JP2002169282A - Photosensitive composition and lithographic printing master plate which uses the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which can be preferably used for a lithographic printing plate for scanning exposure suitable for the CTP(computer to plate) system excellent from the viewpoint of workability and economy. SOLUTION: The photosensitive composition contains (i) a compound having at least one vinyl group in an aromatic ring and at least one site of the ortho and para sites in the ring substituted with a sulfur atom, (ii) a titanocene compound and (iii) a compound which reacts with at least either radicals or acid to change at least either physical characteristics or chemical characteristics and maintains its change.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel photoinitiating system,
In particular, the present invention relates to a photosensitive composition containing a photoinitiating system having high sensitivity and excellent stability. Further, the present invention relates to a photosensitive composition which can be suitably used for a lithographic printing plate for scanning exposure which is particularly suitable for a CTP system excellent in workability and economy.

[0002]

2. Description of the Related Art Hitherto, as a lithographic printing plate, a PS plate having a structure in which a lipophilic photosensitive resin is provided on a hydrophilic support has been widely used, and as a plate making method, usually, a mask is provided via a lith film. After the exposure (surface exposure), the desired printing plate was obtained by dissolving and removing the non-image portion.

In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread. Then, various new image output systems corresponding to such digitizing technology have come into practical use. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light in accordance with digitized image information and directly manufactures a printing plate without passing through a lithographic film has been desired. It is an important technical issue to obtain a printing plate precursor adapted to this.

One of the methods for obtaining such a lithographic printing plate capable of being scanned and exposed is a photopolymerizable composition which has been used as a lipophilic photosensitive resin layer formed on a hydrophilic support and which has a very high photosensitive speed. Has been proposed, and a configuration having an oxygen-blocking protective layer has been proposed and is already on the market. The original plate having the above configuration has a desirable printing plate and printing performance such that the developing process is simple and the resolution, the inking property and the printing durability are excellent.

However, since the conventional CTP system uses a relatively long wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) as a light source, a sensitive material having a high sensitivity near 500 nm is used. To do was a problem. In other words, as a result, operations such as removing the plate from the cardboard packaging, loading the plate setter into the cassette, and inserting the plate into the plate setter all need to be performed under a dark red light safelight. It was remarkably bad. Therefore, it has been strongly desired to construct a CTP system that can be handled under a brighter yellow or white safelight.

Further, gas lasers such as Ar ion lasers and solid-state lasers such as FD-YAG are expensive due to the complicated structure of the laser itself.
The P system has an economically unfavorable problem in terms of the price of the laser exposure apparatus (plate setter) and the cost of replacing the laser.

On the other hand, the progress of laser technology in recent years has been remarkable. For example, a semiconductor laser using an InGaN-based material and capable of continuously oscillating in a range from 360 nm to 450 nm has come into practical use. If a CTP system using these short-wave light sources can be constructed, a light-sensitive material having a short photosensitive area capable of working under a brighter safelight can be used.
Further, the semiconductor laser can be manufactured at a low cost structurally, and is very preferable as a light source for a CTP system.

[0008] From these, from 350nm to 450nm
There has been a strong demand in the industry for obtaining a lithographic printing plate precursor suitable for a CTP system using a semiconductor laser having a relatively short wavelength of nm.

The photopolymerizable composition used for the printing plate precursor basically comprises an ethylenically unsaturated compound, a photopolymerization initiation system, and a binder resin. In image formation, a photoinitiating system absorbs light, generates an active radical, causes addition polymerization of an ethylenically unsaturated compound, and causes insolubilization of a photosensitive layer.

Most of the conventional proposals relating to such a lithographic printing plate capable of scanning exposure using a photopolymerizable photosensitive layer are as follows:
It discloses the use of specific photoinitiators with good photosensitivity, such sensitive initiators are described, for example, by Bruce M. Mon.
Roe et al., Chemical Revue, 93, 435 (1993); and RSDavidso
n, Journal of Photochemistry and biology A: Chemi
stry, 73.81 (1993).

In addition, as a relatively sensitive starting system, a starting system in which a specific dye and a titanocene compound are combined is known. In JP-A-9-80750, a combination of a styryl dye and titanocene is disclosed in JP-A-10-101.
No. 719 discloses a combination of a dye having a 5-membered heterocyclic acidic nucleus and titanocene, respectively. These were indeed sensitive but not sufficient, and
When a laser beam having a wavelength of 0 nm or less is used, practically sufficient sensitivity cannot be obtained, which is not suitable for a short-wavelength light source, and there is no suggestion about suitability for safelight.

Further, the above-mentioned 350 nm to 450 nm
Obtaining a photopolymerizable composition having high photosensitivity to the short-wavelength semiconductor laser region is widely used in industrial fields other than CTP, for example, in laser imaging fields such as stereolithography, holography and color hard copy, and in photoresists and the like. In the field of electronic material production, and in the field of photocurable resin materials such as inks, paints, and adhesives, this is an important technology that is increasingly required.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition which can be suitably used for a lithographic printing plate for scanning exposure which is excellent in workability and economy and is suitable for a CTP system. It is in. Another object of the present invention is to
An object of the present invention is to provide a photosensitive composition which has high sensitivity to the oscillation wavelength of an inexpensive short-wave semiconductor laser, has excellent storage stability, and can be suitably used for a lithographic printing plate for scanning exposure. A further object of the present invention is to provide a lithographic printing plate having a photosensitive layer formed from the above excellent photosensitive composition.

[0014]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that (i) the aromatic ring has at least one vinyl group, and its ortho position and para position A compound in which at least one of them is substituted by a sulfur atom, (ii) a titanocene compound, and (iii) a reaction by at least one of a radical and an acid to change at least one of its physical and chemical properties. It has been found that the above-mentioned object is achieved by using a photosensitive composition containing a retained compound.

In the present invention, the compound in the above (i) is preferably a compound represented by the following general formula (1).

[0016]

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In the formula (1), R ^{1 to} R ⁸ each represent a hydrogen atom or a monovalent nonmetallic atomic group, and can be bonded to each other to form an aliphatic or aromatic ring. . Provided that at least one of R ^1, R ³ and R ⁵ represents a -SR ^9. Here, R ⁹ has the same meaning as R ^{1 to} R ⁸ .

Further, in the present invention, the compound (iii) which is reacted by at least one of the above-mentioned radicals and acids, and which is retained by changing at least one of its physical and chemical properties, is converted to an ethylenically unsaturated diacid. It is preferably an addition polymerizable compound having a heavy bond. The present invention
Further, the present invention provides a photopolymerization method, which comprises exposing the photosensitive composition to a laser beam having a wavelength of 450 nm or less.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. The photosensitive composition of the present invention comprises (A) a photopolymerization initiation system,
(B) an essential component is a compound which reacts with at least one of a radical and / or an acid and changes and retains at least one of its physical and chemical properties, and further comprises (C) Comprising a binder polymer. Hereinafter, these components will be specifically described.

(A) Photopolymerization initiation system The photopolymerization initiation system which is an essential component of the photosensitive composition of the present invention is
It contains (i) a sensitizing dye having a specific structure and (iii) a titanocene compound. It is considered that the initiation system in the present invention mainly absorbs light by the sensitizing dye and promotes generation of the initiation radical from the coexisting titanocene compound (such a process is hereinafter referred to as dye sensitization). One reason that the sensitizing dye of the present invention is particularly excellent is that its absorption wavelength is from 350 to 45.
It is in the 0 nm range. In addition, many of the titanocene compounds described below themselves have weak absorption in the wavelength range from ultraviolet to around 500 nm, and have photosensitivity there, but the sensitizing dye having a specific structure of the present invention increases the photosensitivity of titanocene. For example, by using a relatively small amount of the titanocene compound, the photosensitivity at short wavelengths can be sufficiently increased, and at the same time, 5
The photosensitivity in the 00 nm region can be reduced, and the suitability for safelight can be improved.

The present inventors have found that the above characteristics can be obtained when the sensitizing dye satisfies the following structural characteristics, and have accomplished the present invention. That is, the sensitizing dye has a specific styryl type structure (S-substituted styryl structure) in which a basic nucleus has an aromatic ring directly bonded to at least one of an ortho position and a para position with respect to an acidic nucleus on an aromatic ring. It has been found that when they do, very high sensitivity and excellent absorption properties are obtained. Here, the definitions of “acid nucleus” and “basic nucleus” are based on TH James, “The Theory of The Phot”.
ographic Process "fourth edition, 8th of Macmillan
It is described in the chapter. Sensitizing dyes represented by merocyanines generally have 1) basic (electron-donating) and 2) acidic (electron-accepting) heterocycles at their terminals, but 1) basic (electron-donating) The heterocycle is called a basic nucleus, and the acidic (electron-accepting) heterocycle of 2) is called an acidic nucleus. Examples of acidic nuclei and basic nuclei are described in TH James, "The Theory of The Ph.
Many are described in Chapter 8 of the otographic Process "fourth edition, Macmillan.

The reason why the sensitizing dye having a specific structure in the present invention is particularly excellent in dye sensitizing ability cannot be described in detail because the mechanism of dye sensitization is unknown, but can be considered as follows. That is, the sensitizing dye of the present invention exhibits a high-intensity emission (fluorescence and / or phosphorescence) spectrum. From this, one possibility is that the sensitizing dye of the present invention having the above partial structure has a relatively long excited state lifetime, and thus acts to make the reaction with the activator more efficient. Conceivable.

(A1) Sensitizing dye The sensitizing dye used in the present invention has at least one sensitizing dye on the aromatic ring.
An S-substituted styryl sensitizing dye having two vinyl groups and having its ortho or para position substituted with at least one sulfur atom, and may be a compound represented by the above general formula (1). preferable.

The general formula (1) will be described in detail. R
¹ to R ⁸ each independently represent a monovalent nonmetallic atomic group.
Preferred specific examples of such a substituent include a hydrogen atom,
Alkyl group, substituted alkyl group, halogen atom (-F,-
Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group,
Arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkylamino, N-arylamino, N, N-diarylamino, N-alkyl-N-arylamino Group,
Acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N,
N-diarylcarbamoyloxy group, N-alkyl-
An N-arylcarbamoyloxy group, an alkylsulfoxy group,

Arylsulfoxy, acylthio, acylamino, N-alkylacylamino, N-arylacylamino, ureido, N'-alkylureido, N ', N'-dialkylureido, N' -Arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-
Alkylureido group, N-arylureido group, N'-
Alkyl-N-alkylureido group, N'-alkyl-
N-arylureido group, N ', N'-dialkyl-N
-Alkylureido group, N ', N'-dialkyl-N-
An arylureido group, an N′-aryl-N-alkylureido group, an N′-aryl-N-arylureido group,
An N ′, N′-diaryl-N-alkylureido group,
An N ′, N′-diaryl-N-arylureido group,
An N'-alkyl-N'-aryl-N-alkylureido group, an N'-alkyl-N'-aryl-N-arylureido group,

An alkoxycarbonylamino group, an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, Aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group , N, N-diarylcarbamoyl group,
An N-alkyl-N-arylcarbamoyl group,

An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonato group), an alkoxysulfonyl group,
Aryloxysulfonyl group, sulfinamoyl group, N-
Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group,
N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group ,
N, N-diarylsulfamoyl group, N-alkyl-
An N-arylsulfamoyl group,

A phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as a phosphonate group), a dialkylphosphono group (—PO ₃ (alkyl) ₂ ), a diarylphosphono group (—PO ₃ (aryl) ) _2), alkyl aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group) , monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter,
Referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), Diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and the like conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H
(aryl)) and its conjugate base group (hereinafter, referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, and alkynyl group.

Preferable examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include: Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group,
Examples thereof include a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. The substituent of the substituted alkyl group is optional, but specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, and allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group,

N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl Group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N -(Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolyls Sulfamoyl-propyl group,

N-methyl-N- (phosphonophenyl)
Sulfamoyloctyl group, phosphonobutyl group, phosphonohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-
Methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2- Butynyl group, 3-butynyl group and the like.

Specific examples of the aryl group in these substituents include those in which one to three benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferable.

As specific examples of the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group,
Chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group,
Tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyloxyphenyl, N
-Cyclohexylcarbamoyloxyphenyl group, N-
Phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group,

Sulfophenyl, sulfonatophenyl, sulfamoylphenyl, N-ethylsulfamoylphenyl, N, N-dipropylsulfamoylphenyl, N-tolylsulfamoylphenyl, N-
Methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolyl Phosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl Group, 3-butynylphenyl group, and the like.

As the heteroaryl group, nitrogen, oxygen,
A monocyclic or polycyclic aromatic ring containing at least one sulfur atom is used, and preferably a 5- or 6-membered aromatic substituent such as furan, pyrrole, pyridine and the like can be used.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above-mentioned alkyl groups and aryl groups. Of these substituents, still more preferred are halogen atoms (-F, -Br, -Cl,
-I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-
Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group , N, N-dialkylcarbamoyl, N-arylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulfo, sulfonato, sulfamoyl,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphono Examples thereof include an oxy group, a phosphonateoxy group, an aryl group and an alkenyl group.

As described above, R ¹ to R ⁸ are selected from various viewpoints in practical use in addition to performance such as photosensitivity, photosensitive wavelength, and stability. For example, compatibility in the composition system, viewpoints such as prevention of crystal precipitation, when performing development, solubility in a developing solution, dispersibility, viewpoints such as difficulty in precipitation, raw material price, ease of synthesis, It is appropriately selected in consideration of economic viewpoints such as easiness of purification. From these viewpoints, particularly preferred examples of the substituent include a hydrogen atom and a halogen atom (-
F, -Br, -Cl, -I), lower alkyl groups having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, isopropyl, allyl, and 2-methylpropenyl), and alkyl-substituted aminoalkylene groups (As the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 7 carbon atoms, and an alkylene group having 1 to 3 carbon atoms, such as mono-, Gee,
A tri-methylene group).

Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Specific examples of the substituted aryl group include a biphenyl group, Tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl Group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexyl Carbamoyl oxyphenyl group, N- phenylcarbamoyloxy phenyl group, an acetylamino phenyl group, N- methyl-benzoylamino phenyl group,

Carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, carbamoylphenyl, N-methylcarbamoylphenyl, N, N
-Dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N-
(Sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N
-Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, Diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-
Butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2
-Butynylphenyl group, 3-butynylphenyl group, and the like.

As the heteroaryl group, nitrogen, oxygen,
A monocyclic or polycyclic aromatic ring containing at least one sulfur atom is used, and preferably a 5- or 6-membered aromatic substituent such as furan, pyrrole, pyridine and the like can be used. Examples of substituted heteroaryl groups, can be used a monovalent non-metallic atomic group, and specifically can be used any of those raised as an example of X ₅ from X _1. Examples of particularly preferred heteroaryl groups include, for example, thiophene, thiazulene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine,
Pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole,
Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carbolin, phenanthrin, acridine, perimidine, phenanthroline, phenzarzazine, furazane, and the like, which may be further benzo-condensed, Further, it may have a substituent.

Next, -SR ⁹ in the general formula (1) will be described. -SR ⁹ represents R ¹ , R in the general formula (1)
³ or R ⁵ , wherein the aromatic ring is directly bonded to a sulfur atom, and R ⁹ bonded to the sulfur atom represents a hydrogen atom or a monovalent nonmetallic atomic group, Specific examples thereof include those similar to those described for R ^{1 to} R ⁸ in the general formula (1).

The sensitizing dye represented by the general formula (1) of the present invention comprises an acidic nucleus as described above, an acidic nucleus having an active methylene group, and a substituted or unsubstituted aromatic ring or It is obtained by a condensation reaction with a heterocycle, and these can be synthesized with reference to JP-B-59-28329. Preferred specific examples (D-1) to (D-33) of the compound represented by formula (1) are shown below, but the invention is not limited thereto. Further, it is not clear about the isomer due to the double bond connecting the acidic nucleus and the basic nucleus,
The invention is not limited to either isomer.

[0045]

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[0046]

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[0047]

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[0048]

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The sensitizing dye of the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, by combining a sensitizing dye with an addition-polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, it is possible to increase the strength of the exposed film or to increase the exposure. Unnecessary precipitation of the dye from the subsequent film can be suppressed. In addition, a sensitizing dye and a titanocene compound described later and other radical generating parts (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, etc., borate, amine, trimethylsilylmethyl) Oxidatively decomposable sites such as carboxymethyl, carbonyl, and imine), thereby significantly increasing the photosensitivity, particularly in the case where the concentration of the starting system is low. further,
For the purpose of enhancing the suitability for processing in an (alkali) aqueous developer, which is a preferred mode of use of the present photosensitive layer, a hydrophilic moiety (such as a carboxyl group and its ester, a sulfonic acid group and its ester, an ethylene oxide group, etc.) The introduction of an acid group or a polar group) is effective. Particularly, the ester-type hydrophilic group has a relatively hydrophobic structure in the photosensitive layer and thus has excellent compatibility, and in a developing solution, generates an acid group by hydrolysis to increase the hydrophilicity. Have.
In addition, for example, a substituent can be appropriately introduced for improving compatibility in the photosensitive layer and suppressing crystal precipitation. For example,
In some types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility, and steric hindrance between the dye π planes may be reduced by a method such as introduction of a branched alkyl structure. By introducing, crystal precipitation can be remarkably suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group or the like, it is possible to improve the adhesion to inorganic substances such as metals and metal oxides. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

Which structure of these sensitizing dyes is used,
Details of how to use, such as whether to use them alone or in combination of two or more, and the amount of addition, can be appropriately set according to the final performance design of the light-sensitive material. For example, by using two or more sensitizing dyes in combination, the compatibility with the photosensitive layer can be increased. In selecting a sensitizing dye, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity. By using a dye having a large molar extinction coefficient, the amount of the dye added can be relatively small, which is economical and advantageous from the viewpoint of the physical properties of the photosensitive layer. Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength, the amount of the sensitizing dye to be added is appropriately selected in consideration of these factors. For example, sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film having a thickness of, for example, 5 μm or more, such a low absorbance may sometimes increase the degree of curing. The absorbance is 3
In the high region as described above, most of the light is absorbed on the surface of the photosensitive layer, and curing inside is more hindered.For example, when used as a printing plate, the film strength and the substrate adhesion are considered to be insufficient. Become. When used as a lithographic printing plate having a relatively thin film thickness, the amount of the sensitizing dye added is such that the absorbance of the photosensitive layer is in the range of 0.1 to 1.5, preferably in the range of 0.25 to 1. It is preferable to set so that When used as a lithographic printing plate, this is usually 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the photosensitive layer component.
It is in the range of parts by weight.

(A2) Titanocene Compound The titanocene compound used as a photopolymerizable initiation system in the present invention may be any titanocene compound which can generate an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye. For example, Japanese Patent Application Laid-Open No. Sho 59-1
52396, JP-A-61-151197, JP-A-6-151197
JP-A-3-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, JP-A-3-273
No. 93, JP-A-3-12403, JP-A-6-4117
A known compound described in JP-A No. 0 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,3 4,5,6-pentafluorophenyl-1-yl (hereinafter also referred to as “T-1”), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1- Yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-
Difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-
Yl) phenyl) titanium (hereinafter also referred to as “T-2”).

The titanocene compound of the present invention can also be subjected to various chemical modifications to improve the characteristics of the photosensitive layer, as in the case of the above-mentioned sensitizing dye. For example,
Sensitizing dyes, binding with addition-polymerizable unsaturated compounds and other radical-generating parts, introduction of hydrophilic sites, improved compatibility,
Methods such as introduction of a substituent for suppressing crystal precipitation, introduction of a substituent for improving adhesion, and polymerization can be used.

The method of using these titanocene compounds can be arbitrarily set as appropriate in accordance with the performance design of the photosensitive material, similarly to the aforementioned addition-polymerizable compounds and sensitizing dyes. For example, by using two or more kinds, the compatibility with the photosensitive layer can be enhanced. In addition, these titanocene compounds may be added to the same layer as other components, or another layer may be provided and added thereto. A larger amount of the titanocene compound is generally advantageous in terms of photosensitivity, and is preferably 0.5 to 80 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the photosensitive layer component.
When used in this range, sufficient photosensitivity can be obtained. On the other hand, when used in white lighting such as yellow, which is the main object of the present invention, it is preferable that the amount of titanocene used is small from the viewpoint of fog due to light near 500 nm. The amount of titanocene used is 6 in combination with
Parts by weight or less, further 1.9 parts by weight or less, further 1.4
Sufficient photosensitivity can be obtained even when the amount is reduced to not more than part by weight.

The electron transfer initiator of the present invention accounts for 0.1 to 50% by weight, preferably 0.5 to 30% by weight, and particularly preferably 1 to 20% by weight, based on the total solid content of the coating solution for the photosensitive layer. It can be added to the photosensitive layer coating solution in a proportion. If the amount is less than 0.1% by weight, the sensitivity is lowered, and if it exceeds 50% by weight, the non-image area is stained during printing. One of these initiators may be used alone,
More than one species may be used in combination. Further, these initiators may be added to the same layer as other components, or another layer may be provided and added thereto.

(B) a compound which reacts with at least one of a radical and an acid, changes at least one of its physical and chemical properties, and retains the changed property, and reacts with at least one of a compound radical and an acid A compound (B) in which at least one of its physical and chemical properties is changed to maintain the changed properties
Is a compound whose physical or chemical properties are changed and retained by the action of an active species generated by the photoreaction of the photoinitiating system described above. Here, that the physical or chemical property is changed and held means that once changed, it is irreversible or unchanged.

As the component (B), any one can be used without particular limitation as long as it has such properties. For example, the compounds listed in the above-mentioned starting system themselves often have such properties. . The characteristics of the component (B) that changes due to radicals and / or acids generated from the photoinitiating system include, for example, molecular properties such as absorption spectrum (color), chemical structure, polarizability, solubility, strength, and the like. Includes changes in physical properties such as refractive index, fluidity, adhesiveness, etc.

For example, if a compound whose absorption spectrum changes with pH, such as a pH indicator, is used as the component (B) and an acid or base is generated from the initiation system, the color of only the exposed portion can be changed. However, such compositions are useful as imaging materials. Similarly, component (B)
In the case where a compound whose absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction is used, oxidation, reduction and the like by radicals generated from the initiation system are caused to form an image. Such examples are described, for example, in J. Am. Chem. Soc.,
108, 128 (1986), J. Imaging.Sci., 30, 215 (1986),
Israel. J. Chem., 25, 264 (1986).

Also, by using a compound capable of addition polymerization or polycondensation as the component (B) and combining it with an initiation system, a photocurable resin or a negative photopolymer can be formed.

As the component (B), a radical polymerizable compound (a compound having an ethylenically unsaturated bond, etc.), a cationic polymerizable compound (an epoxy compound, a vinyl ether compound, a methylol compound, etc.), an anionic polymerizable compound (an epoxy compound, etc.) Examples of such a polymer include, for example, Photopolymer Society, edited by Photopolymer Handbook, Industrial Research Council (1989), Polymer, 45, 78
6 (1996). Further, a composition using a thiol compound as the component (B) in combination with a photoradical generating system is also well known.

It is also useful to use an acid-decomposable compound as component (B) and combine it with a photoacid generator. For example, a material that uses a polymer whose side chain or main chain is decomposed by an acid and changes solubility or hydrophilicity / hydrophobicity by light is widely used as a photodecomposable photosensitive resin or a positive photopolymer. Such specific examples include, for example, ACS. Symp. Ser. 242,
11 (1984), JP-A-60-3625, U.S. Pat.
No. 02,771, No. 5,206,317, No. 5,
212,047, JP-A-4-26850, JP-A-3-3
No. 1921731, JP-A-60-10247, JP-A-62-40450 and the like.

The compound (B) which is particularly excellent for obtaining a lithographic printing plate with high sensitivity, which is an addition-polymerizable compound, will be described in detail below.

The addition polymerizable compound having at least one ethylenically unsaturated double bond preferably used as the component (B) is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. .
Such compounds are widely known in the industrial field, and they can be used without particular limitation in the present invention. These have chemical forms such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof. ,
Preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. Also, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or polyfunctional A dehydration-condensation reaction product with a carboxylic acid is also preferably used. Further, unsaturated carboxylic acid esters having an electrophilic substituent such as an isocyanato group or an epoxy group, addition products of amides with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups, tosyloxy Unsaturated carboxylic esters and amides having a leaving substituent such as a group are also suitable for the substitution reaction of monofunctional or polyfunctional alcohols, amines and thiols. Further, as another example, an unsaturated phosphonic acid, styrene,
It is also possible to use a group of compounds replaced with vinyl ether or the like.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate , 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
Examples thereof include 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
And sorbitol tetradicrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Examples of other esters include, for example, JP-B-46-27926 and JP-B-51
Aliphatic alcohol esters described in JP-A-47334 and JP-A-57-196231, and JP-A-59-5240.
JP-A-59-5241, JP-A-2-226149
Having an aromatic skeleton described in JP-A-1-165
No. 613 containing an amino group is also preferably used. Further, the above-mentioned ester monomers can be used as a mixture.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
No. 8-41708, wherein a polyisocyanate compound having two or more isocyanate groups in one molecule is added with a vinyl monomer having a hydroxyl group represented by the following formula (VI), and two or more isomers in one molecule And a vinyl urethane compound containing a polymerizable vinyl group.

CH ₂ ＣC (R ′) COOCH ₂ CH (R ″) OH Formula (VI) (R ′ and R ″ are the same or different and represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable. Further, Japanese Unexamined Patent Application Publication No.
By using addition polymerizable compounds having an amino structure or a sulfide structure in a molecule described in JP-A-3-260909 and JP-A-1-105238, a photopolymerizable composition having a very high photosensitive speed can be obtained. be able to.

Another example is disclosed in JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

The details of the method of using these addition-polymerizable compounds, such as what kind of structure to use, whether to use them alone or in combination, and the amount of addition, depend on the performance design of the final photosensitive material. And can be set arbitrarily. For example, it is selected from the following viewpoints.

From the viewpoint of photosensitive speed, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, a bifunctional or more functional structure is preferable. Further, in order to increase the strength of the image area, that is, the cured film, a trifunctional or higher functional one is preferable.
A method of controlling both photosensitivity and strength by using a combination of different functionalities and different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene compound, vinyl ether compound) is also effective. For compounds with large molecular weight or compounds with high hydrophobicity,
Although excellent in film strength, it may not be preferable in terms of development speed and precipitation in a developer. Also, the selection and use of the addition polymerization compound is an important factor for compatibility and dispersibility with other components (for example, a binder polymer, an initiator, and a colorant) in the photosensitive layer. In some cases, compatibility may be improved by using a low-purity compound or by using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, the overcoat layer, and the like.

With respect to the compounding ratio of the addition polymerizable compound in the photosensitive composition, the larger the proportion, the more advantageous in sensitivity. However, if the proportion is too large, undesired phase separation may occur or the photosensitive layer may become sticky. Problems may occur in the manufacturing process (for example, poor production resulting from transfer or sticking of the photosensitive material component) and problems such as precipitation from the developer. From these viewpoints, the preferred compounding ratio is often 5 to 8 based on all components of the composition.
0% by weight, preferably 25 to 75% by weight. Also,
These may be used alone or in combination of two or more. In addition, the method of using the addition polymerizable compound can be arbitrarily selected from the viewpoints of the degree of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, etc. Depending on the case, a layer structure and a coating method such as undercoating and overcoating may be performed.

(C) Binder Polymer When the photosensitive composition of the present invention is applied to a lithographic printing plate as a preferred embodiment, it is preferable to further use a binder polymer in the photosensitive layer. It is preferable to include a linear organic high molecular polymer as the binder.
Such a “linear organic high molecular polymer” is not particularly limited, and any one may be used. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is selected and used not only as a film-forming agent of the composition but also as a developer for water, weakly alkaline water or an organic solvent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Application Laid-Open No.
44615, JP-B-54-34327, JP-B-58
-12577, JP-B-54-25957, JP-A-5
4-92723, JP-A-59-53836, JP-A-59-71048, that is,
Examples include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain can also be mentioned. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as needed) copolymer,
It is suitable because it has an excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-12004,
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength, and therefore is advantageous in terms of printing durability and low exposure suitability. Also, the binder having an amide group described in JP-A-11-171907 has excellent developability and film strength and is suitable.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone and polyethylene oxide are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

These linear organic high molecular polymers can be incorporated in an arbitrary amount into the whole composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85% by weight. In addition, the compound having a photopolymerizable ethylenically unsaturated double bond and the linear organic high molecular weight are 1/9 to weight ratio.
It is preferred to be in the range of 7/3.

In a preferred embodiment, an alkali-soluble binder polymer which does not substantially require water is used. This makes it possible to use no environmentally unfriendly organic solvent as the developer or to limit the amount to a very small amount. In such a method of use, the acid value (acid content per gram of polymer expressed by chemical equivalent number) and molecular weight of the binder polymer are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 me.
q / g, and the preferred weight average molecular weight is 3000-5.
It is in the range of 10,000. More preferably, the acid value is 0.6 to
2.0, and the molecular weight is in the range of 10,000 to 300,000. The weight average molecular weight is a value in terms of polystyrene measured by the GPC method.

(D) Other Components The photosensitive layer of the present invention may further contain other components suitable for its use, production method and the like. Less than,
Preferred additives will be exemplified.

(D-1) Co-sensitizer The sensitivity can be further improved by using a certain additive (hereinafter, referred to as an additive co-sensitizer).
Although their mechanism of action is not clear, many are thought to be based on the following chemical processes. That is, various intermediate active species (radicals, peroxides, oxidizing agents, reducing agents, etc.) and co-sensitizers generated in the course of the photoreaction initiated by the above-described photoabsorption of the initiation system and the subsequent addition polymerization reaction are used. It is presumed that it reacts to generate new active radicals.
These are largely divided into (a) those that can be reduced to produce active radicals, (b) those that can be oxidized to produce active radicals, and (c) those that react with less active radicals and become more active radicals. Although they can be classified as converting or acting as chain transfer agents, there is often no myth as to which of these individual compounds belong.

(A) Those which can be reduced to generate active radicals Any material which can be reduced to generate an active species through bond cleavage can be used without limitation. An example is shown below. Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active species (for example, Polymer Preprints, Jpn., 41 (3) 542 (1992)
Described in). The active species can generate radicals and acids. Specifically, for example, in addition to halomethyl-s-triazines, MP Hutt, EF Elslager and L.
M. Merbel, Journal of Heterocyclic chemistry, 7 , 5
11 (1970), halomethyloxadiazoles that can be easily synthesized by those skilled in the art by the synthesis method described in German Patents 2641100, 3333450, and 302159.
Compounds described in U.S. Pat.

Compounds having a nitrogen-nitrogen bond or a nitrogen-containing heterocycle-nitrogen-containing heterocycle bond: Reductive bond cleavage occurs (for example, J. Pys. Chem., 96 , 207 (1992)).
It is described in). Specifically, hexaarylbiimidazoles and the like are preferably used. The active species generated are lophine radicals, which, if necessary, are used in combination with a hydrogen donor to initiate a radical chain reaction, and are also known to form images using oxidation reactions with lophine radicals (J. Imag
ing Sci., 30 , 215 (1986)). Compound having an oxygen-oxygen bond: It is considered that the oxygen-oxygen bond is reductively cleaved to generate an active radical (for example, Po
lym. Adv. Technol., 1 , 287 (1990)). Specifically, for example, organic peroxides and the like are preferably used. It can generate radicals as active species.

Onium compound: It is considered that a carbon-hetero bond or an oxygen-nitrogen bond is reductively cleaved to generate an active tumor (for example, J. Photopolm. Sci. Technol., 3 , 1).
49 (1990)). Specifically, for example, European Patent 104143, U.S. Pat.
-150848, iodonium salts described in JP-A-296514, EP370693, 233567,
297443, 297442, 279210, 4225
70, U.S. Patents 3,902,144, 4,933,377, 47
Sulfonium salts, diazonium salts (such as benzenediazonium which may have a substituent), diazonium salt resins (such as formaldehyde resin of diazodiphenylamine), pyridinium salts (such as N-alkoxypyridinium salts) described in US Pat. For example, those described in U.S. Pat. No. 4,743,528, JP-A-63-138345, JP-A-63-142345, JP-A-142346, JP-B-46-42363, and specifically, 1-methoxy- 4-phenylpyridinium tetrafluoroborate, etc.), and further, JP-B-52-147277, 52-1478, 52-1
The compounds described in 4279 are preferably used. Generates radicals and acids as active species.

The onium salts suitably used in the present invention include iodonium salts, diazonium salts and sulfonium salts. In the present invention, these onium salts function not as acid generators but as radical polymerization initiators. Onium salts preferably used in the present invention,
Onium salts represented by the following general formulas (III) to (V).

[0090]

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In the formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a 12 or less carbon atom. Aryloxy groups. Z ^11- represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and is preferably a perchlorate ion or a hexafluorophosphate. And arylsulfonate ions.

In the formula (IV), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and a 12 or less carbon atom. Alkylamino group, dialkylamino group having 12 or less carbon atoms, 1 carbon atom
An arylamino group having 2 or less or a diarylamino group having 12 or less carbon atoms is exemplified. Z ^{21 -} is Z ^11-
Represents a counter ion having the same meaning as

In the formula (V), R ³¹ , R ³² and R ³³ may be the same or different and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the present invention, an onium salt ([OI-1]) represented by the general formula (III) which can be suitably used.
To [OI-10]), onium salts represented by the general formula (IV) ([ON-1] to [ON-5]), and onium salts represented by the general formula (V) ([OS-1] to Specific examples of [OS-5]) are shown below.

[0095]

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[0096]

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[0097]

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[0098]

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Active esters: nitrobenzyl esters of sulfonic acid and carboxylic acid, esters of sulfonic acid and carboxylic acid with N-hydroxy compounds (N-hydroxyphthalimide and oxime, etc.), sulfonic acid esters of pyrogallol, naphtho Quinonediazide-4-sulfonic acid esters and the like can be reductively decomposed. As an active species,
May generate radicals, acids. Specific examples of the sulfonic acid esters include European Patent Nos. 0290750, 046083, 156153, and 271851.
No. 0388343, U.S. Pat.
Nitrobenzul ester compounds described in JP-A-4181531, JP-A-60-198538 and JP-A-53-133022; European Patents 0199672 and 845.
No. 15, 199672, No. 044115, No. 01
01122, U.S. Pat. Nos. 4,618,564 and 4,371.
Nos. 605 and 4431774, JP-A-64-1814.
No. 3, JP-A-2-245756, JP-A-4-3650
No. 48, iminosulfonate compound,
No. 6223, JP-B-63-14340, JP-A-59-1984.
No. 174831 and the like, and further, for example, the following compounds.

[0100]

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(In the formula, Ar represents an aromatic group or an aliphatic group which may be substituted. R represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.) A base as an active species It is also possible to generate
For example, the following compounds are known.

[0102]

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Ferrocene and iron arene complexes: Active radicals can be generated reductively. Specifically, it is disclosed in, for example, JP-A-1-304453 and JP-A-1-152109. Disulfones: They can reductively cause SS bond cleavage to generate an acid. For example, diphenyldisulfones as described in JP-A-61-166544 are known.

(B) Compound which is oxidized to generate an active radical Any compound can be used without limitation as long as it is oxidized to cause bond cleavage and generate an active species. An example is shown below. Alkyl ate complex: It is considered that the carbon-hetero bond is oxidatively cleaved to form an active radical (for example, J. Amer.
Am. Chem. Soc., 112 , 6329 (1990)).
Specifically, for example, triarylalkyl borates (especially JP-A-9-188585 and JP-A-9-18868)
6, acid stable borates described in JP-A-9-188710 are preferred).

Alkylamine compound: It is considered that the CX bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical (for example, J. Am. Chem. So
c., 116 , 4211 (1994)). As X,
A hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group and the like are preferred. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines and the like. Sulfur- and tin-containing compounds: Compounds in which the nitrogen atom of the above-mentioned amines is replaced with a sulfur atom or a tin atom can generate an active radical by the same action. Compounds having an SS bond are also known to be sensitized by SS cleavage.

Α-Substituted methylcarbonyl compound: An active radical can be generated by the cleavage of the bond between carbonyl and α carbon by oxidation. In addition, those obtained by converting carbonyl to oxime ether also show the same action. In particular,
2-alkyl-1- [4- (alkylthio) phenyl]
Examples thereof include -2-morpholinopronones-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH. Sulfinates: Active radicals can be generated reductively. Specific examples include sodium arylsulfinate and the like.

(C) Compounds that react with radicals to convert them into highly active radicals or act as chain transfer agents. For example, compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate a radical by donating hydrogen to a low-activity radical species, or can generate a radical by being oxidized and then deprotonated. Specific examples include 2-mercaptobenzimidazoles.

More specific examples of these co-sensitizers are described in, for example, JP-A-9-236913 as additives for the purpose of improving sensitivity. Hereinafter, some of the examples will be exemplified, but the present invention is not limited thereto.

[0109]

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These co-sensitizers can also be subjected to various chemical modifications to improve the characteristics of the photosensitive layer, as in the case of the above-mentioned sensitizing dyes. For example, binding with sensitizing dyes, activators, addition-polymerizable unsaturated compounds and other parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, introduction of substituents for improving adhesion , Polymerization and the like can be used.

These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.0 to 100 parts by weight of the compound having an ethylenically unsaturated double bond.
A suitable range is 5 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 3 to 50 parts by weight.

(D-2) Polymerization Inhibitor In the present invention, in addition to the above basic components, there is no need for a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent a thermal polymerization. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The amount of the higher fatty acid derivative to be added is about 0.5% by weight of the total composition.
About 10% by weight is preferred.

(D-3) Colorant, etc. For the purpose of coloring the photosensitive layer, a dye or pigment may be added. As a result, so-called plate inspection properties such as visibility after plate making as a printing plate and suitability for an image density measuring device can be improved. As a coloring agent, a pigment is particularly preferable because many dyes cause a decrease in the sensitivity of the photopolymerizable photosensitive layer.

Examples of the pigment used as the component (D-3) in the present invention include commercially available pigments and Color Index (C.I.) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977). , “Latest Pigment Application Technology”
(CMC Publishing, 1986), "Printing Ink Technology" C
MC Publishing, 1984) can be used. Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments,
Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic Soaps" (Koshobo),
"Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in. The pigment particle size is from 0.01 μm to 10
μm, preferably from 0.05 μm to 1 μm.
μm, more preferably 0.1 μm.
It is preferably in the range of m to 1 μm. When the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the coating solution for the image-sensitive layer, and when it exceeds 10 μm, the uniformity of the image-sensitive layer is not preferred.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a bur mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

The dyes that can be used include:
Ethyl violet, crystal violet, azo dyes, anthraquinone dyes, cyanine dyes and the like can be mentioned. The amount of the dye and pigment added is about 0.5% of the total composition.
5% to about 5% by weight is preferred.

(D-4) Other Additives In addition, inorganic fillers and other plasticizers for improving the physical properties of the cured film, oil-sensitizing agents and the like which can improve the ink adhesion of the photosensitive layer surface. Known additives may be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like, and a binder was used. In the case, 10% by weight based on the total weight of the compound having an ethylenically unsaturated double bond and the binder
The following can be added.

Further, a UV initiator, a thermal crosslinking agent and the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later.

In addition, additives for improving the adhesion between the photosensitive layer and the support and improving the removability of the unexposed photosensitive layer by development;
It is also possible to provide an intermediate layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, the adhesion can be improved and the printing durability can be increased. Addition of an acid or a hydrophilic polymer such as polysulfonic acid or undercoating improves the developability of the non-image area and improves the stainability.

Hereinafter, a method for producing a lithographic printing plate using the photosensitive composition of the present invention will be described. A lithographic printing plate is prepared by preparing the photosensitive composition of the present invention as a coating liquid, applying the prepared coating liquid on a support, and drying to form a photosensitive layer. Further, an intermediate layer may be provided between the photosensitive layer and the support.

[Preparation and Coating of Coating Solution] When the photosensitive composition of the present invention is coated on a support, it is dissolved in an organic solvent to prepare a coating solution. As the solvent used here,
Acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran,
Toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol Monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-
Methoxypropanol, methoxymethoxyethanol,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, lactic acid Examples include methyl and ethyl lactate.
These solvents can be used alone or as a mixture. And, the concentration of the solid content in the coating solution is 2 to 50.
% By weight is appropriate.

The amount of the photosensitive layer coated on the support mainly affects the sensitivity of the photosensitive layer, the developability, and the strength and printing durability of the exposed film, and it is desirable to appropriately select the amount according to the application. .
If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, the exposure takes time, and the developing process requires a longer time, which is not preferable. When the lithographic printing plate is a lithographic printing plate for scanning exposure, the coating amount of the photosensitive layer is about 0.1 g / m ^{2 by} weight after drying.
Range of about 10 g / m ² are suitable. More preferably, it is 0.5 to 5 g / m ² .

[Support] In order to obtain a lithographic printing plate, which is one of the main objects of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.),
Paper or plastic film on which the metal is laminated or vapor-deposited as described above is included, and if necessary, hydrophilicity is imparted to these surfaces, if necessary, and known physical and chemical properties suitable for the purpose of improving strength, etc. Processing may be performed.

Particularly preferred examples of the support include paper, a polyester film and an aluminum plate. Among them, it has good dimensional stability, is relatively inexpensive, and has excellent hydrophilicity and strength by surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. In addition, Shoko 4
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-8-18327 is also preferable.

The aluminum substrate is a dimensionally stable metal plate containing aluminum as a main component. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or aluminum (alloy) Is selected from a laminated or vapor-deposited plastic film or paper.

In the following description, the above-mentioned substrates made of aluminum or aluminum alloy are collectively used as aluminum substrates. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and the content of the foreign elements in the alloy is 10% by weight or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and any of conventionally known and used materials such as JIS A 1050 and JISA 110 can be used.
0, JIS A 3103, JIS A 3005, etc. can be used as appropriate. The thickness of the aluminum substrate used in the present invention is approximately 0.1 mm to 0.1 mm.
About 6 mm, preferably 0.15 mm to 0.4 mm,
Particularly preferably, it is 0.2 mm to 0.3 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the desire of the user. The aluminum substrate may be appropriately subjected to a substrate surface treatment described later as necessary. Of course, it need not be applied.

[Roughening Treatment] The aluminum substrate is usually subjected to a roughening treatment. A roughening treatment method is disclosed in
No. 893, such as mechanical surface roughening, chemical etching, and electrolytic graining. Further, an electrochemical surface roughening method of electrochemically roughening in an electrolytic solution of hydrochloric acid or nitric acid, a wire brush graining method for scratching the aluminum surface with a metal wire, and a pole for graining the aluminum surface with a polishing ball and an abrasive. A mechanical roughening method such as a grain method, a brush grain method for roughening the surface with a nylon brush and an abrasive can be used, and the above-described roughening methods can be used alone or in combination. Among them, a method usefully used for surface roughening is an electrochemical method in which the surface is chemically roughened in a hydrochloric acid or nitric acid electrolyte, and a suitable amount of electricity at the time of anode is 50 C / dm ^{2 to} 400 C.
C / d ² range. More specifically, 0.1 to 5
20 to 80 in an electrolyte containing 0% hydrochloric acid or nitric acid
° C, time 1 second to 30 minutes, current density 100 C / dm ² -4
It is preferable to perform AC and / or DC electrolysis under the conditions of 00 C / dm ² .

The aluminum substrate thus roughened may be chemically etched with an acid or an alkali. Preferable etching agents are caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like.
%, 20 to 100 ° C. After etching, pickling is performed to remove dirt (smut) remaining on the surface. The acids used are nitric acid, sulfuric acid, phosphoric acid, chromic acid,
Hydrofluoric acid, borofluoric acid and the like are used. In particular, as a method of removing the smut after the electrochemical surface-roughening treatment, a method of contacting with 15 to 65% by weight of sulfuric acid at a temperature of 50 to 90 ° C as described in JP-A-53-12739 is preferred. And an alkali etching method described in JP-B-48-28123. After the processing as described above, the method conditions are not particularly limited as long as the center line average set Ra of the processing surface is 0.2 to 0.5 μm.

[Anodic Oxidation Treatment] The aluminum substrate subjected to the surface roughening treatment as described above is thereafter subjected to an anodic oxidation treatment to form an oxide film. In the anodizing treatment, an aqueous solution of sulfuric acid, phosphoric acid, oxalic acid, or boric acid / sodium borate is used alone or in combination of two or more kinds as the main component of the electrolytic bath. At this time, at least A
Components normally contained in 1 alloy plates, electrodes, tap water, groundwater and the like may of course be included. Furthermore, the second and third components may be added. The second and third here
Components are, for example, Na, K, Mg, Li, Ca, Ti,
Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn
Cations such as metal ions, ammonium ions, etc., and anions such as nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, silicate ions, and borate ions. And its concentration may be about 0 to 10000 ppm. The condition of the anodizing treatment is not particularly limited, but is preferably 30 to 500 g / liter, and the treatment liquid temperature is 10 to 70 ° C.
At a current density of 0.1 to 40 A / m ² by DC or AC electrolysis. The thickness of the formed anodized film is in the range of 0.5 to 1.5 μm. Preferably it is in the range of 0.5 to 1.0 μm. The support prepared by the above-described process is a micropore present in the anodic oxide film having a pore diameter of 5 to 10 nm and a pore density of 8 × 10 ¹⁵ to
Processing conditions must be selected to fall within the range of 2 × 10 ¹⁶ / m ² .

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in Japanese Patent Application No. 5-304358 is also preferably used.

As another preferred example, there can be mentioned a support in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. As such a surface layer, for example, US30
55295, a layer composed of an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, a titanium oxide, a polyvinyl alcohol, and a silicate described in JP-A-8-507727. Sol-gel films and the like can be raised. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to improve the adhesion of the photosensitive layer. Etc.

[Intermediate Layer] The lithographic printing plate precursor according to the invention may be provided with an intermediate layer for the purpose of improving the adhesion between the photosensitive layer and the substrate and the stain resistance. Specific examples of such an intermediate layer include JP-B-50-7481 and JP-A-54-7481.
72104, JP-A-59-101651, JP-A-6101
Nos. 0-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282637, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, and JP-A-7-159983. 7-314937,
JP-A-8-202025, JP-A-8-320551
JP-A-9-34104, JP-A-9-236911
JP-A-9-269593, JP-A-10-6909
No. 2, JP-A-10-115931, JP-A-10-16
No. 1317, JP-A-10-260536, JP-A-10-260536
-282682, JP-A-11-84674, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270989, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, and Japanese Patent Application No. 9-89646. , Japanese Patent Application Nos. 9-106068, 9-183834, 9-264311,
Japanese Patent Application No. 9-127232, Japanese Patent Application No. 9-245419
No., Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170
No. 202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-1
No. 65861, Japanese Patent Application No. 11-284091, Japanese Patent Application No. 20
Nos. 00-14697 and the like.

"Protective layer" is a desirable embodiment of the present invention.
In a lithographic printing plate for scanning exposure, usually, since the exposure is performed in the air, it is preferable to further provide a protective layer on the layer of the photopolymerizable composition. The protective layer prevents low-molecular compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the photosensitive layer from being mixed into the photosensitive layer, and enables exposure in the atmosphere. I do. Therefore, a desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low, and further, the transmission of light used for exposure is not substantially inhibited, and the adhesion to the photosensitive layer is excellent. In addition, it is desirable that it can be easily removed in a developing step after exposure. Such a device for the protective layer has been conventionally devised, as disclosed in U.S. Pat. No. 3,458,311 and JP-A-55-49729.
It is described in detail in the issue.

Examples of materials that can be used for the protective layer include:
Relatively, it is preferable to use a water-soluble polymer compound having excellent crystallinity. Specifically, water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid are used. Although it is known, use of polyvinyl alcohol as the main component gives the best results in terms of basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component. Specific examples of polyvinyl alcohol include those having a hydrolysis of 71 to 100% and a molecular weight of 300 to 2,400.

Specifically, Kuraray's PVA-
105, PVA-110, PVA-117, PVA-1
17H, PVA-120, PVA-124, PVA-1
24H, PVA-CS, PVA-CST, PVA-H
C, PVA-203, PVA-204, PVA-20
5, PVA-210, PVA-217, PVA-22
0, PVA-224, PVA-217EE, PVA-2
17E, PVA-220E, PVA-224E, PVA
-405, PVA-420, PVA-613, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), the amount of coating, and the like are selected in consideration of fogging properties, adhesion, and scratch resistance in addition to oxygen blocking properties and development removability. Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen-barrier property is extremely increased, there arises a problem that an unnecessary polymerization reaction occurs during production or raw storage, and unnecessary fogging and thickening of an image occur during image exposure. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling is likely to occur due to insufficient adhesive force, and the peeled portion causes defects such as poor film curing due to inhibition of oxygen polymerization.

On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Pat. No. 292,501 and U.S. Pat. No. 44,563 describe that a hydrophilic polymer mainly comprising polyvinyl alcohol includes
It is described that sufficient adhesion can be obtained by mixing 5 to 80% by weight of an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer and laminating the mixture on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer,
For example, U.S. Pat. No. 3,458,311;
No. 9729.

Further, other functions can be imparted to the protective layer. For example, 350nm to 450n used for exposure
The addition of a coloring agent (such as a water-soluble dye) having excellent light transmittance of m and capable of efficiently absorbing light having a wavelength of 500 nm or more can further enhance the safelight suitability without lowering the sensitivity.

When a photosensitive material using the photopolymerizable composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. . Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate are JP-B-57-74.
No. 27, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate and tertiary phosphorus. Ammonium acid,
Aqueous solutions of inorganic alkali agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Also, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

In the plate making process of the lithographic printing plate precursor according to the invention, if necessary, the entire surface may be heated before exposure, during exposure, or between exposure and development. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity can be brought about. Furthermore, for the purpose of improving image strength and printing durability,
It is also effective to post-heat or expose the entire surface of the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high,
There is a problem that the non-image portion is covered. Very strong conditions are used for heating after development. Usually 200 ~
It is in the range of 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

As the method of exposing a lithographic printing plate for scanning exposure according to the present invention, known methods can be used without limitation. Desirable wavelength of the light source is from 350 nm to 450 nm, and specifically, an InGaN semiconductor laser is suitable. The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type, and the like. The photosensitive layer component of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one. After loading on the top, a system such as exposure-development can be performed on the machine.

Other light rays for exposure to the photopolymerizable composition according to the present invention include ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet lamps. Various laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can also be used. The following can be used as the available laser light source of 350 nm to 450 nm. As a gas laser, an Ar ion laser (364 nm,
351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He-
Cd laser (441 nm, 325 nm, 1 mW-10
0mW), Nd: YAG (YVO)
₄ ) and SHG crystal x 2 times (355 nm, 5
mW to 1 W), a combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW), and a KNbO ₃ ring resonator (430 nm, 30 m) as a semiconductor laser system.
W), waveguide type wavelength conversion element and AlGaAs, InGaAs
Combination of s semiconductors (380 nm to 450 nm, 5 m
W-100 mW), waveguide type wavelength conversion element and AlGaIn
Combination of P and AlGaAs semiconductors (300 nm to 3
50 nm, 5 mW to 100 mW), AlGaInN (3
50nm~450nm, 5mW~30mW) Other, N ₂ laser (337 nm as a pulse laser, pulse: 0.1 to 10), XeF (351 nm, pulse 10
In particular, an AlGaInN semiconductor laser (commercially available In
GaN-based semiconductor laser 400 to 410 nm, 5 to 30
mW) is preferable in terms of wavelength characteristics and cost.

As the lithographic printing plate exposure apparatus of the scanning exposure type, there are an inner drum type, an outer drum type, and a flat bed type as an exposure mechanism, and a light source capable of continuous oscillation among the above light sources is preferably used. be able to. Actually, the following exposure apparatus is particularly preferable in relation to the sensitivity of the photosensitive material and the plate making time.・ Single beam to triple beam exposure equipment using one or more gas lasers or solid-state laser light sources so that the internal drum method becomes a semiconductor laser with a total output of 20 mW or more. Multi-beam (1 to 10) using one or more semiconductor laser, gas laser or solid-state laser
Multi-beam (1 to 9) using one or more semiconductor lasers, gas lasers, or solid-state lasers so that the total output becomes 20 mW or more with the exposure apparatus of the present invention and the external drum method.
1) A semiconductor laser or solid-state laser is used so that the total output is 20 mW or more with the exposure apparatus and external drum method
In a laser direct-writing type lithographic printing plate such as a multi-beam (10 or more) exposure device or more used,
In general, the sensitivity of the photosensitive material X (J / cm ² ), the exposed area S of the photosensitive material
(Eq 2) between (cm ² ), the power q (W) of one laser light source, the number n of lasers, and the total exposure time t (s).
Holds. X · S = n · q · t − (eq 1) i) In the case of the inner drum (single beam) system, the laser rotation speed f (radian / s), the sub-scanning length Lx (c) of the photosensitive material
m), resolution Z (dots / cm), total exposure time t (s)
Equation (eq 2) is generally established between. f · Z · t = Lx − (eq 2)

Ii) In the case of the external drum (multi-beam) system, the drum rotation speed F (radian / s) and the sub-scanning length L of the photosensitive material
x (cm), resolution Z (dot / cm), total exposure time t
(S) and the number of beams (n) generally have the formula (eq 3)
Holds. F ・ Z ・ nt ・ L = Lx-(eq 3)

Iii) In the case of the flat head (multi-beam) system, the rotation number H (radian / s) of the polygon mirror,
Sub-scanning length Lx (cm), resolution Z (dot / c)
m), the total exposure time t (s), and the number of beams (n), the equation (eq 4) generally holds. F · Z · nt · Lx
−− (eq 4)

The resolution required for the actual printing plate (256
0 dpi), plate size (A1 / B1, sub-scanning length 42 in)
ch), exposure conditions of about 20 sheets / hour and the photosensitive properties of the photosensitive composition of the present invention (photosensitive wavelength, sensitivity: about 0.1 mJ /
By substituting cm ² ) into the above equation, it can be understood that the photosensitive material of the present invention is preferably combined with a multi-beam exposure system using a laser having a total output of 20 mW or more. However, when a laser having a necessary and sufficient output (30 mW or more) is used, the combination with an internal drum type semiconductor laser single beam exposure apparatus is most preferable in terms of operability and cost.

After image exposure with a conventionally known actinic ray,
Before the development, by providing a heating process at a temperature of 50 ° C. to 150 ° C. for 1 second to 5 minutes at a temperature of 50 ° C. to 150 ° C. for the purpose of increasing the curing rate of the photopolymerizable photosensitive layer, thereby improving the curability of the non-image portion, This is more preferable because the printing durability can be further improved.

The photopolymerizable composition according to the present invention can be used without limitation in lithographic printing plates for scanning exposure and those widely known as photocurable resins. For example, when applied to a liquid photopolymerizable composition used in combination with a cationic polymerizable compound as needed, a highly sensitive stereolithographic material can be obtained. In addition, a hologram material can be formed by utilizing a change in refractive index due to photopolymerization. It can be applied to various transfer materials (peeling-sensitive material, toner-developing material, etc.) by utilizing the change in surface tackiness accompanying photopolymerization. It can also be applied to light curing of microcapsules. It can also be applied to the production of electronic materials such as photoresists, and photocurable resin materials such as inks, paints and adhesives.

Further, the combination of the S-substituted styryl dye and the titanocene initiator according to the present invention is a photoinitiating system having excellent photosensitivity and excellent stability, other than the photopolymerizable composition described in detail above. Again, various uses can be used. For example, radical generation with high efficiency by light can cause, for example, oxidative coloring of a triphenylmethane-based leuco dye with high sensitivity. In addition, it can cause a decolorization reaction due to radical addition to certain polymethine dyes.

[0153]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. "Reference experiment" The emission intensity distribution of a safelight, which is generally used, was measured, and the position where the emission intensity distribution on the short wave side rises was measured. The workability under each safelight was evaluated.

[0154]

[Table 1]

As described above, considering the workability, a yellow lamp is desired, and a photosensitive material that can be handled under the yellow lamp needs to have a low photosensitivity at a wavelength of at least 520 nm, preferably 490 nm.

"Examples 1 to 20, Comparative Examples 1 and 2" (Preparation of Support) An aluminum plate having a thickness of 0.3 mm was
After etching by immersion in 60% by weight of sodium hydroxide at 60 ° C for 25 seconds, it was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was subjected to electrolytic surface roughening treatment in a 1% by weight nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode electricity of 300 coulomb / dm ² . Followed by 1
After immersion in a 30% by weight aqueous solution of sulfuric acid at 40 ° C. for 5 seconds, immersion in a 30% by weight aqueous solution of sulfuric acid and desmutting at 60 ° C. for 40 seconds, a current density of 2 A / dm ² in a 20% by weight aqueous solution of sulfuric acid 2.7 g of anodized film
/ m ² for 2 minutes. The surface roughness was measured to be 0.3 μm (JIS B0601
Ra display).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater,
The support was then provided with a back coat layer having an applied amount of 70 mg / m ² after drying.

Sol-gel reaction liquid Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 part by weight

When the above components were mixed and stirred, exotherm started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a backcoat coating solution.

Pyrogallol formaldehyde condensation resin (molecular weight: 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant 0.7 parts by weight (N-butyl perfluorooctane sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 2) 10,000) methanol silica sol 50 parts by weight (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by weight) methanol 800 parts by weight

(Preparation of Photosensitive Layer) A photopolymerizable composition having the following composition was coated on the aluminum plate treated in this manner so that the dry coating amount was 1.4 g / m ^2, and the coating was performed at 80 ° C. for 2 minutes. It was dried to form a photosensitive layer.

Pentaerythritol tetraacrylate 1.5 g Benzyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 75/25) 2.0 g Photopolymerization initiation system (Table 2) Sensitizing dyes (D1 to D20, DR- 1, DR-2) 0.05 g titanocene compound (T-2) 0.03 g fluorinated nonionic surfactant (F-177P) 0.03 g thermal polymerization inhibitor N-nitrosophenylhydroxyl 0.01 g amine aluminum salt Pigment dispersion Product 2.0 g Composition of pigment dispersion Composition: Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83/17) Cyclohexanone 15 parts by weight Methoxypropyl acetate 20 parts by weight Propylene glycol monomethyl ether 40 parts by weight Methyl ethyl ketone 20 g Pro Pyrene glycol monomethyl ether 20 g

The structures of the sensitizing dyes D1 to D20 are as described above, and the structures of the sensitizing dyes DR-1, DR-2 and the titanocene compound T-2 will be described later.

(Preparation of Protective Layer) On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (98% by mole of saponification, degree of polymerization of 550) was applied so as to have a dry coating weight of 2 g / m ² . Dry at 100 ° C. for 2 minutes.

(Evaluation of photosensitivity and safelight suitability) On the thus obtained photosensitive material, a Fuji Step Guide (透過 D = 0.15, discontinuous transmission optical density at Fuji Photo Film Co., Ltd.) was applied. (A gray scale in which the value changes), and exposure was performed by a xenon lamp passing through an optical filter so as to have a known exposure energy. Thereafter, the film was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, and the maximum number of steps at which an image was completely removed was read to calculate the sensitivity. The higher the number of stages, the higher the sensitivity. For the purpose of estimating the suitability for exposure to short-wavelength semiconductor lasers, Kenko BP-40 was used as an optical filter, and exposure was performed with monochromatic light of 400 nm.
Exposure was performed with 490 nm monochromatic light using -49. It is desirable that the sensitivity at 400 nm is high and the sensitivity at 490 nm is low. Table 1 shows the ratio of 400 nm sensitivity (mJ / cm ² ) / 490 nm sensitivity (mJ / cm ² ) thus determined. The larger the value, the more desirable. The results are shown in Table 2 together with the absorption maximum of the sensitizing dye in the solution and the solvent used for the measurement.

(Composition of Developer) DP-4 (Fuji Photo Film Co., Ltd.) 65.0 g Water 880.0 g Lipomin LA (20% aqueous solution, manufactured by Lion Corporation) 50.0 g

[0167]

[Table 2]

As described above, the lithographic printing plate according to the present invention has a 400 mm wavelength corresponding to the oscillation wavelength of the short-wavelength semiconductor laser in comparison with the photosensitivity at a wavelength of 490 nm corresponding to fog under yellow light.
The lithographic printing plate has a remarkably high sensitivity in nm and excellent suitability for safelight. On the other hand, a lithographic printing plate of a comparative example using a conventionally known carbomerocyanine sensitizing dye is rather 490n.
m, and has no suitability for safelight at all.

Examples 21 to 34 and Comparative Examples 3 to 9 A lithographic printing plate was prepared according to the following procedure, and the printing performance was evaluated. Table 3 shows the results.

(Preparation of Support) Thickness 0.24 mm, width 1
Using a 030 mm JIS A 1050 aluminum plate, the treatment was continuously performed as follows. (A) Specific gravity 1.12 using an existing mechanical roughening device
While the suspension of the polishing agent (pumice) and water was supplied to the surface of the aluminum plate as a polishing slurry liquid, the surface was mechanically roughened with a rotating roller-shaped nylon brush.
The average particle size of the abrasive is 40-45 μm and the maximum particle size is 200 μ
m. The nylon brush was made of nylon 6/10, and had a bristle length of 50 mm and a bristle diameter of 0.3 mm. Nylon brushes were made by making holes in a stainless steel cylinder of φ300 mm and densely implanting the hairs. 3 rotating brushes
Used this book. Two support rollers at the bottom of the brush (φ20
0 mm) was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus the load before pressing the brush roller against the aluminum plate. The rotating direction of the brush is the same as the moving direction of the aluminum plate, and the number of rotation is 20.
It was 0 rpm. (B) An aluminum plate was prepared by adding a caustic soda concentration of 2.6% by weight,
The aluminum plate was subjected to an etching treatment by spraying at an aluminum ion concentration of 6.5% by weight and a temperature of 70 ° C. to dissolve 0.3 g / m ^{2 of the} aluminum plate. Thereafter, washing with water was performed by spraying. (C) Desmut treatment with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions) was performed by spraying, and then water washing was performed by spraying. As the nitric acid aqueous solution used for the desmutting, a waste liquid from a step of performing electrochemical surface roughening using an alternating current in a nitric acid aqueous solution was used.

(D) Electrochemical surface roughening treatment was continuously performed using an AC voltage of 60 Hz. The electrolytic solution at this time was a 1% by weight aqueous nitric acid solution (containing 0.5% by weight of aluminum ion and 0.007% by weight of ammonium ion) at a temperature of 40 ° C. In the AC power supply, the time TP until the current value reaches a peak from zero is 2 msec, and the duty ratio is 1:
1. Using a trapezoidal rectangular wave alternating current, electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The current density is 3 at the peak value of the current.
0 A / dm ² , and the amount of electricity was 255 C / cm ² in total of the amount of electricity when the aluminum plate was an anode. 5% of the current flowing from the power supply was diverted to the auxiliary anode. Thereafter, water washing by spraying was performed. (E) The aluminum plate was spray-etched at a concentration of 26% by weight of caustic soda and a concentration of 6.5% by weight of aluminum ion at 32 ° C.
g / m ² , and removal of a smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening is performed using alternating current at the preceding stage, and dissolution of an edge portion of the generated pit, Edges are smoothed. Then, it was washed with a spoon. (F) A desmutting treatment was performed by spraying with a 25% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) at a temperature of 60 ° C., followed by washing with water by spraying.

(G) Anodizing apparatus of the existing two-stage power supply electrolysis treatment method (each of the first and second electrolytic unit lengths 6 m, the first power supply unit length 3 m, the second power supply unit length 3 m, the first and second power supply electrode lengths) 2.4m) using a sulfuric acid concentration of 170 g / liter (containing 0.5% by weight of aluminum ions) in the electrolytic section, at a temperature of 3
Anodizing treatment was performed at 8 ° C. Thereafter, washing with water was performed by spraying. At this time, in the anodizing apparatus, the current from the power supply flows to the first power supply electrode provided in the first power supply unit, flows to the plate-shaped aluminum via the electrolytic solution, and is supplied to the plate-shaped aluminum in the first electrolytic unit. An oxide film is generated on the surface, and returns to the power supply through the electrolytic electrode provided in the first power supply unit. On the other hand, the current from the power supply flows to the second power supply electrode provided in the second power supply unit, similarly flows to the plate aluminum through the electrolytic solution, and forms an oxide film on the surface of the plate aluminum in the second electrolytic unit. The amount of electricity supplied from the power supply to the first power supply unit and the amount of electricity supplied from the power supply to the second power supply unit are the same, and the power supply current density on the oxide film surface in the second power supply unit is approximately It was 25 A / dm ² . In the second power supply unit:
Power was supplied from the surface of the oxide film of 35 g / m ² .
The final oxide film amount was 2.7 g / m ² . The aluminum support so far is referred to as [AS-1].

(Hydrophilic treatment) Aluminum support [AS
-1], a silicate treatment was performed to increase the hydrophilicity of the printing plate non-image portion. For the treatment, a 1.5% aqueous solution of sodium silicate No. 3 was maintained at 70 ° C., passed through the aluminum web so that the contact time was 15 seconds, and further washed with water. The amount of Si deposited was 10 mg / m ² . This support is referred to as [AS-
2].

(Coating of Intermediate Layer) A liquid composition (sol solution) of the SG method was prepared by the following procedure. The following composition was weighed into a beaker and stirred at 25 ° C. for 20 minutes. Tetraethoxysilane 38g 3-methacryloxypropyltrimethoxysilane 13g 85% phosphoric acid aqueous solution 12g Deionized water 15g Methanol 100g

The solution was transferred to a three-necked flask, fitted with a reflux condenser, and immersed in a room-temperature oil bath. The contents of the three-necked flask were heated to 50 ° C. in 30 minutes while being stirred with a magnetic stirrer. While maintaining the bath temperature at 50 ° C., the reaction was further performed for 1 hour to obtain a liquid composition (sol liquid). This sol solution was diluted with methanol / ethylene glycol = 20/1 (weight ratio) to 0.5% by weight, applied to the aluminum substrate [AS-1] by a boiler, and dried at 100 ° C. for 1 minute. . The coating amount at that time was 3.5 mg / m ² . With respect to this coating amount, the amount of Si element was obtained by a fluorescent X-ray analysis method, and the obtained amount was used as the coating amount. The support thus formed is referred to as [AS-3].

Next, a solution having the following composition was applied to an aluminum support [AS-2] using a wire bar, and dried at 90 ° C. for 30 seconds using a hot air drier. The coating amount after drying was 10 mg / m ² .

Copolymer of ethyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15 0.1 g 2-aminoethylphosphonic acid 0.1 g methanol 50 g ion-exchanged water 50 g The support thus prepared is referred to as [AS-4].

(Coating of photosensitive layer) On a support shown in Table 3, a photosensitive solution having the following composition was prepared, and the coating amount was 1.0 to 2.0.
0g / m ² , apply with a wheeler, 100 ℃
For 1 minute.

(Photosensitive solution) Addition polymerizable compound (compound described in Table 2) 1.5 g Binder polymer (compound described in Table 2) 2.0 g Sensitizing dye (compound described in Table 2) 0 0.1 g initiator (compounds listed in Table 2) 0.4 g co-sensitizer (compounds listed in Table 2) 0.2 g colored pigment dispersion 2.0 g (composition of pigment dispersion) Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83/17) thermal polymerization cyclohexanone 15 parts by weight methoxypropyl acetate 20 parts by weight propylene glycol monomethyl ether 40 parts by weight Thermal polymerization inhibitor (N- Nitrosophenylhydroxylamine aluminum salt) 0.01 g Surfactant (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.) .02g ethyl ketone 20.0g Polo propylene glycol monomethyl ether 20.0g

(Coating of Protective Layer) A 3% by weight aqueous solution of polyvinyl alcohol (a saponification degree of 98 mol% and a polymerization degree of 550) was applied onto the photosensitive layer so that the dry coating weight was 2 g / m ^2. And dried at 100 ° C. for 2 minutes.

(Exposure of lithographic printing plate precursor) Using the lithographic printing plate precursor obtained as described above as a light source, monochromatic light of 400 nm, and a plate surface exposure energy density of 200 µJ / c
The exposure power was adjusted to m ^2, and solid image exposure and halftone image exposure at 175 lines / inch in 1% increments from 1 to 99% were performed.

(Development / plate making) A predetermined developing solution (described in Table 2) and a finisher FP-manufactured by Fuji Photo Film Co., Ltd. were added to an automatic developing machine LP-850 manufactured by Fuji Photo Film Co., Ltd.
2 W each was charged and the developer temperature was 30 ° C. and the development time was 18
The plate that had been exposed under the conditions of seconds was developed / plate-making to obtain a lithographic printing plate.

[0183]

[Table 3]

(Addition polymerizable compound in Table 3) (M-1) pentaerthritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester A-TMM)
T) (M-2) Glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .; UA101H)

(Binder polymer in Table 3) (B-1) Allyl methacrylate / methacrylic acid / N-
Isopropylacrylamide (copolymerization molar ratio 67/13
/ 20), measured acid value 1.15 determined by NaOH titration
meq / g, weight average molecular weight 130,000 determined by GPC measurement (B-2) allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17), measured acid value 1.55 meq / g determined by NaOH titration (B-3) Polyurethane resin which is a condensation polymer of the following diisocyanate and diol: 4,4'-diphenylmethane diisoisocyanate (MDI) Hexamethylene diisocyanate (HMDI)・ Polypropylene glycol, weight average molecular weight 1000
(PPG1000) • 2,2-bis (hydroxymethyl) propionic acid (DMPA) ｛copolymerization molar ratio (MDI / HMDI / PPG1000 /
DMPA) 40/10/15/35 °. An acid value of 1.05 meq / g measured by NaOH titration and a weight average molecular weight of 45,000 determined by GPC measurement.

(Developer in Table 3) (DV-1) Aqueous solution of pH 12 having the following composition (Developer) 1.5 parts by weight of triethanolamine 0.16 part by weight of potassium hydroxide Compound of the following formula (22) 5.0 parts by weight Water 93.3 parts by weight

[0187]

Embedded image

(DV-2) An aqueous solution having the following composition and having a pH of 10: monoethanolamine 0.1 part by weight triethanolamine 1.5 part by weight Compound of the above formula (22) 4.0 parts by weight Compound of the following formula (24) 2.5 parts by weight Compound of the following formula (25) 0.2 parts by weight Water 91.7 parts by weight

[0189]

Embedded image

(DV-3) pH 13 aqueous solution having the following composition 1K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight Compound of formula (25) 0.2 parts by weight Water 95.3 parts by weight

As described above, the planographic printing plate of the present invention has a very high sensitivity, and shows sufficient sensitivity for the scanning exposure method. Further, the initiator system of the present invention has higher sensitivity than when no sensitizing dye is used, and shows a sufficient sensitivity even when the initiator is added in a small amount.

Examples 35 to 48 A lithographic printing plate was prepared according to the following procedure, and the printing performance was evaluated. Table 4 shows the results.

"Pretreatment of support" Material 1 having a thickness of 0.3 mm
After graining the surface of the aluminum plate of S using a No. 8 nylon brush and an aqueous suspension of 800 mesh pumice stone. Washed well with water. After etching by dipping in 10% by weight of sodium hydroxide at 70 ° C. for 60 seconds, the plate was washed with running water, neutralized and washed with 20% by weight of nitric acid, and then washed with water. This was subjected to electrolytic surface roughening treatment in a 1% by weight nitric acid aqueous solution at an anode electricity of 300 coulomb / dm ² using a sine wave alternating waveform current under the condition of VA = 12.7V.
The surface roughness was measured to be 0.45 μm (JIS
Ra display according to B0601).

[0194] The above support "hydrophilizing treatment of the surface of support", sodium silicate No. 3 _(SiO 2 = _28~30%, Na
₍₂ O = 9 to 10%, Fe = 0.02% or less), 2.5% by weight, pH = 11.2, 70 ° C. for 13 seconds, followed by washing with water. From the amount of Si element determined by X-ray fluorescence analysis of the surface, the amount of surface silicate was 10 mg / m2.
² was asked.

"Coating of Intermediate Layer" A coating liquid having the composition shown in the following (A) was prepared so that the coating amount of phenylphosphonic acid was 20 mg / m ² on the surface of the above-mentioned hydrophilic support. Then, after coating with a wheeler under the condition of 180 rpm, 80
Dry at 30 ° C. for 30 seconds.

(Intermediate layer coating liquid A) Phenylphosphonic acid 0.07 g to 1.4 g Methanol 200 g

A photosensitive solution having the following composition was prepared on a support provided with the above-mentioned intermediate layer, and was applied with a wheeler so that the coating amount was 1.0 to 2.0 g / m ^2. Dried for minutes.

(Photosensitive solution) Addition polymerizable compound (compound described in Table 3) 2.0 g Binder polymer (compound described in Table 3) 1.8 g Electron transfer type initiation system (initiator / sensitizing dye / Co-sensitizer) (described in Table 3) Colored pigment dispersion 2.0 g (Pigment dispersion composition) Pigment Blue 60 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83 / 17) Thermal polymerization Cyclohexanone 15 parts by weight Methoxypropyl acetate 20 parts by weight Propylene glycol monomethyl ether 40 parts by weight Thermal polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum salt) 0.01 g Surfactant (Dainippon Ink & Chemicals, Inc.) 0.02 g methyl ethyl ketone 30.0 g polopylene glycol monomethyl Ether 30.0g

"Coating of Protective Layer" A 3% by weight aqueous solution of polyvinyl alcohol (98 mol% saponification degree, polymerization degree 550) was applied onto the photosensitive layer so that the dry coating weight was 2 g / m ^2. And dried at 120 ° C. for 3 minutes.

[Printing durability test] R201 manufactured by Roland was used as a printing machine and G was manufactured by Dainippon Ink and Chemicals, Inc.
EOS-G (N) was used. The printed matter in the solid image area was observed, and the printing durability was examined based on the number of sheets at which the image began to fade. The larger the size, the better the printing durability.

"Dot-dot Printing Durability Test" R201 manufactured by Roland was used as a printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as an ink. 5 from the start of printing
On the 000 th sheet, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked into a printing sponge, halftone dots were wiped off, and the ink on the plate surface was washed. Then, 10,0
The printing of 00 sheets was performed, and the presence or absence of halftone dot skipping in the printed matter was visually observed.

"Stain test" R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink Co., Ltd.
EOS-G (S) was used. The printed matter in the non-image area (unexposed area) was observed, and the stain property was evaluated.

[0203]

[Table 4]

As is clear from Table 4, the lithographic printing plate according to the present invention provides an excellent lithographic printing plate even under conditions that allow plate making with high productivity by scanning exposure, that is, under very low energy exposure conditions. . Further, by selecting an appropriate addition-polymerizable compound, a binder polymer and a developing solution, one having high printing durability was obtained.

Example 49 A lithographic printing plate precursor was prepared in the same manner as in Example 1, except that the starting system was changed to the composition shown in Table 5 below, and the thickness of the photopolymerized layer was changed to 1.5 g / m ² . .

[0206]

[Table 5]

The obtained lithographic printing plate precursor was subjected to oscillation wavelength
Using a 400 nm InGaN-based semiconductor laser, a beam system on the plate surface of 25 μm, and an exposure energy density of 0.2 mJ / c
Scanning exposure was performed under the condition of m ² . Next, add 10 plates
After heating at 0 ° C. for 10 seconds, the aforementioned developing treatment was performed.
A planographic printing plate having a blue image with excellent visibility was obtained. Using the obtained plate, Heidelberg KOR-D
When offset printing was performed using a printing machine, 200,000 or more printed matters having excellent image density and stain resistance were obtained.

Example 50 The plate of Example 49 was stored under a forced storage condition of 65% humidity and 45 ° C. for 3 days, and plate making and printing were performed in the same manner as in Example 49. The same good results as in Example 49 were obtained.

Example 51 A lithographic printing plate precursor was prepared in the same manner as in Example 49, except that the starting system was changed to the composition shown in Table 6 below, and the thickness of the photopolymerized layer was changed to 2.0 g / m ² . .

[0210]

[Table 6]

The obtained lithographic printing plate precursor was irradiated with a beam system of 25 μm and an exposure energy density of 0.15 mJ using an InGaN-based semiconductor laser having an oscillation wavelength of 400 nm.
Scanning exposure was performed under the conditions of / cm ² . Next, the plate was heated at 100 ° C. for 10 seconds, and then the above-described developing treatment was performed. A planographic printing plate having a blue image with excellent visibility was obtained. The obtained plate was further heated at 300 ° C. for 5 minutes, and then subjected to offset printing using a Heidelberg KOR-D machine. As a result, it was possible to obtain 200,000 or more printed matter having excellent image density and stain resistance. Was.

Example 52 The plate of Example 51 was exposed to a yellow light for 30 minutes before exposure, and plate making and printing were performed in exactly the same manner. The same excellent results as in Example 51 were obtained.

The structural formula of each compound used in the above examples is shown below.

[0214]

Embedded image

[0215]

The lithographic printing plate precursor according to the present invention provides a lithographic printing plate having sufficient sensitivity suitable for scanning exposure with a short-wavelength semiconductor laser such as InGaN, and excellent in printing durability and stain resistance. . The lithographic printing plate precursor for scanning exposure according to the present invention has remarkably improved fog under yellow light, and the workability of handling the plate can be greatly improved. Further, the photopolymerizable composition of the present invention has excellent sensitivity and also has extremely excellent storage stability.

Claims (4)

[Claims] (1) a compound having at least one vinyl group on an aromatic ring and at least one of the ortho and para positions thereof being substituted with a sulfur atom, (ii) a titanocene compound, and (iii) A) a photosensitive composition containing a compound which reacts with at least one of a radical and an acid and which is retained while changing at least one of its physical and chemical properties. 2. The photosensitive composition according to claim 1, wherein the compound (i) is a compound represented by the following general formula (1). Embedded image In the formula (1), R ^{1 to} R ⁸ each represent a hydrogen atom or a monovalent nonmetallic atomic group, and can be bonded to each other to form an aliphatic or aromatic ring. Provided that at least one of R ¹ , R ³ and R ⁵ is-
Representing the SR ^9. Here, R ⁹ has the same meaning as R ^{1 to} R ⁸ . 3. A compound (ii) which reacts with at least one of the radical and the acid and changes and retains at least one of its physical and chemical properties.
3. The photosensitive composition according to claim 1, wherein i) is an addition polymerizable compound having an ethylenically unsaturated double bond. 4. A photopolymerization method, comprising exposing the photosensitive composition according to claim 1 to a laser beam having a wavelength of 450 nm or less.