WO2009128302A1

WO2009128302A1 - Lithographic printing plate material, and method for production of lithographic printing plate

Info

Publication number: WO2009128302A1
Application number: PCT/JP2009/054289
Authority: WO
Inventors: 孝彰黒木
Original assignee: コニカミノルタエムジー株式会社
Priority date: 2008-04-17
Filing date: 2009-03-06
Publication date: 2009-10-22

Abstract

Disclosed is a lithographic printing plate material which comprises: a support; and a photosensitive layer comprising (A) a compound having an ethylenically unsaturated bond, (B) a photopolymerization initiator, (C) a polymeric binder and (D) a sensitizing dye, wherein the photosensitive layer contains a compound (E) having an ethylenically unsaturated bond, a thiourethane bond (-SCONH-) and a tertiary amine structure in the molecule as the compound (A) having an ethylenically unsaturated bond. The lithographic printing plate material has high sensitivity and excellent printing durability.

Description

Lithographic printing plate material and lithographic printing plate preparation method

The present invention relates to a lithographic printing plate material used in a computer-to-plate system (hereinafter referred to as CTP) and a method for producing a lithographic printing plate using the same, and more particularly to a lithographic printing plate material suitable for exposure with a laser beam having a wavelength of 350 to 450 nm. The present invention also relates to a method for producing a planographic printing plate using the same.

In recent years, CTP that directly records digital image data 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, as described in JP-A-1-105238 and JP-A-2-127404, a polymerization type containing a polymerizable compound is used. It is known to use a negative photosensitive lithographic printing plate material having a photosensitive layer.

Furthermore, a printing plate material is known that can be exposed to light with a laser having a wavelength of 390 nm to 430 nm and has improved safe light properties from the viewpoint of handling of the printing plate.

In addition, a high-power and small-sized blue-violet laser having 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 Document 1).

Furthermore, as described in, for example, JP-A-63-277653, a printing plate material containing a biimidazole in a photosensitive layer is known which has improved safe light property under a yellow light.

Examples of the polymerizable compound include a plurality of double bonds and a plurality of alcoholic hydroxyl groups such as an ester compound of an aliphatic polyhydric alcohol compound such as pentaerythritol diacrylate and dipentaerythritol diacrylate and an unsaturated carboxylic acid. A compound having a hydroxyl group, for example, a urethane-based addition-polymerizable compound produced by the addition reaction of an isocyanate and a hydroxyl group described in JP-B-48-41708, an addition-polymerizability having an amino structure and a urethane bond in the molecule Compounds (see Patent Documents 2 and 3) and the like are known.

However, the printing plate material has problems such as insufficient printing durability and insufficient sensitivity, and it is difficult to satisfy both sensitivity and printing durability at the same time.
JP 2001-264978 A JP-A 63-277653 JP-A-63-260909

An object of the present invention is to provide a lithographic printing plate material having high sensitivity and excellent printing durability, and is particularly suitable for exposure with a laser beam having an emission wavelength in the range of 350 nm to 450 nm. An object of the present invention is to provide a lithographic printing plate material having excellent printing properties.

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

1. A lithographic printing plate material having a photosensitive layer containing (A) an ethylenically unsaturated bond-containing compound, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a sensitizing dye on a support. The photosensitive layer contains (A) a compound (E) having an ethylenically unsaturated bond, a thiourethane bond (—SCONH—) and a tertiary amine structure in the molecule as the ethylenically unsaturated bond-containing compound. A lithographic printing plate material characterized by:

2. 2. The lithographic printing plate material according to 1, wherein the compound (E) has two or more thiourethane bonds.

3. The lithographic printing plate material according to 1 or 2, wherein the compound (E) has two or more ethylenically unsaturated bonds.

The lithographic printing plate material according to any one of 4.1 to 3 is subjected to image exposure using a laser beam having an emission wavelength in the range of 350 nm to 450 nm as a light source, and development processing is performed after the image exposure. A method for preparing a lithographic printing plate.

The above configuration of the present invention can provide a lithographic printing plate material having high sensitivity and excellent printing durability, and is particularly suitable for exposure with a laser beam having an emission wavelength in the range of 350 nm to 450 nm. A lithographic printing plate material excellent in printing durability can be provided.

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

In the present invention, a photosensitive layer containing (A) an ethylenically unsaturated bond-containing compound, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a sensitizing dye is lithographically formed on a support. In the printing plate material, the photosensitive layer is a compound (E) having an ethylenically unsaturated bond, a thiourethane bond (—SCONH—) and a tertiary amine structure in the molecule as the (A) ethylenically unsaturated bond-containing compound (E). A lithographic printing plate material comprising:

In the present invention, a lithographic printing plate material having high sensitivity and excellent printing durability can be provided because the polymerizable component has a thiourethane bond and a tertiary amine structure.

Each component used in the photosensitive layer according to the present invention will be described.

((A) ethylenically unsaturated bond-containing compound)
The photosensitive layer contains, as the ethylenically unsaturated bond-containing compound, a compound (E) having an ethylenically unsaturated bond, a thiourethane bond (—SCONH—) and a tertiary amine structure in the molecule.

Having a tertiary amine structure according to the present invention means having the following structure in the molecule. However, the nitrogen atom of the following formula is not bonded to a hydrogen atom.

Compound (E) has an ethylenically unsaturated bond, a thiourethane bond (—SCONH—) and a tertiary amine structure in the molecule, and preferably has at least two thiourethane bonds, and more preferably an ethylenically unsaturated bond. Is preferably 2 or more from the viewpoints of sensitivity and printing durability.

As a method for synthesizing the compound (E), the following methods are typically mentioned.
(1) A method of reacting an aminothiol compound with a (meth) acrylate having an isocyanato group (2) A compound having a tertiary amine structure and an isocyanato group is reacted with a (SH) -containing (meth) acrylate Method (3) Method of reacting aminothiol, diisocyanate compound, -OH group-containing (meth) acrylate, or -SH group-containing (meth) acrylate (4) A tertiary amine structure and an isocyanato group Method of reacting compound having polythiol compound with (meth) acrylate having isocyanato group Method of (1) An aminothiol compound is a compound having a secondary or tertiary amine moiety and at least one thiol group at the end. It is. For example, 2-aminoethanethiol, 3-aminopropanethiol, 3- (N-methyl) aminopropanethiol, 3- (N, N-dimethyl) propanethiol, 3- (N-ethyl) aminopropanethiol, 3- (N, N-diethyl) propanethiol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2- (N-methyl) aminothiophenol, 3- (N-methyl) aminothiophenol, 4- (N-methyl) aminothiophenol, 2- (N, N-dimethyl) aminothiophenol, 3- (N, N-dimethyl) aminothiophenol, 4- (N, N-dimethyl) aminothiophenol, etc. Is mentioned.

(Meth) acrylates having an isocyanato group are acrylates or methacrylates having an isocyanato group at the terminal.

Examples of (meth) acrylates having an isocyanato group include 2- (meth) acryloyloxyethyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, and further known diisocyanate compounds and hydroxyl group-containing (meth). Reaction products with acrylate, acrylic acid, methacrylic acid, and other acid group-containing (meth) acrylates can also be suitably used.

As the known diisocyanate, the following compounds can be preferably used.

Diisocyanate compounds 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.

Further, for example, norbornene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric Diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 5-isocyanate-1- (isocyanatemethyl) -1,3,3-trimethylcyclohexane, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene- 1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene 1,2-diisocyanate, butylene 1,2-diisocyanate, cyclohexylene 1,2-diisocyanate, can be mentioned diisocyanates such as cyclohexylene-1,4-diisocyanate.

Still further, triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and toluene-2,4,6-triisocyanate, 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5 ′ -Tetraisocyanates such as tetraisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of 2,4-tolylene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, hexanetriol addition of tolylene diisocyanate And isocyanate prepolymers such as products.

Or a known diisocyanate and a known hydroxy acrylate, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl diacrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy Examples include compounds obtained by reacting -3-phenoxypropyl acrylate, pentaerythritol triacrylate, and the like. Preferably, 5-isocyanate-1- (isocyanatomethyl) -1,3,3-trimethylcyclohexane and 2- Adducts of hydroxyethyl acrylate, 2- (5-isocyanate-1,3,3-trimethyl-cyclohexylmethylcarbamoyloxy) -ethyl acrylate, 2- (3-isocyanate Methyl-3,5,5-trimethyl-cyclohexylcarbamoyloxy) -ethyl acrylate, 2- (4'-isocyanate-4-diphenylmethanecarbamoyloxy) -ethyl acrylate, 2- (5-isocyanate-1-carbamoyloxy) -ethyl Acrylate, 4- (5-isocyanate-1,3,3-trimethyl-cyclohexylmethylcarbamoyloxy) -butyl acrylate, 4- (3-isocyanatemethyl-3,5,5-trimethyl-cyclohexylcarbamoyloxy) -butyl acrylate, 4- (4'-isocyanate-4-diphenylmethanecarbamoyloxy) -butyl acrylate, 4- (5-isocyanate-1-carbamoyloxy) -butyl acrylate, 2-methacryloyloxy Chill isocyanate, and the like.

Of these, 2- (meth) acryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate are preferable. Used.

The compound (E) can be obtained by reacting the aminothiol compound as described above with a (meth) acrylate having an isocyanato group.

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

Method (2) The compound having a tertiary amine structure and an isocyanato group is a compound having a tertiary amine structure in the molecule and an isocyanato group. For example, a known tertiary amino alcohol and a bifunctional or higher functional isocyanate It can be obtained as a reaction product of a group-containing compound.

As the tertiary amino alcohol, both monoalcohols and polyols can be suitably used.

Examples of tertiary amino alcohols include ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-methylethanolamine, N-aminoethylethanolamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 3-aminopropanol, 1-amino-propan-2-ol, 4-aminobutanol, 5-amino-pentan-1-ol, 3,3'-iminodipropanol, N -Ethyl-2,2'-iminodiethanol and the like can be mentioned. In addition, 2-amino-2- (hydroxymethyl) propane-1,3-diol, 2-amino-2-methylpropane-1,3-diol, 3-amino-1-propanol, ilopropanolamine, 4- Amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol 2- (ethylamino) ethanol, 2-amino-2-ethyl-1,3-propanediol, N-aminoethylethanolamine, 2- (3-aminopropylamino) ethanol, 2- (2-aminoethoxy) Ethanol is exemplified, and among these, preferred amino alcohol is a compound represented by the following (I).

In the formula, R ¹ is an alkylene group or a divalent group in which two or more alkylene groups are linked by an ether bond. R ² and R ³ are each a hydrogen atom or an alkyl group. The alkylene group and the alkyl group may have a substituent. The alkylene group and the alkyl group may be linear, branched, or cyclic. Examples of the substituent of the alkylene group and alkyl group include (alcoholic) hydroxyl group, amino group, substituted amino group, alkoxy group, substituted alkoxy group, aryl group, substituted aryl group, aryloxy group and substituted aryloxy group. included. Two or more compounds of the formula (I) may be combined to form a polymer. For example, a derivative in which an amino group is introduced as a substituent into a polymer having an alcoholic hydroxyl group (eg, polyvinyl alcohol or cellulose) can also be used.

The —SH group-containing (meth) acrylate is an ester compound of acrylic acid or methacrylic acid having a —SH group in the molecule. For example, phenylthiol (meth) acrylate, naphththiol (meth) acrylate, 4-chlorophenylthiol ( (Meth) acrylate, 2-thiolethyl methacrylate, 2-thiolpropyl methacrylate, 2-thiolethyl acrylate, 2-thiolpropyl acrylate, 4-thiolbutyl acrylate, 2-thiol-3-methacryloyloxypropyl methacrylate, 2-thiol-3 -Acryloyloxypropyl methacrylate, etc.

(E) can be obtained by reacting the above-mentioned compound having a tertiary amine structure and an isocyanato group with -SH group-containing (meth) acrylates.

Method (3) As the aminothiol compound, the same aminothiol compound used in the method (1) can be used.

As the diisocyanate compound, the above-mentioned compounds can be preferably used.

As the —SH group-containing (meth) acrylate, the above-mentioned compounds can be preferably used.

The —OH group-containing (meth) acrylate is an ester compound of acrylic acid or methacrylic acid having an —OH group in the molecule, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-methacryloyloxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

The compound (E) can be obtained by reacting an aminothiol compound, an isocyanate compound, and an —OH group-containing (meth) acrylate.

Method (4) The compound having a tertiary amine structure and an isocyanato group may be the same as the compound having a tertiary amine structure and an isocyanato group used in the method (2).

Examples of (meth) acrylates having an isocyanato group include the same (meth) acrylates having an isocyanato group as described in (1).

The polythiol compound is a compound having a plurality of —SH groups.

Specific examples of the polythiol compound include the following.

1,1-methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, , 2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, -Methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2, 3-dimercapto-1-propanol (3-mercaptopropionate ), Diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) ) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate) , Trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis ( Rukaputomechiru) aliphatic polythiol compound such as methane.

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (me Captoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane.

1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1 , 2,4-Tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) ) Benzene, 1,3,5-tris (mercaptoethylthio) benzene and the like.

Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) Propane, 1,2,3-tris (2 Mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl- 1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1, 11-mercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3- Dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5- Mercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis Aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as (mercaptoethyl) disulfide and bis (mercaptopropyl) disulfide, and esters of these thioglycolic acid and mercaptopropionic acid.

Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl Sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bi (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1, 4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thio Dipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) Ester), 4,4-di Odibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2, 3-dimercaptopropyl ester), bis (2,3-dimercaptopropyl ester) dithiodipropionate and other mercapto groups, an aliphatic polythiol compound containing a sulfur atom and an ester bond, 3,4-thiophenedithiol , Heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole.

2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercapto Propionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis ( - mercaptopropionate), hydroxymethyl - tris (mercaptoethylthiomethyl) methane, compounds containing a hydroxy group other than the mercapto group such as 1-hydroxyethyl-thio-3-mercaptoethylthio benzene.

1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-Dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4- Bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-pro Dithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercapto) Methylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis ( Mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) Tan, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1 , 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12, 14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8, 10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto- 2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathia Hexadecane, 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4 , 6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7- Mercapto-2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-di Anilthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-bis (mercaptomethylthio) propane, 1- { 4- (6-Mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetra Thiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -2,4 , 6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithiee Nyl)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3- Dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -6 -{4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1 , 11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Zimmer Capto-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl-1,9-dimercapto-2,4,6 , 8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1,3 -Dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis (mercaptomethyl) E) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio)- 8-mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-di Thiahexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} mercaptomethylthiomethyl-1,3-dithietane, 2 -{3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio} mercap Methylthiomethyl-1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1 , 3-dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [Bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithietane, 4- {4- (5-mercaptomethylthio-1,3-dithi Oranyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, and dithioacetal or dithioketal skeletons of these oligomers A compound having

Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl] (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-di Acyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4 -Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -1-thiaethyl] methane, tris [3,3 -Bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] Tan, 2,4,6-tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl ] Compounds having an ortho trithioformate skeleton such as methane and these oligomers.

3,3'-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2'-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof Examples include compounds having an orthotetrathiocarbonate skeleton, but are not limited to these exemplary compounds. These exemplary compounds may be used alone or in combination of two or more.

A compound (E) can be obtained by reacting a tertiary amine compound and a compound having an isocyanate group, a polythiol compound, and a (meth) acrylate having an isocyanate group.

Examples of compounds used for synthesizing compound (E) are further shown below.

(Aminothiol compound)

(Isocyanato group-containing acrylates)

(Compound having tertiary amine structure and isocyanate group)
It can be synthesized by a reaction between the following polyol compound and the following isocyanato group-containing compound.

(-SH group-containing acrylate)

The content of the compound (E) thus obtained in the photosensitive layer is preferably from 3 to 85% by mass, particularly preferably from 20 to 75% by mass, based on the photosensitive layer in terms of sensitivity and printing durability.

Further, (A) 10% by mass to 100% by mass of the whole ethylenically unsaturated bond-containing compound is preferable, and 20% by mass to 95% by mass is particularly preferable.

Specific examples of the compound (E) are shown below, but the present invention is not limited thereto.

The photosensitive layer may contain an ethylenically unsaturated bond-containing compound other than the compound (E) as the (A) ethylenically unsaturated bond-containing compound.

Examples of the ethylenically unsaturated bond-containing compound that can be used in combination include general radical-polymerizable monomers, and many compounds having a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for ultraviolet curable resins. Functional 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 acrylates 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 obtained by replacing these acrylates 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.

Also, prepolymers can be used in the same manner 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 in which (meth) acrylic acid is introduced into polyester obtained by the combination of polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates 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, hydroxyethyl phthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate As described above, urethane acrylates in which (meth) acrylic acid is introduced into a urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, and other oil-modified alkyd resins (meth) Examples thereof include prepolymers such as alkyd-modified acrylates and spirane resin acrylates into which acryloyl groups are introduced.

Photosensitive layer is phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, alkylene glycol type Addition-polymerizable oligomers and prepolymers having monomers such as acrylic acid-modified and urethane-modified acrylate and structural units formed from the monomers can be contained.

Furthermore, examples of the ethylenically unsaturated bond-containing compound that can be used in combination with the present invention include a phosphoric ester compound 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 Nos. 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Furthermore, “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.

Furthermore, an ethylenically unsaturated bond-containing compound other than the compound (E) containing a tertiary amino group in the molecule is also preferably used.

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. The reaction product can be used.

Here, the polyhydric alcohol containing a tertiary amino group in the molecule includes 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.

Diisocyanate compounds 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. In Not a constant.

Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3. -Dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate and the like.

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

((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.

(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-di Toxiphenyl) 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 mass, preferably 0.5 to 20% by mass, based on the total mass of the non-volatile components of the photosensitive composition.

<Iron arene complex compound>
The iron arene complex compound 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, pyrene and the like. 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.

The iron arene complex compound is preferably contained in a proportion of 0.1 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the compound having a polymerizable group.

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 2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti- Bis-2,6-difluorophenyl (IRGACURE 727L: manufactured by Ciba Japan), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRGACURE 784: Ciba・ Made in Japan), 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.

(Polyhalogen compound)
The polyhalogen compound is a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group, and includes a trihalomethyltriazine compound, a compound represented by the following general formula (I), and an oxadiazole ring having the above group in the oxadiazole ring. Diazole compounds are preferably used. Of these, compounds having a trihalogenmethyl group are preferably used.

Examples of trihalomethyltriazine compounds include 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, such as 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)- 4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis-trichloromethyl-S-triazine, and the compounds described in German Patent No. 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.

Next, the general formula (I) will be described.

Formula (I) R ¹ —C (Y) ₂ — (C═O) —R ²
In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group. R ² represents a monovalent substituent. R ¹ and R ² may be bonded to form a ring. Y represents a halogen atom.

The monovalent substituent represented by R ² is substituted, unsubstituted alkyl group, substituted, unsubstituted aryl group, substituted, unsubstituted heterocyclic group, substituted, unsubstituted alkoxy group, substituted, unsubstituted Represents an aryloxy group, a substituted, an unsubstituted amino group or a hydroxyl group.

Of these, polyhalogen compounds represented by the following general formula (II) are particularly preferably used.

Formula (II) C (Y) ₃ — (C═O) —XR ³
In the formula, R ³ represents a monovalent substituent. X represents —O— or —NR ⁴ —, and R ⁴ represents a hydrogen atom or an alkyl group. When X is —NR ⁴ —, R ³ and R ⁴ may be bonded to each other to form a ring. Y represents a halogen atom.

The monovalent substituent represented by R ³ represents a substituted, unsubstituted alkyl group, a substituted, unsubstituted aryl group, or a substituted, unsubstituted heterocyclic group.

Among the compounds represented by the general formula (I), those having a trihalogenacetylamide group are particularly preferable.

Moreover, an oxadiazole compound having a polyhalogenmethyl group in the oxadiazole ring is also preferably used. Furthermore, oxadiazole compounds described in JP-A-5-34904 and 8-240909 are also preferably used.

Examples of the oxime derivatives include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyl And oxyimino-1-phenylpropan-1-one.

Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-1050242 and JP-A-62-143044, and more preferable 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, tetra -N-butylammonium.n-hexylroot- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium.n-hexylroot- (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.

Preferably, a vinyl copolymer obtained by copolymerization of an acrylic monomer is preferable. 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 methacrylate esters and alkyl methacrylate 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 Cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate, in addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate, and dodecyl acrylate Substituted alkyl such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Also included are esters.

Furthermore, for the polymer binder, the 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 methacrylamide such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

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

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

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

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

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

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) Monomers having amino groups 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 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 examples include (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.

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 under the boiling point of the solvent used (under reflux), 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. Specifically, examples of the amine-based material include triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, and 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 these are used as a catalyst, they may be added in an amount of 0.01 to 20.0% by mass relative to the alicyclic epoxy group-containing unsaturated compound to be used. Polymerization inhibitors include 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 thereof used is 0.01 to 5.0% by mass with respect to the alicyclic epoxy group-containing unsaturated compound 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% by mass relative to the compound having a double bond to be used. Polymerization inhibitors include 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 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 vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably 50 to 100% by mass and more preferably 100% by mass in the total polymer binder.

The water-soluble polymer binder is preferably used as the polymer binder according to the present invention.

The water-soluble polymer compound refers to a compound having a solubility in water (g number dissolved in water 100 at 25 ° C.) of 1.0 or more and a molecular weight (mass average) of 500 or more.

Examples of water-soluble polymer compounds include polyvinyl alcohols having various saponification degrees, polymers of hydroxystyrene and copolymers thereof, polyamide resins, copolymers of polyvinylpyrrolidone and vinylpyrrolidone, polyethylene oxide, polyethyleneimine, and polyacrylic. Examples include acid amide, corn starch, mannan, pectin, agar, dextran, pullulan, glue, hydroxymethylcellulose, alginic acid, carboxymethylcellulose, sodium polyacrylate, and the like.

As the water-soluble polymer compound, a polymer compound having a nonionic hydrophilic group is particularly preferably used.

The molecular weight is preferably in the range of 1,000 to 100,000, particularly preferably in the range of 1,000 to 50,000 in terms of printing durability and image reproducibility.

The photosensitive layer according to the present invention may contain a compound other than the water-soluble polymer compound as a binder, but the proportion of the water-soluble polymer compound in the binder is from 80 to 100 based on the total binder. % By mass is preferred, and 90 to 100% is particularly preferred.

The content of the binder is preferably 10% by mass to 95% by mass, particularly preferably 30% by mass to 90% by mass with respect to the photosensitive layer.

Examples of the binder that can be used in combination include polyvinyl butyral resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins.

(High molecular compound having nonionic hydrophilic group)
The nonionic hydrophilic group of the polymer compound having a nonionic hydrophilic group is a group or bond that exhibits hydrophilicity without being ionized in water. For example, an alcoholic hydroxyl group, an aromatic hydroxyl group, an acid Examples include an amide group, a sulfonamide group, a thiol group, a pyrrolidone group, a polyoxyethylene group, a polyoxypropylene group, and a sugar residue.

As the polymer compound having a nonionic hydrophilic group, a compound containing 30% by mass or more of a nonionic hydrophilic group is particularly preferable from the viewpoint of developability.

The nonionic hydrophilic group-containing compound is preferably an oligomer or polymer having a mass average molecular weight of 1,000 to 50,000 in terms of developability and image reproducibility. For example, the nonionic hydrophilic group described above is used. Examples thereof include polymers obtained by polymerizing one or more unsaturated monomers having a functional group in the side chain, polyvinyl alcohol polymers, cellulose polymers that are polysaccharides, and glucose polymers.

For example, unsaturated monomers having an amide group in the side chain include unsubstituted or substituted (meth) acrylamide, itaconic acid, fumaric acid, maleic acid and other dibasic acid amidation monomers, N-vinylacetamide, N- Examples include vinyl formamide and N-vinyl pyrrolidone.

More specific examples of unsubstituted or substituted (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, butoxymethyl (meth) ) Acrylamide, propyl (meth) acrylamide, (meth) acryloylmorpholine, and the like.

Further, in the case of an amidation monomer of a dibasic acid such as itaconic acid, a monoamide in which one carboxyl group is amidated, a diamide in which both carboxyl groups are amidated, and further one carboxyl group is amidated, An amide ester in which the other carboxyl group is esterified may be used.

Examples of unsaturated monomers having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and monomers obtained by adding ethylene oxide or propylene oxide to these (meth) acrylates. And methylol (meth) acrylamide, and methoxymethyl (meth) acrylamide and butoxymethyl (meth) acrylamide which are condensates of methylol (meth) acrylamide and methyl alcohol or butyl alcohol.

The description such as “(meth) acryl”, “(meth) acrylate”, “(meth) acryloyl” means acryl or methacryl, acrylate or methacrylate, acryloyl or methacryloyl, respectively.

The polyvinyl alcohol polymer will be described in more detail. A polymer obtained by completely or partially hydrolyzing a homopolymer or copolymer of a fatty acid vinyl monomer such as vinyl acetate or vinyl propionate, and a partial formalization or acetalization of this polymer. Examples include butyralized polymers.

The compound containing 30% by mass or more of the nonionic hydrophilic group may have a crosslinkable functional group that reacts with the crosslinker. Specific examples of the crosslinkable functional group vary depending on the type of the crosslinking agent to be used, but nonionic ones are preferable, and examples thereof include a hydroxyl group, an isocyanate group, a glycidyl group, and an oxazoline group. In order to introduce these crosslinkable functional groups, unsaturated monomers having these functional groups, for example, unsaturated monomers having a hydroxyl group described above, glycidyl (meth) acrylate, etc. as other unsaturated monomers having a glycidyl group ( What is necessary is just to copolymerize with a meth) acrylate monomer.

In order to further improve the effect of the present invention, the compound containing 30% by mass or more of the nonionic hydrophilic group is other than the unsaturated monomer having the nonionic hydrophilic group and the unsaturated monomer having a crosslinkable functional group. In addition, other copolymerizable unsaturated monomers can be copolymerized.

Other copolymerizable unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, methoxy (C1 to C50) ) Ethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, isopolonyl (meth) acrylate, adamantyl (meth) acrylate, cyclohexyl ( And (meth) acrylate, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, and α-olefin (C4 to C30).

Reaction described in “Crosslinking agent handbook” (Tosuke Kaneko, Junzo Yamashita, Taiseisha, 1981) as a crosslinking agent used to crosslink a compound containing 30% by mass or more of a nonionic hydrophilic group A combination of a crosslinking agent and a functional group can be selected.

For example, known polyhydric alcohol compounds that react with a hydroxyl group, a glycidyl group, or an amide group as the crosslinkable functional group in a compound containing 30% by mass or more of a nonionic hydrophilic group as a crosslinking agent, Carboxylic acid compounds and their anhydrides, polyvalent glycidyl compounds (epoxy resins), polyvalent amine compounds, polyamide resins, polyvalent isocyanate compounds (including block isocyanates), oxazoline resins, amino resins And glyoxal.

Among the crosslinking agents described above, various curing agents for epoxy resins such as various polyvalent glycidyl compounds (epoxy resins), oxazoline resins, amino resins, polyvalent amine compounds, and polyamide resins are known in terms of developability and printability. And glyoxal are preferred.

Examples of amino resins include known melamine resins, urea resins, benzoguanamine resins, glycoluril resins, and modified resins of these resins, such as carboxy-modified melamine resins. In order to accelerate the crosslinking reaction, tertiary amines are used in combination with the above-described glycidyl compounds, and acidic compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and ammonium chloride are used in combination with amino resins. May be. When the photosensitive resin composition is heated with hot air, heated with a roller, heated with a laser, or the like, these crosslinking agents react to crosslink with a compound containing 30% by mass or more of a nonionic hydrophilic group.

In the present invention, among the water-soluble polymer compounds, polymer compounds having vinylpyrrolidone as a constituent monomer unit are particularly preferably used, and examples thereof include the following.
1. Vinylpyrrolidone-vinyl acetate copolymer (60/40) mass average molecular weight 34000
Product name: Lubiscol 64, manufactured by BASF Japan, VP / VA = 60 mol% / 40 mol% copolymer Vinylpyrrolidone-1 / butene copolymer (90/10) Mass average molecular weight 17000
Product Name: GANEX P-904 LC ISP chemicals
3. Vinylpyrrolidone-glycidyl methacrylate copolymer (70/30) mass average molecular weight 10,000
The content of the polymer binder in the photosensitive layer is preferably in the range of 10 to 90% by weight, more preferably in the range of 15 to 70% by weight, and the use in the range of 20 to 50% by weight from the viewpoint of sensitivity. Particularly preferred.

(Sensitizing dye)
The sensitizing dye according to the present invention is a dye having absorption at the emission wavelength of a light source used for image exposure and is not particularly limited. However, in the present invention, a dye having an absorption maximum wavelength of 350 to 450 nm is preferably used. .

The sensitizing dye having an absorption maximum in the wavelength range of 350 to 450 nm is not particularly limited in terms of structure. Polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, stilbenes, distyrylbenzenes, Distyrylbiphenyls, divinylstilbenes, triazinylaminostilbenes, stilbenyltriazoles, stilbenylnaphthotriazoles, biphenyl -Triazolestilbenes, benzoxazoles, bisphenylbenzoxazoles, stilbenylbenzoxazoles, bis-benzoxazoles, furans, benzofurans, bis-benzimidazoles, diphenylpyrazolines, diphenyl Oxadiazoles, naphthalimides, xanthenes, carbostyrils, pyrenes and 1,3,5-triazinyl-derivatives, barbituric acid derivatives, thiobarbituric acid derivatives, etc. As long as the absorption maximum satisfies the requirement, any of them can be used.

Specifically, JP-A No. 2002-296664, JP-A No. 2002-268239, JP-A No. 2002-268238, JP-A No. 2002-268204, JP-A No. 2002-221790, JP-A No. 2002-202598, JP-A No. 2001 are disclosed. -042524, JP-A-2000-309724, JP-A-2000-258910, JP-A-2000-206690, JP-A-2000-147663, JP-A-2000-098605, JP-A-2003-295426, etc. However, the present invention is not limited to this. Coumarin derivatives and distyrylbenzenes are particularly preferred.

Hereinafter, various additives that can be added to the photosensitive layer in the present invention, a support as a photosensitive lithographic printing plate, a protective layer, a coating of the photosensitive composition on the support, and an image forming method for the photosensitive lithographic printing plate Etc. will be sequentially described.

(Various additives)
In addition to the components described above, a polymerization inhibitor is added to the photosensitive layer to prevent unnecessary polymerization of the ethylenic double bond monomer that can be polymerized during the production or storage of the photosensitive lithographic printing plate. It is desirable to do. 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 higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

In addition, a colorant can also be used, and as the colorant, conventionally known ones can be suitably used, including commercially available ones. 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 pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. 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. The addition 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.

From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, it is preferable to use a purple pigment or a blue pigment. 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.

In addition, the composition can contain a surfactant as a coating property improving agent as long as the performance of the present invention is not impaired. Of these, fluorine-based surfactants are preferred.

In order to improve the physical properties of the cured film, additives such as inorganic fillers and plasticizers 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.

Examples of the solvent used for the photosensitive layer coating solution prepared for providing the photosensitive layer according to the present invention include, for example, alcohol: polyhydric alcohol derivatives: 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: di Preferred examples include acetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

Although the photosensitive layer according to the present invention has been described above, the lithographic printing plate material according to the present invention is constituted by mixing and preparing the above-mentioned compositions so as to have the above ratios, and coating the mixture on an aluminum support. Is done.

(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.

The protective layer (oxygen barrier layer) preferably has high solubility in a developer (described below, generally an alkaline aqueous 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 the lithographic printing plate material of the present invention has a protective layer, 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. . A preferred protective layer composition includes 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 and i-propanol.

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

(Support)
The support according to the present invention is a plate or film capable of carrying a photosensitive layer, and preferably has a hydrophilic surface on the side where the photosensitive layer is provided.

Examples of the support according to the present invention include a metal plate such as aluminum, stainless steel, chromium and nickel, or a laminate obtained by laminating or vapor-depositing the above metal thin film on a plastic film such as a polyester film, a polyethylene film and a polypropylene film. .

Also, a surface of a polyester film, vinyl chloride film, nylon film or the like that has been subjected to a hydrophilic treatment can be used, but an aluminum support is preferably used.

In the case of an aluminum support, pure aluminum or an aluminum alloy is 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. . Further, the aluminum support having a roughened surface is used for water retention.

In the case of an aluminum support, it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). 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, 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 performed, for example, by rotating a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle diameter of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. For roughening by honing, for example, volcanic ash particles having a particle size of 10 to 100 μm are uniformly dispersed in water, sprayed by applying pressure from a nozzle, and subjected to roughening by colliding with the surface of the support at an angle. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are coated on the surface of the support so as to exist 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 amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

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. Electrolytic surface roughening is performed for 10 seconds to 120 seconds at a current density of / dm ² or more and 100 A / dm ² or less. 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 100 ~ 5000C / dm ^2, still preferably selected from the range of 100 ~ 2000C / dm ^2.

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.

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 amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . 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 anodic oxidation treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid or the like 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 anodic oxidation coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (produced by dissolving 85% phosphoric acid solution: 35 ml, chromium oxide (IV): 20 g in 1 L of water), dissolving the oxide coating, It is calculated | required from the mass change measurement etc. before and after melt | dissolution of the coating.

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 higher and 70 ° C. or lower 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 lithographic printing plate material can be prepared by adjusting a coating solution for a photopolymerizable photosensitive layer containing a photosensitive composition, applying the coating solution on a support by a conventionally known method, and drying. 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, and if it 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 exposure)
In the image exposure according to the present invention, an image is formed by curing the photosensitive layer in the exposed portion by polymerization. In the present invention, a laser beam having an emission wavelength of 350 to 450 nm is used as the light source. preferable.

As a light source, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid state laser, KNbO 3 as a semiconductor laser system, a ring resonator (430 nm), AlGaInN (350 nm to 450 nm) And an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm).

In the case of laser exposure, light can be narrowed down in the form of a beam and scanning exposure according to the image data is possible, which is suitable for direct writing without using a mask material.

Further, 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 a recording material is wound, and the rotation of the drum is used as main scanning, and the movement of laser light is used as sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. 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 to 300 mJ / cm ² . For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by Ophir Optronics can be used.

(Developer)
The exposed portion of the photosensitive layer subjected to image exposure is cured. By developing this with a developing solution, the unexposed area is removed and image formation becomes possible. As the developer, alkaline, neutral or acidic developers can be used.

As the alkaline 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. The developer may contain the following additives.

(Surfactant)
A surfactant or an organic solvent can be added to the developer as necessary for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area.

Examples of the surfactant include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ether, ester polyoxyethylene alkyl phenyl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ethers, glycerin fatty acid partial ester , Sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester , Polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid Branched esters, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene-polyoxypropylene block copolymer adducts of ethylenediamine, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, Nonionic surfactants such as polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, Linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene aryl ether carboxylic acid, polyoxyethylene naphthyl ether Acid ester salts, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether ether sulfate, N-methyl-N-oleyl taurine sodium salt, N -Alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester, polyoxy Ethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxy Siethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene / maleic anhydride copolymers, partially saponified olefin / maleic anhydride copolymers, naphthalene sulfone Anionic surfactants such as acid salt formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, cationic surfactants such as polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, carboxybetaines And amphoteric surfactants such as aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

A preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned.

The above surfactants can be used alone or in combination of two or more, and are added in the developer in a range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

(Development stabilizer)
The developer may contain various development stabilizers. 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 such as diphenyliodonium chloride. A salt is a preferred example.

Furthermore, there are water-soluble cationic polymers described in JP-A-55-95946 and water-soluble amphoteric polymer electrolytes described in JP-A-56-142528. Further, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, an alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene as described in JP-A-60-129750, and JP-A-61-215554. Polyethylene glycol having a weight average molecular weight of 300 or more described in Japanese Patent Publication No. JP-A-2-39157, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound. Can be mentioned.

(Organic solvent)
If necessary, an organic solvent may be added to the developer. 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-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine.

The content of the organic solvent is preferably 1% by mass or less, particularly preferably not contained, relative to the total mass of the developer used. “Substantially not contained” means 1% by mass or less.

(Reducing agent)
A reducing agent is added to the developer as necessary. This is to prevent stains on the printing plate. 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, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are 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. 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. 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.

Aromatic carboxylic acids are compounds in which a benzene ring, naphthalene ring, anthracene ring or the like is substituted with a carboxyl group, and specifically include o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic 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. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but a preferable addition amount is 0.1 to 10% by mass with respect to the developer at the time of use. 5 to 4% by mass.

(Other additives)
In addition to the above, the following additives can be added to the developer according to the present invention 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 Ampholytic polymer electrolytes such as vinylbenzyltrimethylammonium chloride and sodium acrylate copolymer described in JP-A-142258, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, And organic boron compounds described in JP-A-59-84241. The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softener, and the like, if 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 water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetrimethyl. Aminopolycarboxylic acids such as acetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), Ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid) Hydroxyethyl ethylene diamine tri (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. The mass is preferably in the range of 0.01 to 0.5 mass%. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water. The electric conductivity of the obtained developer is more preferably in the range of 5 to 50 mS.

It is advantageous in terms of transportation that the developer according to the present invention is a concentrated solution in which the water content is less than that in use, and is diluted with water at the time of use. The degree of concentration in this case is appropriate so that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizer, so-called hydrotropes such as toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 are preferably used.

(Automatic processor)
It is advantageous to use an automatic processor for developing the lithographic printing plate material.

The automatic developing machine may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development process. This pretreatment section is preferably provided with a mechanism for spraying the pretreatment liquid onto 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 development, and the waste liquid is reused as dilution water for the developer 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.

(Protective gum solution)
It is preferable to add an acid or a buffer to the protective gum solution to remove the alkali component of the developer. In addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like may be added. it can. When the protective 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 a cleaning solution for pre-development cleaning by adjusting the temperature, and the temperature is preferably in the range of 10 to 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 the pre-development washing step, or the development treatment may be performed 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.

Hereinafter, although an example is given and the present invention is explained in detail, the mode of the present invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
(Synthesis of polymer binder)
In a three-necked flask under a nitrogen stream, 58.0 parts (0.58 mol) of methyl methacrylate, 35.0 parts (0.41 mol) of methacrylic acid, 6.0 parts (0.05 mol) of ethyl methacrylate, ethanol 100 parts and 1.23 parts of α, α′-azobisisobutyronitrile were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a high molecular polymer.

Thereafter, 1 part of triethylbenzylammonium chloride and 28.0 parts (0.2 mol) of glycidyl methacrylate (epoxy group-containing unsaturated compound) were added to this polymer and reacted at a temperature of 25 ° C. for 3 hours. A molecular binder A was obtained. The mass average molecular weight measured using GPC was about 70,000.

Hereinafter, the monomer unit ratio shown in Table 1 and the ratio of the epoxy group-containing unsaturated compound to be reacted with the carboxyl group are changed by changing the charged amount, and the mass average molecular weight is adjusted by adjusting the reaction time of the polymer. The same operations were performed, and polymer binders A and B were obtained.

Resins A and B both had a solubility in pure water at 25 ° C. of less than 0.1% by mass.

[Preparation of lithographic printing plate materials 1 to 11]
<Production of support>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was subjected to an electrolytic surface roughening treatment for 20 seconds in an alternating current having a hydrochloric acid concentration of 11 g / L, a temperature of 25 ° C., a frequency of 50 Hz, and 50 A / dm ² . After electrolytic surface roughening, it was washed with water, desmutted for 10 seconds in a 1% aqueous sodium hydroxide solution maintained at 50 ° C., washed with water, and then washed in 30% sulfuric acid maintained at 50 ° C. for 30 seconds. Neutralization treatment was performed and washed with water. Next, anodization was performed for 30 seconds in a 30% sulfuric acid solution at 25 ° C., a current density of 30 A / dm ² , and a voltage of 25 V, followed by washing with water. Further, a 0.44% polyvinylphosphonic acid aqueous solution was dipped at 75 ° C. for 30 seconds, then washed with distilled water and dried at a drying temperature of 60 ° C. to obtain a support for a lithographic printing plate. At this time, the center line average roughness (Ra) of the surface was 0.50 μm.

On the aluminum support, a photosensitive layer coating solution having the following composition was applied using a wire bar coater so that the film thickness after drying was 1.5 g / m ² , first drying; 0.5 m / sec, second drying; drying at 100 ° C. for 60 seconds and air velocity of 1.0 m / sec to form a photosensitive layer, on which a protective layer coating solution having the following composition is dried to give a film thickness of 1 Coating was performed using an extrusion coater so as to be 0.7 g / m ² , and the first drying; 60 ° C. for 20 seconds, and the second drying; 80 ° C. for 60 seconds were performed to obtain lithographic printing plate materials 1 to 11.

<Photopolymerizable photosensitive layer coating solution>
Polymer binder (polymer binder A or B (shown in Table 2)) 44.0 parts Sensitizing dye (A) 3.0 parts Iron arene compound: Irgacure 261 (manufactured by Ciba Japan) 1.2 parts Triazine compound: TAZ-107 (manufactured by Midori Chemical Co., Ltd.) 1.0 part Compound having ethylenically unsaturated bond (compound (E)): (shown in Table 2) 34 parts Compound having ethylenically unsaturated bond: (tri Ethylene glycol dimethacrylate, NK ester 3G (Shin-Nakamura Chemical Co., Ltd.) 10 parts Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd., 30% MEK dispersion) 5.0 parts Fluorosurfactant (F178K: Dainippon Ink) 0.1 part ANCAMIN (K-54: made by Air Products) 1.5 parts propire Glycol monomethyl ether 820 parts "protective layer coating solution"
Polyvinyl alcohol (degree of saponification 98%, ash content 1.5%) 95 parts Polyvinylpyrrolidone copolymer (VA64W: manufactured by BASF) 5 parts Surfactant (Surfinol 465: manufactured by Nisshin Chemical Co., Ltd.) 0.5 parts Water 900 copies

(Image forming method)
For the lithographic printing plate materials 1 to 11 produced in this way, a plate setter (Tiger Cat: a modified product manufactured by ECRM) equipped with a light source with a laser of 408 nm and 30 mW output was used, and 2400 dpi (1 dpi is 1 inch). In other words, it represents the number of dots per 2.54 cm.) Image exposure was performed with a halftone dot Euclidian with a resolution of 150 lpi.

Next, a heating unit before development, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition 1, a washing part for removing the developer adhering to the plate surface, and a gum solution for protecting the image area ( Developed with a CTP automatic developing machine Raptor Polymer (produced by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted twice), developed at a temperature of 28 ° C. and a development time of 25 seconds. A printed version was obtained.

The heating part conditions were a plate surface temperature of 110 ° C. ± 5 ° C.

The plate surface temperature was measured when it was applied to the roughened surface of the support on which the thermolabel [manufactured by NOF Corporation] was produced.

<< Developer Composition 1 >>
A Potassium silicate ((SiO ₂ : 26% by mass, K ₂ O: 13.5% by mass) 40% aqueous solution) Nippon Chemical Co., Ltd. 8.0 parts New Coal B-13SN (Nippon Emulsifier Co., Ltd.) 3.0 parts Ethylenediaminetetraacetic acid disodium salt dihydrate 0.1 parts Caustic potash adjusted to pH = 12.45 (Evaluation)
The lithographic printing plate material and lithographic printing plate obtained as described above were evaluated as follows.

(sensitivity)
Using the image forming method described above, the exposure energy was changed, and the exposure energy at which the stairs and steps were two stages was visually evaluated.

(Suitable for printing)
-Printing conditions-
Printing machine: DAIYA1F-1: Mitsubishi Heavy Industries, Ltd. Paper: Coated paper (Recycled pulp content 20%, Hokuetsu Paper Industries)
Blanket: SR100 (manufactured by SRI Hybrid)
Printing ink: Soybean oil ink Naturalis 100 (Y, M, C, K): Dainippon Ink & Chemicals, Inc. Dampening water: Fountain Solution 3451U (2.3 mass%), Alkaless 6000 (1.5 mass%) Prisco Print speed: 4,000 sheets / hour, compared to PNV (made by Fujifilm), water-ink balance was evaluated according to the following criteria: Good: Water width equal to or better Deterioration: Water width narrowed (printing durability)
Under the printing conditions described above, the number of sheets until 3% halftone dots on the plate were lost by 10% was measured and used as an index of printing durability.

Example 2
Lithographic printing plate materials 12 to 17 were prepared in the same manner as in Example 1 except that the photosensitive layer coating solution was changed to the following, and the same evaluation was performed.

<Photopolymerizable photosensitive layer coating solution>
Polymer binder (polymer binder A or B: shown in Table 3) 44.0 parts Sensitizing dye: 1,4-bis (4-methoxystyryl) benzene 3.0 parts 2,2'-bis (2 -Chlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole 1.2 parts Mercaptobenzotetrazole 1.0 part Compound having ethylenically unsaturated bond (compound (E)): (shown in Table 3) 34 parts Compound having an ethylenically unsaturated bond: (triethylene glycol dimethacrylate, NK ester 3G (Shin Nakamura Chemical Co., Ltd.)) 10 parts phthalocyanine pigment (MHI454: 30% MEK dispersion manufactured by Mikuni Dye Co.) 0 part Fluorosurfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.1 part ANCAMIN K-54: manufactured by Air Products and Chemicals, Inc.) 820 parts 0.5 parts Propylene glycol monomethyl ether "polymerizable compound"
PM-2: reaction product of 2- (2-hydroxyethyl) piperidine (1 mol), hexamethylene diisocyanate (2 mol), 2-hydroxyethyl methacrylate (2 mol)

Tables 2 and 3 show that the lithographic printing plate material of the present invention has high sensitivity and excellent printing durability while maintaining good printability.

Claims

A lithographic printing plate material having a photosensitive layer containing (A) an ethylenically unsaturated bond-containing compound, (B) a photopolymerization initiator, (C) a polymer binder, and (D) a sensitizing dye on a support. The photosensitive layer contains (A) a compound (E) having an ethylenically unsaturated bond, a thiourethane bond (—SCONH—) and a tertiary amine structure in the molecule as the ethylenically unsaturated bond-containing compound. A lithographic printing plate material characterized by:
The lithographic printing plate material according to claim 1, wherein the compound (E) has two or more thiourethane bonds.
The lithographic printing plate material according to claim 1 or 2, wherein the compound (E) has two or more ethylenically unsaturated bonds.
The lithographic printing plate material according to any one of claims 1 to 3, wherein the lithographic printing plate material is subjected to image exposure using a laser beam having an emission wavelength in the range of 350 nm to 450 nm as a light source, and development processing is performed after the image exposure. A method for preparing a lithographic printing plate, comprising: