aqueous solution according to the present invention preferably also contains the components of the developer described above.

  Hereinafter, a synthesis example, a support preparation example, and a photosensitive lithographic printing plate preparation example will be specifically described, but embodiments of the present invention are not limited thereto. In the examples, “parts” means “parts by mass” unless otherwise specified.

(Example 1)
<< Synthesis of Polymer Binder: Acrylic Copolymer 1 >>
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 were put into a three-necked flask under a nitrogen stream. The reaction was performed for 6 hours in an oil bath at ℃. Then, after refluxing for 1 hour at the boiling point of isopropyl alcohol, 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.

<< Preparation of photosensitive lithographic printing plate >>
(Preparation of support)
A 0.3 mm-thick aluminum plate (material 1050, tempered H16) was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. The degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute to neutralize, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening in an aqueous 0.3% by mass nitric acid solution at a temperature of 25 ° C. and a current density of 100 A / dm ^{2 with} an alternating current for 60 seconds, and then maintained at 60 ° C. Desmut treatment was performed for 10 seconds in the 5% aqueous sodium hydroxide solution. The desmutted roughened aluminum plate was subjected to anodizing treatment in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute, and further 1% polyvinyl phosphonic acid was added. The substrate was subjected to a hydrophilic treatment at 75 ° C. to prepare a support. At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of photosensitive lithographic printing plate)
A coating solution of a photopolymerizable photosensitive layer having the following composition was applied on the support with a wire bar so as to be dried at 1.5 g / m ² and dried at 95 ° C. for 1.5 minutes. Got. Further, an oxygen barrier layer coating solution having the following composition was applied to the photopolymerized photosensitive layer coated sample with an applicator so that the coating liquid became 1.8 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes. A photosensitive lithographic printing plate sample of the present invention having a oxygen blocking layer on the photosensitive layer was prepared (Sample 1 of the present invention).

(Coating solution for photopolymerizable photosensitive layer)
Addition-polymerizable ethylenic double bond-containing monomer shown in Table 1 Amount shown in Table 1 Photopolymerization initiator composition shown in Table 1 Amount shown in Table 1 Acrylic copolymer 1 40.0 parts N-phenyl Glycine benzyl ester 4.0 parts Phthalocyanine pigment (MHI454: manufactured by Mikuni Color 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 part Fluorinated surfactant (F-178K; manufactured by Dainippon Ink) 0.5 part Methyl ethyl ketone 80 parts Cyclohexanone 820 parts Addition polymerization in sample 1 of the present invention is possible. The inventive sample was prepared in the same manner as in the inventive sample 1, except that the various ethylenic double bond-containing monomers and the photopolymerization initiator composition were changed to those shown in Tables 1 to 6. 2 was produced present invention sample 60.

  Further, the same as the sample 1 of the present invention except that the addition-polymerizable ethylenic double bond-containing monomer and the photopolymerization initiator composition in the sample 1 of the present invention were changed to those shown in Tables 1 to 6 and the amounts thereof. Comparative Sample 1 to Comparative Sample 16 were produced.

  The chemical structural formulas of I-1 to I-6 and D-1 to D-4 in the column of the photopolymerization initiator composition in Tables 1 to 6 are as follows. In addition, λmax in D-1 to D-4 is the maximum absorption wavelength of each dye.

(Oxygen barrier coating solution)
Polyvinyl alcohol (GL-05: manufactured by Nippon Gosei Kagaku) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries) 10 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industries) 0.5 part Water 900 Part 《Evaluation of photosensitive lithographic printing plate》
(Measurement of sensitivity)
Each of the photosensitive lithographic printing plates prepared above was exposed at 2400 dpi using a plate setter (Tiger Cat: ECRM) equipped with a 532 nm light source. The term “dpi” in the present invention indicates the number of dots per 2.54 cm. As the exposure pattern, a 100% image area and 175 lpi (lpi represents the number of lines per 2.54 cm) square dots of 50% were used. After exposure, a preheating section for heating the photosensitive lithographic printing plate at 105 ° C. for 10 seconds, a washing section for removing an oxygen barrier layer before development, a developing section filled with a developer of the following composition, and a developer attached to the plate surface Developing with a CTP automatic developing machine (PHW23-V: Techniggraph) equipped with a water washing unit for removing oil and a gum solution (GW-3: manufactured by Mitsubishi Chemical Co., 2 times diluted) for protecting the image area. Processing was performed to obtain a lithographic printing plate.

The sensitivity was defined as an index of sensitivity, using the minimum exposure energy (μJ / cm ² ) at which no film loss was observed in the 100% image area recorded on the plate surface of the lithographic printing plate as the recording energy. The smaller the recording energy, the higher the sensitivity.

  The results are shown in Tables 1 to 6 above.

<Developer composition>
A potassium silicate 8.0 mass%
Newcol B-13 (manufactured by Nippon Emulsifier) 3.0% by mass
Caustic potash Addition amount when pH = 12.3 (Evaluation of printing durability)
A lithographic printing plate prepared by exposing and developing an image of 175 lines at 200 μJ / cm ² was coated on a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) with coated paper and printing ink (manufactured by Dainippon Ink and Chemicals, Inc.). Printing using soybean oil ink "Naturalis 100") and a fountain solution (Tokyo Ink Co., Ltd., H-solution SG-51 concentration 1.5%) to produce spots in highlights. The number of sheets was used as an index of printing durability.

  The results are shown in Tables 1 to 6 above. Tables 1 to 6 show that the sample of the present invention has higher sensitivity and better printing durability than the comparative sample.

(Example 2)
Except that the addition-polymerizable ethylenic double bond-containing monomer and the photopolymerization initiator composition in Sample 1 of the present invention were changed to those shown in Tables 7 to 9 in the same manner as in Sample 1 of the present invention, Inventive Samples 61 to 90 were prepared. Further, the same as Sample 1 of the present invention except that the addition-polymerizable ethylenic double bond-containing monomer and the photopolymerization initiator composition in Sample 1 of the present invention were changed to those shown in Tables 7 to 9 and the amounts thereof. To prepare Comparative Samples 17 to 25.

  The chemical structural formulas of D-5 to D-7 in the column of the photopolymerization initiator composition in Tables 7 to 9 are as follows. In addition, λmax in D-5 to D-7 is the maximum absorption wavelength of each dye.

<< Evaluation of photosensitive lithographic printing plate >>
(Measurement of sensitivity)
Example 1 except that the plate setter (Tigercat: ECRM) provided with a 532 nm light source in Example 1 was replaced with a plate setter (Tigercat: ECRM) improved with a 408 nm, 30 mW output laser. Performed in the same manner as 1.

(Evaluation of printing durability)
Performed in the same manner as in Example 1.

  The results are shown in Tables 7 to 9 above. Tables 7 to 9 show that the sample of the present invention has higher sensitivity and better printing durability than the comparative sample.

Claims (19)

In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the following general formula (1). A photosensitive composition comprising a bromine compound represented by the formula:
General formula (1) R ¹ —CBr ₂ — (C ＝ O) —R ²
In the formula, R ¹ represents a hydrogen atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group. R ² represents a monovalent substituent. Also, R ¹ and R ² may combine to form a ring. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition has at least the following general formula (2): A photosensitive composition comprising a bromine compound represented by the formula:
General formula (2) CBr _3- (C = O) -XR ³
In the formula, R ³ represents a monovalent substituent. X is -O- or -NR ⁴ - represents a. R ⁴ represents a hydrogen atom or an alkyl group. Further, R ³ and R ⁴ may combine to form a ring. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound represented by the formula (1) and a titanocene compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound represented by the formula (1) and a monoalkyltriarylborate compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound represented by the formula and an iron arene complex compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound represented by the formula (1) and a titanocene compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound represented by the formula (1) and a monoalkyltriarylborate compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound represented by the formula and an iron arene complex compound. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising the bromine compound represented and a dye having an absorption maximum at 390 nm to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound, a titanocene compound and a dye having an absorption maximum at 390 to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound, a monoalkyltriarylborate compound, and a dye having an absorption maximum at 390 nm to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (1). A photosensitive composition comprising a bromine compound, an iron arene complex compound, and a dye having an absorption maximum at 390 nm to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising the bromine compound represented and a dye having an absorption maximum at 390 nm to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound, a titanocene compound and a dye having an absorption maximum at 390 to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound, a monoalkyltriarylborate compound, and a dye having an absorption maximum at 390 nm to 430 nm. In a photosensitive composition containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator composition, and a polymer binder, the photopolymerization initiator composition is at least represented by the general formula (2). A photosensitive composition comprising a bromine compound, an iron arene complex compound, and a dye having an absorption maximum at 390 nm to 430 nm. 17. The photosensitive composition according to claim 1, wherein the addition-polymerizable ethylenic double bond-containing monomer has a tertiary amino group in the molecule. The addition-polymerizable ethylenic double bond-containing monomer is a polyhydric alcohol compound having a tertiary amino group in the molecule, a diisocyanate compound and an addition-polymerizable ethylenic double bond having a hydroxyl group in the molecule. The photosensitive composition according to any one of claims 1 to 17, which is a reaction product with a compound containing the same. 19. A photosensitive lithographic printing plate comprising the support having a hydrophilic surface and the photosensitive composition according to claim 1 applied thereon.