JP2003122002A - Photopolymerizable composition, photosensitive lithographic printing plate, and method for making printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition and a photosensitive lithographic printing plate excellent in sensitivity and fastness. SOLUTION: In the photopolymerizable composition containing ethylenic monomers and a photopolymerization initiating system, it is characterized in that the ethylenic monomers contain a urethane compound (C) having four or more urethane bonds and four or more addition polymerizable double bonds in one molecule, and a layer for the purpose of cutting oxygen is not prepared on the photopolymerizable composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition, and further to a photosensitive lithographic printing plate, a copper etching resist for wiring boards, a copper etching resist for gravure, a dry film, a color filter, and a plasma. The present invention relates to a highly sensitive photopolymerizable composition that can be used for various pattern forming materials such as a pigment-dispersed resist for displays, a photosensitive lithographic printing plate, and a plate making method for the printing plate.

[0002]

2. Description of the Related Art Conventionally, many image forming methods utilizing a photopolymerization system are known. For example, a photopolymerizable composition layer made of a photopolymerizable composition containing an addition-polymerizable ethylenic double bond-containing compound, a photopolymerization initiator, and optionally an organic polymer binder is provided on a support. A method for forming a cured relief image by exposing a desired image to the provided photosensitive material to polymerize and cure the exposed portion and dissolving and removing the unexposed portion is provided between two supports, at least one of which is transparent. A photosensitive material provided with a layer of a polymerizable composition is exposed to light from the transparent support side to cause a change in adhesive strength by light, and a method of forming an image by peeling the support, and other photopolymerizable composition layers There is an image forming method utilizing a change in toner adhesion due to light.

Various types of photopolymerization initiation systems for such photopolymerizable compositions are known. For example, a combination of a titanocene and a sensitizer (for example, JP-A-4-219756).
JP-A No. 4-241338, JP-A No. 7-5685, a system of a pyrromethene complex sensitizer and a radical generator.
JP-A-7-225474) and the like are known to have relatively high sensitivity. However, any of the above photopolymerizable compositions is desired to be further improved in terms of sensitivity. For example, when an image is recorded at a high speed by a low-power argon laser or FD-YAG laser, the sensitivity is further increased. The composition must be

On the other hand, it has been known to use various acrylate compounds as the polymerizable component of the photopolymerizable composition. For example, an acrylate compound which is an ester of (meth) acrylic acid with a hydroxyl group-containing compound and a diisocyanate compound are used. Urethane acrylate compounds obtained by reacting a compound containing a hydroxyl group and an acrylate group are known (for example, JP-A No. 11-271969).

[0005]

However, it has been practically necessary for such a photopolymerizable composition to block oxygen during exposure. This is because oxygen remarkably hinders the polymerization reaction due to exposure, making it impossible to form a sufficient image. Therefore, it was necessary to vacuumize the environment of the photopolymerizable composition at the time of exposure, or to coat the surface of the photopolymerizable composition with a film for the purpose of blocking oxygen. The necessity of blocking oxygen is particularly essential for laser scanning exposure. This is because the photopolymerizable composition used in this application requires high sensitivity especially for shortening the scanning time. On the other hand, however, the provision of a new oxygen barrier layer for the purpose of blocking oxygen has the drawback that the number of manufacturing steps is increased by one and the steps such as development processing are complicated accordingly. Further, even when the environment is evacuated during exposure, it is necessary to newly provide a waiting time and equipment, which is not desirable.

[0006]

According to the study of the present inventor, a specific compound as a urethane compound, that is,
(C) A urethane-based compound having four or more urethane bonds and four or more addition-polymerizable double bonds in one molecule, and more specifically,

[0007]

[Chemical 2]

[In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, and Ra represents alkylene, arylene, alkyleneoxy or a repeating group derived from aryleneoxy. Having a unit, Rb represents alkylene, arylene, alkyleneoxy, aryleneoxy, Rc independently represents a C1-20 alkylene, arylene group, Rd is hydrogen or a C1-20 organic residue or an alkali metal group. And represents an organic residue having at least 1 to 10 (meth) acrylic groups,
Ra, Rb, Rc, and Rd may each independently have a substituent. It has been surprisingly found that a sufficiently cured image is formed even when the oxygen-barrier layer, which was conventionally required, is not used, and the present invention has been accomplished. That is, the gist of the present invention is, in a photopolymerizable composition containing an ethylenic monomer and a photopolymerization initiation system, 4 or more urethane bonds and 4 or more urethane bonds in one molecule as an ethylenic monomer. And a photopolymerizable composition containing a urethane compound (C) having a double bond capable of addition polymerization, which is not provided on the photopolymerizable composition. It exists in things. Another subject matter of the present invention lies in a photosensitive lithographic printing plate having a layer comprising the photopolymerizable composition on a support. In addition, another gist of the present invention is
The photosensitive lithographic printing plate is imagewise exposed to a laser beam to photo-cure the photosensitive layer imagewise, and then the unexposed portion of the layer comprising the photopolymerizable composition is removed from the support to form a photocurable photosensitive layer. A method of forming an image, which comprises a method of making a printing plate, which comprises developing an alkali developing solution after the image exposure to remove the unexposed portion of the photosensitive layer from the support.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The addition-polymerizable ethylenic double bond-containing compound (hereinafter abbreviated as “ethylenic monomer”) in the photopolymerizable composition of the present invention means that when the photopolymerizable composition is irradiated with actinic rays, It is a monomer having an ethylenic double bond that undergoes addition polymerization by the action of the photopolymerization initiation system, which is the second essential component, and is cured. Incidentally, the meaning of the monomer in the present invention is a concept opposite to a polymer binder having a film-forming ability, and therefore, in addition to the narrowly defined monomer, a dimer, a trimer, and an oligomer. It also includes.

The photopolymerizable composition of the present invention comprises, as an ethylenic monomer, (C) four or more urethane bonds in one molecule.
[—NH— (C═O) —O—] and a urethane-based compound having four or more addition-polymerizable double bonds, and more specifically, a compound having the following structure Is.

[0011]

[Chemical 3]

[In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, and Ra represents alkylene, arylene, alkyleneoxy or aryleneoxy-repeat. Having a unit, Rb represents alkylene, arylene, alkyleneoxy, aryleneoxy, Rc independently represents a C1-20 alkylene, arylene group, Rd is hydrogen or a C1-20 organic residue or an alkali metal group. And represents an organic residue having at least 1 to 10 (meth) acrylic groups,
Ra, Rb, Rc, and Rd may each independently have a substituent. The method for producing the urethane compound is not particularly limited, but since a urethane bond can be easily formed by an addition reaction of an isocyanate group and a hydroxyl group,
Preferably, (A) a compound having four or more isocyanate groups in one molecule, and (B) a compound having one or more hydroxyl groups and two or more addition-polymerizable double bonds in one molecule. Obtained by reacting. Examples of the compound (A) containing four or more isocyanate groups in one molecule include, for example, a compound having two or more alcoholic hydroxyl groups (hereinafter referred to as polyhydric alcohols) and two isocyanate groups. Examples thereof include compounds in which four or more isocyanate groups have been introduced by the reaction with the above compounds.

Specifically, a compound having four or more alcoholic hydroxyl groups in one molecule such as pentaerythritol and polyglycerin is added to a diisocyanate compound such as hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and trimethylhexamethylene diisocyanate. A compound obtained by reacting ## STR3 ## with a compound containing two or more alcoholic hydroxyl groups in one molecule such as ethylene glycol, Duranate 24A-100, 22A-75PX, 2 manufactured by Asahi Kasei Corporation.
Biuret type such as 1S-75E, 18H-70B;
P-301-75E, E-402-90T, E-405
Examples thereof include compounds obtained by reacting a compound containing at least three or more isocyanate groups in one molecule such as an adduct type compound such as -80T.

It is also possible to obtain a compound having an average of four or more isocyanate groups in one molecule by copolymerizing isocyanate ethyl methacrylate alone or with other components in a range not capable of forming a film. Specific examples of the compound (A) include, for example, duranate ME20-100.
(Asahi Kasei Co., Ltd. product name). The number of isocyanate groups in the compound (A) is preferably 6 or more, particularly preferably 7 or more. If the isocyanate group is less than 4, the sensitivity will be poor. The upper limit is not particularly limited, but it is preferably 20 or less because synthesis is difficult if it is too large. The number of isocyanate groups can be adjusted by the number of hydroxyl groups of the polyhydric alcohols and the kind and compounding ratio of the compound having two or more isocyanate groups.

Further, it is preferable that the compound (A) is not capable of forming a film, specifically, it is a liquid at room temperature and atmospheric pressure, or
It is preferably powder and not capable of forming a film. The molecular weight of the compound (A) is usually 500 or more, preferably 10
00 or more and 50000 or less, preferably 1000
It is 0 or less. If it deviates from this range, the sensitivity may decrease. The compound (A) preferably has no isocyanurate skeleton in its structure in terms of sensitivity and developability.

The compound (B) containing one or more hydroxyl groups and two or more addition-polymerizable double bonds in one molecule has a plurality of alcoholic hydroxyl groups such as polyhydric alcohols. A compound obtained by an esterification reaction between a compound and a compound containing a carboxyl group and a (meth) acryloyl group, the compound having one or more alcoholic hydroxyl groups, that is, at least one alcoholic hydroxyl group remains. An example is a reaction product obtained by reacting the above-mentioned carboxyl group-containing compound with a ratio. More specifically, 3 mol of acrylic acid was reacted with 1 mol of pentaerythritol, 2 mol of acrylic acid was reacted with 1 mol of pentaerythritol, and 5 mol of acrylic acid was reacted with 1 mol of dipentaerythritol. The compound, a hydroxyl group-containing polyfunctional acrylate compound having one or more alcoholic hydroxyl groups, which is an ester of polyhydric alcohol such as a compound obtained by reacting 4 mol of acrylic acid and 1 mol of dipentaerythritol and acrylic acid, Specific compounds include pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate. There is. These compounds may be used alone or in a mixture.

Further, as another example of the compound of the component (B), a compound containing an epoxy group such as glycidyl methyl ether, a double-polymerizable with at least one carboxyl group and at least one addition polymerization compound. Reaction with a compound having a bond; or reaction of a compound having at least one or more epoxy groups and at least one or more addition-polymerizable double bonds simultaneously with a compound containing at least one or more carboxyl groups Or a compound having at least one or more carboxyl group and at least one or more addition-polymerizable double bond, and at least one or more epoxy group and at least one or more addition-polymerizable double bond A reaction product with a compound; For example, a reaction product of glycidyl methacrylate and (meth) acrylic acid is cited as an example of this).

Among them, the compound (B) preferably has three or more double bonds capable of addition polymerization, from the viewpoint of sensitivity. The reaction between the compound (A) and the compound (B), that is, the reaction between the isocyanate group of the compound (A) and the hydroxyl group of the compound (B) to obtain the urethane compound (C) is performed according to a known method. Can be done. Specifically, it is carried out by reacting the isocyanate group of the compound (A) with the hydroxyl group of the compound (B) at a ratio of 1/10 to 10,
For example, a method of diluting both with an organic solvent such as toluene or ethyl acetate and then heating at 10 to 150 ° C. for about 5 minutes to 30 hours; or a method of adding a catalytic amount of a catalyst such as n-butyltin dilaurate; The method of diluting the compound (B) in a suitable organic solvent, and subsequently dropping the compound (A) sequentially thereto, or the reverse method.

Further, when the urethane compound (C) is produced, an addition-polymerizable double bond may not be partially introduced for the purpose of controlling various performances of the photopolymerizable composition.
For example, a functional group other than the double bond may be introduced. For example, a compound (D) having a hydroxyl group and a carboxyl group in one molecule is used in combination with the compound (B) to react with the compound (A), thereby adding four or more urethane bonds in one molecule. A compound having a polymerizable double bond and a carboxyl group can be obtained. More specifically, a compound (A1) having four isocyanate groups in one molecule
A compound (B1) having one hydroxyl group and two addition-polymerizable double bonds in one molecule and a compound (D1) having one hydroxyl group and one carboxyl group in one molecule, A1: When the reaction is carried out at a molar ratio of B1: D1 of 1: 3: 1, a compound (C1) having 4 urethane bonds in one molecule and having 6 double bonds and 1 carboxyl group on average is obtained. It can be manufactured.

Specific examples of the compound (D) (compound having a hydroxyl group and a carboxyl group in one molecule) which can be used in combination with the compound (B) to react with the compound (A) include 2-hydroxyoctane. Acids, 2-hydroxyhexanoic acid, 2-hydroxydecanoic acid, 3-hydroxyoctanoic acid, 8-hydroxyoctanoic acid and the like are preferably aliphatic carboxylic acids having a hydroxyl group, and among them, carbon having a hydroxyl group at the α-position of the carboxylic acid. Carboxylic acids of the number 4 to 20 are preferred. The molecular weight of the urethane compound (C) is preferably 6000 or more and 300,000 or less. When it is 6000 or less, the fastness of the layer (uncured film) made of the photopolymerizable composition tends to be poor.
It is disadvantageous in terms of availability. The molecular weight can be controlled by adjusting the types and esterification rates of the compounds (A) and (B) and controlling the reaction conditions.

In particular, when the present urethane compound (C) is obtained, a double bond in the molecule is partially cleaved so that the average molecular weight is 10,000 or more by intramolecularly or partially crosslinked with other molecules. Further, it is particularly desirable that it is 20,000 or more. It is not clear why the increase in molecular weight due to crosslinking is advantageous for image formation without an oxygen barrier layer, but it is presumed that the pre-crosslinked structure has a function of compensating the inhibition of crosslinking / polymerization reaction by oxygen. To be done. Urethane compound (C)
Has four or more addition-polymerizable double bonds in terms of sensitivity of the photopolymerizable composition, but preferably has six or more double bonds,
It is more preferable to have eight or more. As the urethane compound (C),

[0022]

[Chemical 4]

[In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, and Ra represents alkylene, arylene, alkyleneoxy or a repeating group derived from aryleneoxy. Having a unit, Rb represents alkylene, arylene, alkyleneoxy, aryleneoxy, Rc independently represents a C1-20 alkylene, arylene group, Rd is hydrogen or a C1-20 organic residue or an alkali metal group. And represents an organic residue having at least 1 to 10 (meth) acrylic groups,
Ra, Rb, Rc, and Rd may each independently have a substituent. ]

In the formula, Ra is particularly preferably a repeating unit of an alkyleneoxy group or an aryleneoxy group. As the alkyleneoxy group, alkyleneoxy residues such as glycerin, pentaerythritol, and propylenetriol are used, and as the aryleneoxy group used for the repeating unit of Ra, phenoxy residues such as pyrogallol and 1,3,5-benzenetriol are used. Can be mentioned. x is 4 ~
15 is an integer, y is an integer of 1 to 10, z is an integer of 1 to 10, Ra and Rc are independently C1 to C5 alkylene groups, and Rd is an organic compound having 1 to 7 (meth) acrylic groups. Those which represent residues are preferred. More preferably, R
a is

[0025]

[Chemical 5]

(However, k is 2 to 10), and Rb, R
c -C ₂ H ₄ to separate _{-, - CH 2 C (CH} 3) -, or,
_{-C 3 H 6 -, - C} 2 H 4 O -, - CH 2 C (CH 3) is O-, Rd is

[0027]

[Chemical 6]

[0028] The proportion of the urethane compound (C) in the ethylenic monomer is usually 5 to 100% by weight, preferably 10 to 100% by weight. The urethane compound (C) may be used alone or in a mixture. In particular, when the raw material of the urethane-based compound is a mixture, the urethane compound (C) is used as a mixture of the reactants.

Examples of the ethylenic monomer other than the urethane compound include a compound having one ethylenic double bond in one molecule and a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. Specific examples of the former include (meth) acrylic acid, alkyl esters of (meth) acrylic acid, acrylonitrile, styrene, a carboxylic acid compound having one ethylenically unsaturated bond, and a poly (monomer). ) Examples include monoesters of polyhydric alcohols. When an ethylenic monomer other than urethane type is used together, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Examples thereof include esters obtained by an esterification reaction of a polyhydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polycarboxylic acid.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but includes ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate glycerol acrylate, etc. Methacrylic acid ester in which the acrylate of the exemplified compound is replaced with methacrylate Le similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced Kuroneto.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate and pyrogallol triacrylate. Examples thereof include methacrylic acid ester. The ester obtained by the esterification reaction of unsaturated carboxylic acid, polyvalent carboxylic acid and polyvalent hydroxy compound is not necessarily a single substance, but representative specific examples include acrylic acid, phthalic acid, and ethylene glycol. Examples thereof include condensates, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of the polyfunctional ethylenic monomer used in the present invention include urethane acrylates such as addition reaction products of tolylene diisocyanate and hydroxyethyl acrylate; addition of diepoxy compound and hydroxyethyl acrylate. Epoxy acrylates such as reactants; acrylamides such as ethylene bis acrylamide; allyl esters such as diallyl phthalate;
Vinyl group-containing compounds such as divinyl phthalate are useful. In the present invention, as the ethylenic monomer used in combination with the urethane compound (C), a phosphoric acid ester compound containing at least one (meth) acryloyl group is particularly preferable. Although not particularly limited, specific examples thereof include compounds represented by the following general formulas (II) and (III).

[0033]

[Chemical 7]

(In the general formulas (II) and (III), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 25, and m represents an integer of 1 to 3.) General formula ( II), (I
Among the compounds represented by II), those in which n is 1 to 10 are preferable from the viewpoint of improving the printing durability and the non-image area removal property. Among the compounds represented by the general formulas (II) and (III), specific examples of particularly preferable compounds include methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, and methacryloxyethylene glycol phosphate. Etc. The phosphoric acid ester compound used in the present invention may be a single compound or a mixture of a plurality of compounds. The content of the ethylenic monomer other than the urethane compound (C) is 0 to 0 in the ethylenic monomer.
It is 95% by weight, preferably 0 to 90% by weight.

Next, the photopolymerization initiation system used when used as a photopolymerizable composition will be described. The photopolymerization initiation system is usually composed of a radical generator and a sensitizer, and optionally contains a polymerization accelerator. As the radical generator, any one that can initiate the polymerization of the ethylenic monomer can be used. Among these, examples of radical generators that generate active radicals by interacting with photosensitized sensitizers include, for example, titanocenes, hexaarylbiimidazoles, organic boron anions (borates), and halogenated carbons. Examples thereof include hydrogen derivatives (halomethyl group-containing compounds), diaryliodonium salts, organic peroxides and the like.

Examples of titanocenes include, for example, JP-A-59.
It can be appropriately selected and used from various titanocenes described in JP-A-152396 and JP-A-61-151197. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5. , 6-Pentafluorophen-1-yl, di-cyclopentadienyl-Ti-
Bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4
6-trifluorophen-1-yl, dicyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-
Di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis -2,6-Difluorophenyl-1-
Di-cyclopentadienyl-Ti-bis-2,6
-Difluoro-3- (pyrr-1-yl) -phen-1-
Examples thereof include titanocene compounds having a dicyclopentadienyl group such as yl. You may use these in combination of 2 or more types.

Hexaarylbiimidazoles include, for example, 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-Tetra (p-fluorophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-Tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4'5,5'-tetra (p-chlorophenyl) biimidazole , 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-)
p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4'5,5 '
-Tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4 '
5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4'5,5'-tetra (o, p-di) Hexaarylbiimidazoles having halogen substituents on the benzene ring such as chlorophenyl) biimidazoles are preferred.

These hexaarylbiimidazoles can be used in combination with various kinds of biimidazoles, if necessary. Biimidazoles are, for example, Bul
l. Chem. Soc. Japan. 33,565 (1
960) and J. Org. Chem. 36 [16] 22
62 (1971) and can be easily synthesized.

Examples of the organic boron anion include, for example, JP-A-62-143044 and JP-A-62-150242.
JP-A-9-188685 and JP-A-9-18868.
6, JP-A-9-188710, Patent No. 276476.
Publications such as No. 9 and Kunz, Martin “Rad Tech'98.Pro
ceeding April 19-22, 1998, Chicago ”and the like, but those represented by the following general formula (IV) are particularly preferable.

[0040]

[Chemical 8]

[In the formula (IV), R ² , R ³ , R ⁴ , and R ⁵
Are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent which may have a substituent. It represents a good aryl group or a heterocyclic group, which may be linked to each other to form a cyclic structure, and at least one of them is an alkyl group which may have a substituent. ]

Here, when R ² , R ³ , R ⁴ and R ⁵ in the formula (IV) are alkyl groups, the number of carbon atoms is usually 1 to 1.
5, preferably 1 to 5, the number of carbon atoms in the case of an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5,
When it is an aryl group, the number of carbon atoms is usually 6 to 20, preferably 6 to 15, and when it is a heterocyclic group, the number of carbon atoms is usually 4 to
It is 20, preferably 4 to 15, and examples of the substituents therefor include a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, a trimethylsilyl group and the like. Among them, R ^{2 to} R ⁴ are each independently a phenyl group which may be substituted with a halogen atom, and R ⁵ has 1 carbon atom.
It is preferably an alkyl group of ˜6.

Specific examples of these organic boron anions include n-butyl-methyl-diphenylboron anion, n-butyl-triphenylboron anion, and n-butyl-triphenylboron anion.
-Butyl-tris (2,4,6-trimethylphenyl)
Boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-
Fluorophenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3) , 4, 5, 6
-Pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (trifluoromethyl) boron anion, n
Examples include -butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion.

Examples of counter cations include onium compounds such as alkali metal cations, ammonium cations, phosphonium cations, sulfonium cations and iodonium cations, pyrylium cations, thiapyrylium cations and indolium cations. However, organic ammonium cations such as tetraalkylammonium are preferred, and particularly those having 1 to 6 carbon atoms.
The tetraalkylammonium cation of the alkyl group of is preferred.

The halomethyl group-containing compound is mono,
An s-triazine compound having a di- or trihalogen-substituted methyl group bonded to an s-triazine ring is preferable, and a compound represented by the following general formula (V) is particularly preferable.

[0046]

[Chemical 9]

[In the formula (V), X represents a halogen atom,
W represents an aryl group or a heterocyclic group which may have a substituent, R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group,
Alternatively, it represents an aryl group, and r is an integer of 0 to 2. ]

Examples of these s-triazine compounds include:
Specifically, for example, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-
4,6-bis (trichloromethyl) -s-triazine,
2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-chlorophenyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
[1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2 -(P-methoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-Tolyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (4-methoxynaphthyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
Phenylthio-4,6-bis (trichloromethyl) -s
-Triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6
-Bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like can be mentioned, among which 2-methyl-4,6-bis (trichloromethyl). -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 , 4-Epoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-i-propyloxystyryl)-
4,6-bis (trichloromethyl) -s-triazine and the like are preferable because of their excellent stability over time.

These radical generators can be appropriately selected and used according to the exposure wavelength. For example, when the exposure wavelength is in the range of 350 to 650 nm, titanocenes and / or
Alternatively, it is preferable to use hexaarylbiimidazoles because the sensitivity, storability, and adhesion of the coating film to the substrate are particularly good. Further, when the exposure wavelength is 650 to 1300 nm, it is preferable to use an organic boron anion and / or a halomethyl group-containing compound because the sensitivity, storability and adhesion to the base of the coating film are particularly good. Next, the sensitizer of the photopolymerization initiator will be described. The sensitizer in the present invention means
When coexisting with the above-mentioned activator, it means a compound capable of effectively generating an active radical upon irradiation with light.

Examples of typical sensitizers include erythrosine, a triphenylmethane type leuco dye such as leuco crystal violet and leuco malachite green disclosed in US Pat. No. 3,479,185. And photoreducible dyes such as Eosin Y, US Pat. No. 3,549,367, US Pat. No. 3,652,
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in Japanese Patent No. 275,
Β-shown in US Pat. No. 3,844,790
Diketones, indanones found in U.S. Pat. No. 4,162,162, ketocoumarins disclosed in JP-A-52-112681, JP-A-59-56403.
Aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in Japanese Patent No. 4,594,3
Aminophenyl heterocycles shown in No. 10, julolidine heterocycles shown in US Pat. No. 4,966,830, pyrromethene dyes and other cyanine dyes shown in JP-A-5-241338, Examples thereof include dialkylbenzene compounds.

These sensitizers can be appropriately selected and used according to the exposure wavelength, but the exposure wavelength is 390 to 430n.
m is preferably a dialkylbenzene compound,
When the exposure wavelength is 400 to 650 nm, ketocoumarins and pyrromethene dyes are preferable, and the exposure wavelength is 650.
A cyanine dye is preferable if it is ˜1300 nm.

The dialkylaminobenzene compound has a dialkylaminobenzene structure and may have any substituent. Among them, the dialkylaminobenzophenone compound and the p- group for the amino group on the benzene ring are preferable. Compounds having an aromatic heterocyclic group as a substituent at the carbon atom at the position, and the alkyl groups constituting the dialkylamino groups of these compounds are bonded to each other, and / or the alkyl group is on the benzene ring. The compound having a structure in which a nitrogen-containing heterocyclic structure is formed by bonding to a carbon atom adjacent to the carbon atom to which the amino group is bonded is preferable. In the above, the amino groups constituting the dialkylamino group may be the same or different and preferably have 1 to 6 carbon atoms.

Particularly preferred dialkylaminobenzene compounds are represented by the following general formulas (VI) and (VII).

[0054]

[Chemical 10]

(In the formula (VI), R ^{7 to} R ¹⁰ each independently represent an alkyl group having 1 to 6 carbon atoms and R ^{11 to} R 10;
¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R ¹² , R ⁹
And R ¹³ and R ¹⁰ and R ¹⁴ may be independently bonded to form a ring. )

[0056]

[Chemical 11]

(In the formula (VII), R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁷ and R ^{18 each} independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Q
Is an oxygen atom, a sulfur atom, a dialkylmethine group, or-
N (R ¹⁹ )-is shown, wherein R ¹⁹ is a hydrogen atom or carbon 1-6.
Is an alkyl group. However, R ¹⁵ and R ¹⁶ , R ¹⁵ and R ^17, or R ¹⁶ and R ¹⁸ may be independently bonded to form a ring. The carbon number of the alkyl group of dialkylmethylene is 1 to 6, preferably 1. Formulas (VI) and (VI
When any of R ^{7 to} R ¹⁸ in I) is bonded to form a ring, it is preferably a 5- or 6-membered ring, and particularly preferably a 6-membered ring. As the compound represented by the formula (VI),
4,4'-Dimethylaminobenzophenone, 4,4'-
Examples include diethylaminobenzophenone and compounds having the following structures.

[0058]

[Chemical 12]

The compounds represented by the general formula (V) include 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole and 2- (p-dimethylaminophenyl). Benzo [4,5] benzoxazole, 2- (p-
Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylamino) Examples thereof include phenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole and compounds having the following structures.

[0060]

[Chemical 13]

The cyanine dye has a basic structure having a structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is bonded by a polymethine (-CH =) n chain. A so-called cyanine dye in a broad sense, which has a structure in which atoms form a heterocycle and the heterocycles are bonded via a polymethine chain, specifically, for example, a quinoline dye (so-called cyanine dye), an indole dye (So-called indocyanine-based), benzothiazole-based (so-called thiocyanine-based), pyrylium-based, thiapyrylium-based, squarylium-based, croconium-based, azurenium-based, etc., and an acyclic heteroatom bound via a polymethine chain Examples include so-called polymethine dyes having a structure, and among them, indole dyes and benzothiazole dyes are preferable. As the indole-based and benzothiazole-based dyes, those represented by the following general formula (VIII) are particularly preferable.

[0062]

[Chemical 14]

[In the formula (VIII), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R 1
²⁰ and R ²¹ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent,
The alkynyl group which may have a substituent or the phenyl group which may have a substituent is shown, and the penta, hepta, nona, or undecamethine group which may have a L ¹ substituent is shown. The two substituents on the penta, hepta, nona, or undecamethine group are linked to each other and have 5 to 7 carbon atoms.
May form a cycloalkene ring, a cycloalkene ring, a cycloalkenedione ring, or a cycloalkenethione ring, and the fused benzene ring may have a substituent, in which case two adjacent substituents May be linked to each other to form a condensed benzene ring. Xa- represents a counter anion. ]

Here, R ²⁰ and R ²¹ in the formula (VIII) are
When it is an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and when it is an alkenyl group or an alkynyl group, the number of carbon atoms is usually 2 to 15, preferably 2 to 10, and is a phenyl group. Examples of those substituents including also include an alkoxy group having usually 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, a phenoxy group, a hydroxy group, a phenyl group and the like, and the substituent in L ¹ is directly Or, an aromatic ring or a heterocyclic ring through an ether or thioether bond, an alkyl group, an amino group, a halogen atom or the like can be mentioned, and as a substituent in the condensed benzene ring,
Examples thereof include an alkyl group, an alkoxy group, a nitro group, and a halogen atom. Among these, a cyanine dye having a heterocycle on L1 directly or through an ether or thioether bond is preferable.

Further, in the photopolymerization initiation system used in the present invention, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto may be used as a polymerization accelerator, if necessary.
Mercaptobenzoxazole, 3-mercapto-1,
The photopolymerization initiation ability can be further enhanced by adding a hydrogen donating compound such as 2,4-triazole, N-phenylglycine and its derivatives, and N, N-dialkylbenzoic acid alkyl ester. Of these, particularly preferable are those having a mercapto group such as N-phenylglycine or a derivative thereof, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 3-mercapto-1,2,4-triazole. It is a compound or an alkyl ester of N, N-dialkylbenzoic acid.

The photopolymerizable composition of the present invention generally preferably contains a polymer binder capable of forming a film. Specific examples of the polymer binder include, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, and maleimide alone. Alternatively, copolymers and the like, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, polyvinyl butyral and the like can be mentioned. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth)
A copolymer containing a carboxyl group in the molecule containing at least one optionally substituted (meth) acrylic acid ester such as acrylate or benzyl (meth) acrylate and (meth) acrylic acid as a copolymerization component (hereinafter , "Carboxyl group-containing copolymer") are preferred. In addition, in this specification, (meth) acryl means methacryl or acryl.

The preferable acid value of the carboxyl group-containing polymer binder is 10 to 250 KOH · mg / g, and the preferable polystyrene-converted weight average molecular weight (hereinafter abbreviated as Mw) is 10,000 to 2,000,000. These polymer binders preferably have an unsaturated bond in the side chain, and examples thereof include resins obtained by reacting the carboxyl group-containing copolymer with a compound having both an epoxy group and an unsaturated group. Examples of the compound having both an epoxy group and an unsaturated group include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, and itaconic acid. Aliphatic epoxy group-containing unsaturated compounds such as monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, and maleic acid monoalkyl monoglycidyl ester, or 3,4-epoxycyclohexylmethyl (meth) acrylate. it can.

Among them, allyl glycidyl ether, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is more preferable. The resin having both the carboxyl group and the side chain double bond mentioned above preferably has a Mw of 10,000 to 1,000,000, preferably 20.
It is in the range of 000 to 500,000. Furthermore, the side chain double bond is 1 to 50 with respect to the main chain monomer unit 100,
It is preferable that 5 to 40 units are introduced. The main constituents of the photopolymerizable composition of the present invention have been described above in detail, and a suitable use ratio thereof is 100% by weight of the ethylenic monomer, and the inner sensitizer of the photopolymerization initiator. Is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight, the radical activator is preferably 0.1 to 80 parts by weight, and particularly preferably 0.5 to 6 parts by weight.
0 parts by weight, the polymerization accelerator is preferably 0.1 to 80 parts by weight, particularly preferably 0.5 to 60 parts by weight, and the polymer binder is preferably 10 to 400 parts by weight, particularly preferably 2 parts by weight.
It is in the range of 0 to 200 parts by weight.

For the purpose of improving the sensitivity, the photopolymerizable composition of the present invention contains an amine compound having a pKb (dissociation constant) at 25 ° C. of 7 or less in the photosensitive layer, or a primitive group [N-
It is preferable to contain an amine compound having CH2]. More preferably, pKb at 25 ° C. in the photosensitive layer
Is 7 or less, and is an amine compound having an atomic group [N—CH ₂ ] in the molecule. The amine may be an aliphatic, alicyclic or aromatic amine as long as the above conditions are satisfied, and the hydrocarbon group in the amine may have a substituent. Further, the amine is not limited to monoamine, and may be polyamine such as diamine and triamine, and may be any of primary amine, secondary amine, and tertiary amine. However, from the viewpoint of pKb, it is substantially selected from aliphatic amines having a hydrocarbon group which may have a substituent. The pKb of the amine is preferably 5 or less.
The lower limit of pKb is preferably 3 or more. Also,
It is more preferable that the amine has an atomic group [CH ₂ —N—CH ₂ ] in the molecule.

Preferred amine compounds include aliphatic amines having a hydrocarbon group which may have a substituent, and specific examples include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, Hexylamine, dihexylamine, trihexylamine, benzylamine, dibenzylamine, tribenzylamine, triethanolamine, allylamine, diallylamine, triallylamine, and other aliphatic amines that may be substituted with a hydroxyl group or a phenyl group. To be

The photopolymerizable composition of the present invention may further contain other substances in addition to the above-mentioned essential components depending on the purpose. For example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, and 2,6-di-t-butyl-p-cresol; coloring agents composed of organic or inorganic dyes and pigments; dioctyl phthalate, didodecyl phthalate, tricresyl. Plasticizers such as phosphates, sensitivity characteristic improving agents such as tertiary amines and thiols, and other additives such as dye precursors can also be added. Further, the photopolymerizable composition of the present invention may contain a surfactant as a coating property improving agent. Among them, the fluorine-based surfactant is particularly preferable.

The above-mentioned additives are preferably added in an amount of 2 parts by weight or less of the thermal polymerization inhibitor, 20 parts by weight or less of the colorant, 40 parts by weight or less of the plasticizer, and 100 parts by weight of the dye precursor per 100 parts by weight of the ethylenic monomer. The range is 30 parts by weight or less of the body and 10 parts by weight or less of the surfactant. The photopolymerizable composition described above is diluted with an appropriate solvent, coated on a support and dried to form a photosensitive layer. The solvent is not particularly limited, for example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethyl sulfoxide, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, lactic acid. Methyl, ethyl lactate, cyclohexanone, diacetone alcohol, 4
-Hydroxy-2-butanone, methyldiglycol, water or a mixture thereof is used. In the present invention, if it is not intended to block oxygen, a film or layer may be further provided thereon. The content is not particularly limited, for example, a protective film for protecting the photopolymerizable composition from scratches, a slipping layer for improving sliding,
An example thereof is matte adhesion.

In the present invention, the support is not particularly limited, but a plastic film or various metals can be adopted, but an aluminum plate (including an aluminum alloy plate)
Is particularly preferable, and the thickness thereof is usually about 0.01 to 10 mm, preferably about 0.05 to 1 mm. The surface of this support is roughened, then desmutted, and then anodized. In addition to this, degreasing treatment, sealing treatment, undercoating treatment, and the like may be performed as necessary.
Usually, degreasing treatment is performed before the roughening treatment, but the degreasing treatment is a method of wiping with a solvent, dipping or steam cleaning, dipping with an alkaline aqueous solution, or spraying followed by neutralization with an acid aqueous solution. And a method of dipping or spraying with a surfactant. The roughening treatment (graining treatment) is a mechanical treatment method such as a ball polishing method, a brush polishing method, a blast polishing method, a honing polishing method, or a buff polishing method, or an ordinary method such as an electrolytic etching method or a chemical etching method. As a result, the average roughness Ra specified in JIS B0601 is about 0.1 to 1.5 μm, preferably about 0.2 to 1.0 μm. Of these, electrolytic etching with hydrochloric acid or nitric acid is particularly preferable.

Desmutting treatment is performed with sulfuric acid, nitric acid, hydrochloric acid,
Immersion or spraying with an acid such as phosphoric acid or chromic acid or an aqueous solution of alkali such as sodium hydroxide, potassium hydroxide, sodium metasilicate, sodium phosphate, sodium pyrophosphate, potassium phosphate or sodium aluminate It is done according to the usual methods. Although not particularly limited, as the degree of desmutting treatment, when the reflection density immediately after the roughening treatment step is A and the reflection density after the anodizing treatment step is B, A
It is desirable to set −B ≦ 0.1. This desmutting treatment is carried out to remove the smut on the surface of the support, which is generated by the roughening treatment, but in fact, this smut is largely concerned with the adhesiveness between the support and the photosensitive layer. The reflection density is measured using a reflection densitometer in a visual mode without using a filter. The desmutting treatment which is the condition of the present invention depends on the alkaline aqueous solution used and the state of the surface roughening treatment.
1 to 10 in 4% by weight NaOH aqueous solution with a liquid temperature of 5 to 30 ° C
The conditions include immersion for about a second.

The aluminum plate thus obtained is usually anodized, but particularly preferably, a method of treating with an electrolytic solution containing sulfuric acid can be mentioned. The method of anodic oxidation with an electrolytic solution containing sulfuric acid is performed according to a conventionally known method, for example, the method described in JP-A-58-213894. Specifically, for example, 5 to 50% by weight of sulfuric acid, preferably 15 to 30% is used, the temperature is about 5 to 50 ° C, preferably 15 to 35 ° C, and the current density is 1 to 60.
It is carried out at A / dm ² for about 5 to 60 seconds. The amount of oxide film formed by this is 1 to 100 mg / d
It is preferably m ² , especially 10 to 50 mg / dm ² . Further, if necessary, treatment with alkali silicate such as sodium silicate treatment or hot water, and immersion in an aqueous solution containing a resin having a cationic quaternary ammonium group or an aqueous polymer compound such as polyvinylphosphonic acid or carboxymethylcellulose. It is possible to perform a surface treatment such as

The photosensitive composition can be applied by a known method such as dip coating, coating rod, spinner coating, spray coating or roll coating. The amount applied varies according to the application, the range of 0.5 to 100 g / m ² is preferable as dry coating film thickness preferably 0.5 to 5 g / m ² in the planographic printing plate. The drying temperature is, for example, about 30 to 150 ° C,
Preferably about 40 to 110 ° C. for about 5 seconds to 60 minutes,
It is preferably about 10 seconds to 30 minutes. The exposure light source applicable to the composition of the present invention is not particularly limited, for example, carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, helium cadmium laser, violet laser, blue laser. , Argon ion laser, FD-YAG laser, semiconductor infrared laser, YAG laser, helium neon laser and the like can be particularly preferably used. In particular, since the photosensitive lithographic printing plate of the present invention is suitable for laser scanning exposure, it is advantageous to use a laser as a light source. For example, an indium gallium nitride semiconductor laser having a wavelength of about 410 nm, an argon ion laser having a wavelength of about 488 nm, 5 of FD-YAG laser
32 nm, semiconductor laser 780 nm, semiconductor laser 830 nm, YAG laser 106
A specific example is a laser that oscillates each wavelength around 4 nm.

In the image forming method of the present invention, after the image forming material is imagewise exposed with such a laser exposure machine, the support is developed by using an aqueous solution containing a surfactant and an alkali and / or an organic solvent. An image can be formed on it. The developing solution may further contain an organic solvent, a buffer, a dye or a pigment. Suitable alkali agents include inorganic alkalis such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and sodium bicarbonate. Examples thereof include agents and organic amine compounds such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine and triethanolamine, and these can be used alone or in combination. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acid The pH of the anionic surfactant image liquid such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts is usually 9 to 14. Further, as the organic solvent, for example, isopropyl alcohol agent; amphoteric surfactants such as alkyl betaines and amino acids can be used. Alkali, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve,
Propylene glycol, diacetone alcohol and the like can be contained if necessary.

The developing method is not particularly limited, but it is a method of immersing and shaking in a developing solution, a method of physically removing a non-image portion which is about to be dissolved in the developing solution with a brush, or a developing solution in a spray form. Examples include a method of spraying to remove the non-image area. The developing time may be appropriately selected from the range of 5 seconds to 10 minutes depending on the developing method as long as the unexposed portion can be sufficiently removed. Further, in order to maintain the same developing performance for a long period of time, it is general to use a developing replenisher separately from the developing solution. Basically, the developer replenisher may contain an appropriate alkali agent or surfactant as in the case of the developer, if necessary, at a ratio lower than or equal to that of the developer, or at a higher ratio. The amount of the alkaline agent or the surfactant contained in the developer replenisher is not particularly limited, but it is generally within a range of 0.1 to 50 times the amount contained in the developer. is there. Preferably 0.5 times to 30
Double. Further, both the developing solution and the developing replenishing solution may be concentrated several times as much as in actual use for the purpose of simplifying transportation. The concentration ratio is usually 1.1 to 50 times, more preferably 2 to 3 times.
It is 0 times. After the development, it may be placed on a printing plate and optionally subjected to a hydrophilic treatment such as gum arabic if necessary.

Further, as a support for the photosensitive lithographic printing plate, the support is hydrophilized, and the gum tape obtained from the peel strength measurement method using the gum tape from the hydrophilized support is used. When the peel strength is 500 g / cm or less, it is possible to employ a plate-making method of developing on a printing machine without using an alkali developing solution. Specifically, this plate-making method comprises exposing the photosensitive layer of the photosensitive lithographic printing plate imagewise to photo-cur the photosensitive layer imagewise, and then removing the unexposed portion of the photosensitive layer from the support to form a light-sensitive layer. A method for forming a cured photosensitive image, which comprises mounting a photopolymerizable lithographic printing plate after image exposure on a plate cylinder of a printing machine, dampening water and a printing ink on the photosensitive layer of the photopolymerizable lithographic printing plate. When the ink is transferred to the roller surface of the blanket roller by transferring the unexposed portion to the roller surface of the blanket roller by transferring the unexposed portion together with the ink to the roller surface of the blanket roller. It is characterized by being removed from the support.

In the present invention, the image intensity can be further enhanced by performing the whole surface exposure after the above development processing. The light source for the entire surface post-exposure is not particularly limited, but examples thereof include carbon arc, high-pressure mercury lamp, ultra-high-pressure mercury lamp, low-pressure mercury lamp, deep UV lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, excimer UV lamp, etc. Is mentioned. The light emitted from these light sources may be used after being wavelength-limited by a filter or the like. Preferably, the light source for post-exposure has a bright line with a half width of 30 nm or less. As specific examples of preferable light sources, excimer UV lamps, mercury lamps and metal halide lamps are preferable, and excimer UV lamps, high pressure mercury lamps and low pressure mercury lamps are particularly preferable.

Although not particularly limited, the plate surface reaching exposure intensity (exposure amount per unit time) at the time of whole surface exposure is 5 mW / cm.
^It is preferably ² or more. If the light intensity is lower than 5 mW, the effect may be insufficient even if the total exposure amount is the same. The method of increasing the exposure intensity reaching the plate surface at the time of post-exposure to 5 mW / cm ² or more is not particularly limited, but one method is to increase the lamp output (W) of the exposure light source. For example, there is a method of simply increasing the lamp output, or a method of increasing the output per unit length (W / cm) in the case of a rod type lamp. The other is, for example, a method of simply bringing the exposure light source close to the image forming material. With this method, it is possible to easily increase the light intensity reaching the image forming material even when the lamp output of the exposure light source is relatively weak. Not particularly limited, preferred light intensity 5mW / cm ² ~1W / cm ² or less, and more preferably ^{10mW / cm 2 ~500mW / cm 2} . Further, as a lighting method of various light sources, for example, an ordinary stationary light lamp, a flash irradiation type, an instant lighting type, etc. may be mentioned. The wavelength of post-exposure is 200 to 1100 nm
The light of the wavelength of can be used.

As a method of post-exposure, the image was stopped.
The image is continuously conveyed in the processing direction even when
It's okay to go there. Also, the amount of exposure is not particularly limited.
The larger the effect, the greater the effect.
10 mJ / cm to streamline the image forming process²Since
Above, preferably 50 mJ / cm²Above, 10 J / cm ²
Below, preferably 8 J / cm²The following is desirable. After exposure
If the temperature of the image forming material at that time is 40 ° C to 300 ° C,
Keeping the
Is particularly effective in improving the strength of. The condition and person
The method is not particularly limited, but a hot plate or dryer
Such as hot air, radiation from ceramic heaters and powerful light sources
Heat etc. are mentioned. Particularly preferably used for post-exposure
It is simple and preferable to use the radiant heat of the light source. High
If the temperature becomes too high, problems such as deformation of the support may occur.
So that it stays within an appropriate temperature range, a cooling device or IR
Cold mirror and IR cut filter to reduce radiant heat
It is also desirable to use the appropriate. The present invention also provides the above
After the development process, the whole surface is post-heated to further
The image intensity can also be increased.

The heating method is not particularly limited, and examples thereof include a method using radiant heat from an IR ceramic heater, a method using an oven, a method using a hot plate, and a method using a heating roller. Further, the use of radiant heat from the post-exposure light source mentioned above can also be mentioned similarly. After heating,
The process may be performed with the plate stopped or while the plate is continuously conveyed in the processing direction. The heating temperature is preferably about 80 ° C. to 300 ° C. on the plate surface, and particularly preferably about 100 ° C. to 250 ° C. The heating time is not particularly limited, but about 1 second to 15 minutes is preferable, and about 1 second to 10 minutes is particularly preferable. Further, if necessary, in addition to the processing method described in the present invention, it is also effective to add a heating step immediately after laser exposure (before development) in order to improve the image strength in some cases. In this case as well, the conditions and method are not particularly limited, but examples of the image forming material include hot air from a hot plate or a dryer at 50 to 300 ° C., radiant heat from a ceramic heater or a powerful light source, and the like. The heating may be performed while the image is stopped or while the image is continuously conveyed in the processing direction.

[0084]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Synthesis Example 1 <Synthesis of Urethane Compound-1 by Reaction of Compound (A) and Compound (B)> In a four-necked flask, 100 ml of ethyl acetate, 180 mg of n-butyltin dilaurate, 60 mg of paramethoxyphenol, A-9530 ( Shin-Nakamura Chemical Co., Ltd .: A compound containing dipentaerythritol pentaacrylate as a main component, which contains one hydroxyl group and five double bonds capable of addition polymerization, and has a molecular weight of about 530 (theoretical value). Was added. ME20 was added so that the isocyanate group was 0.9 times the molar amount of the hydroxyl group of A-9530.
-100 (manufactured by Asahi Kasei Co., Ltd .: containing an average of 9 isocyanate groups in one molecule; the molecular weight is about 5000) was added dropwise with stirring. After completion of dropping, heat to 70 degrees and IR
The reaction was carried out until the peak of isocyanate disappeared. The reaction product contains a compound having at least 9 or more urethane bonds and theoretically 45 double bonds, and this reaction product is referred to as "urethane compound-1". (Weight average molecular weight is about 10,000.)

Synthesis Example 2 <Synthesis of Urethane Compound-2 by Reaction of Compound (A) and Compound (B)> In Synthesis Example 1, 90 ml of ethyl acetate and A-953 were used.
0 is NK701A (manufactured by Shin-Nakamura Chemical Co., Ltd .: reaction product of glycidyl methacrylate and acrylic acid, having one hydroxyl group and two double bonds, theoretical molecular weight 214.) 9.4
The reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of ME20-100 was changed to g and the number of moles of hydroxyl groups of NK701A was changed to 0.9 times the isocyanate groups. The reaction product contains a compound having at least 9 or more urethane bonds and theoretically 18 double bonds, and this reaction product is referred to as "urethane compound-2" (weight average molecular weight is about 7,000).

Synthesis Example 3 <Synthesis of Urethane Compound-3 by Reaction of Compound (A) and Compound (B)> In a four-necked flask, 150 ml of cyclohexanone, 180 mg of n-butyltin dilaurate, 60 mg of paramethoxyphenol, A- 9530 (manufactured by Shin-Nakamura Chemical Co., Ltd .: a compound having dipentaerythritol pentaacrylate as a main component) and 34.7 g and 2-hydroxy-n-octanoic acid (0.35 g, molecular weight: 160) were sequentially added. Thereafter, in the same manner as in Synthesis Example 1, the ME20-1 was adjusted so that the isocyanate groups were 0.9 times the total molar amount of hydroxyl groups.
00 was used to carry out the reaction. At least 9 reactants
It contains a compound having one or more urethane bonds and theoretically approximately 35 to 40 double bonds, and this reaction product is referred to as "urethane compound-3" (weight average molecular weight is about 9400).

Synthetic Example 4 <Urethane Compound-1 Molecular Weight Increased Product> The reaction was carried out in exactly the same manner as in Synthetic Example-1 except that the synthetic scale was changed to a 400 L cauldron. The obtained reaction product contained a compound having at least 9 or more urethane bonds and theoretically 45 double bonds, and this reaction product was designated as "urethane compound-4". (Weight average molecular weight is about 70,000) Synthesis Example 5 <Synthesis of polymer binder-1> Methyl methacrylate / methacrylic acid = 80/20 m
An ol% (preparation ratio) copolymer, Mw = 70,000 (hereinafter abbreviated as “polymer binder-1”) was synthesized. This binder
A-200 (manufactured by Daicel Chemical Industries, Ltd., a cycloaliphatic epoxy group- and acryloyl group-containing compound) is reacted with 50% of the entire methacrylic acid component 1 to give a weight average molecular weight of about 80,000.
Polymer binder-1 of was obtained.

Synthesis Example 5 <Synthesis of Polymer Binder-2> Vinyl methacrylate / acrylonitrile / allyl glycidyl ether methacrylate / methacrylic acid = 40 /
A copolymer of 15/30/15 mol% (preparation ratio) and a weight average molecular weight of about 1,000,000 (hereinafter abbreviated as "polymer binder-2") were synthesized. <Production of Aluminum Support> Support-1 An aluminum plate having a thickness of 0.2 mm was degreased with 3% sodium hydroxide, and this was 25 in a 18.0 g / l hydrochloric acid bath.
Electrolytic etching was carried out for 15 seconds at a current density of 80 A / dm @ 2 at 80.degree. C., followed by desmutting treatment with a 1% sodium hydroxide aqueous solution at 50.degree. C. for 5 seconds, and then neutralization with a 10% nitric acid aqueous solution at 25.degree. C. for 5 seconds. After washing with water, 30 ℃ in 30% sulfuric acid bath,
10A / dm for 16 seconds anodized in ² conditions, washing with water, and dried to a lithographic printing plate aluminum plate (hereinafter "support -
Abbreviated as 1 ”. ) Got. The anodic oxide film formed is 2.
It is 1 g / m ² .

The following photopolymerizable composition coating liquid-1 was prepared on the above-mentioned support-1, and this coating liquid was applied to a dry film thickness of 2 g / m @ 2 using a bar coater and dried. ,
A photosensitive lithographic printing plate was prepared. Incidentally, only in Comparative Example 4, polyvinyl alcohol / polyvinylpyrrolidone (weight ratio 7: 3) was used for the purpose of blocking oxygen on the photopolymerizable composition film.
The mixed aqueous solution of is dried with a bar coat to a dry film thickness of 3 g / m.
^It was applied so as to be ² .

[0090]

[Table 1] (Photopolymerizable composition coating liquid-1) Polymer binder Type and weight part Ethylenic monomer described in Table-1 Type and weight part Sensitizer-A 2.4 Parts by weight Radical generator-A 15 parts by weight S-381 (Asahi Glass Fluorosurfactant) 0.3 parts by weight Emulgen 104P (Surfactant manufactured by Kao Corporation) 2 parts by weight Phthalocyanine pigment (P.B. 15: 6) 10 parts by weight Disperbyk 161 (manufactured by BYK Chemie) 5 parts by weight tribenzylamine 10 parts by weight The total solid content is applied to a coating solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diacetone alcohol in a weight ratio of 1).
0:50:40) and adjusted to 8.5% by weight. The ethylenic monomers in Table-1 are as follows.

[0091]

[Chemical 15]

PM-2 Mixture of methacryloxyethyl phosphate and bis (methacryloxyethyl) phosphate (manufactured by Nippon Kayaku Co., Ltd.) SP4060S Special orthocresol novolac type (without urethane bond; Showa High Polymer Co., Ltd.) Company made) DPHA dipentaerythritol hexaacrylate

[0093]

[Chemical 16]

Radical generator-A 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine; 5 parts The obtained photosensitive lithographic printing plate was evaluated for the following items. The results are shown in Table-1. <Evaluation of Sensitivity> With a step tablet (manufactured by Konica Corporation) attached on the photosensitive lithographic printing plate, a near infrared exposure device (trend setter 3224-T: oscillation wavelength 83 manufactured by Creo)
0 nm) was used to perform image exposure with various exposure amounts. Next, it was developed by immersing it in an aqueous solution containing 3% by weight of sodium A silicate and 5% by weight of an anionic surfactant (Perex NBL manufactured by Kao Corporation) at 28 ° C. for 30 seconds. After development, the maximum step number obtained was read and the step number was used as an index for sensitivity evaluation. Incidentally, only in the case of Comparative Example 4, similarly, after the exposure, the oxygen barrier layer was previously washed with water and then the same alkali development treatment was performed. <Evaluation of Image Forming Degree> The image obtained by the above exposure and development treatment was air-dried and then rubbed with a finger to confirm the image strength.
As a result, the case where no image was formed at all was evaluated as ◯, and the case where the image was rubbed and partly removed or disappeared was evaluated as x.

[0095]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/031 G03F 7/031 7/033 7/033 7/038 501 7/038 501 F term (reference) 2H025 AA01 AA12 AB03 AB05 AB11 AB13 AB15 AB17 AC01 AC08 AD01 BC32 BC42 BC66 BC92 CA14 CA28 CA41 CA50 CC20 FA03 FA17 2H096 AA07 AA15 AA26 AA27 AA28 BA06 BA20 EA04 GA08 4J027 AG01 AG12 AG14 AG15 AG07 BA10 CB10 BA16 CB10

Claims (17)

[Claims] 1. A photopolymerizable composition containing an ethylenic monomer and a photopolymerization initiation system, wherein as an ethylenic monomer, 4 or more urethane bonds and 4 or more addition polymerizations in one molecule. A photopolymerizable composition comprising a urethane-based compound (C) having a possible double bond and having no layer for the purpose of blocking oxygen on the photopolymerizable composition. 2. The photopolymerizable composition according to claim 1, wherein the urethane compound (C) is represented by the following general formula (I). [Chemical 1] [In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, Ra represents alkylene,
It has an arylene, alkyleneoxy or a repeating unit derived from aryleneoxy, Rb represents alkylene, arylene, alkyleneoxy, aryleneoxy, Rc
Each independently represents a C1-20 alkylene or arylene group, Rd represents hydrogen or a C1-20 organic residue or an alkali metal group, and represents an organic residue having at least 1 to 10 (meth) acryl groups. , Ra, Rb, R
c and Rd may each independently have a substituent. ] 3. A urethane compound (C), which is a compound (A) having four or more isocyanate groups in one molecule,
(B) The photopolymerization according to any one of claims 1 to 2, which is obtained by reacting one or more hydroxyl groups with a compound having two or more addition-polymerizable double bonds in one molecule. Sex composition. 4. The photopolymerizable composition according to claim 1, wherein the urethane compound (C) has an average molecular weight Mw of 6000 or more and 300,000 or less. 5. The photopolymerizable composition according to claim 1, wherein the urethane compound (C) has an average molecular weight Mw of 10,000 or more and 200,000 or less. 6. The photopolymerizable composition according to claim 1, wherein the compound (A) having four or more isocyanate groups in one molecule has a molecular weight of 500 or more. 7. The photopolymerizable composition according to claim 1, wherein the photopolymerizable initiation system contains a sensitizer having absorption in the infrared region. 8. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiation system contains a sensitizer having absorption in the visible light region. 9. The photopolymerizable composition according to claim 1, which contains a polymer binder. 10. A photosensitive lithographic printing plate having a layer comprising the photopolymerizable composition according to any one of claims 1 to 9 on a support. 11. The photosensitive lithographic printing plate according to claim 10, which is for laser scanning exposure. 12. The photopolymerizable composition according to claim 7, wherein the sensitizer is a cyanine dye. 13. The photopolymerizable composition according to claim 10, wherein the cyanine dye has a heterocycle on the polymethine chain. 14. A photopolymerization initiation system comprising an organic boron anion and / or
Alternatively, a compound containing a halomethyl group is contained.
The photopolymerizable composition according to 1. 15. The photopolymerizable composition according to claim 1, which contains an amine compound having at least an atomic group [N—CH 2]. 16. The photosensitive layer further has a pKb at 25 ° C.
1 to 15 containing an amine compound in which is 7 or less.
The photosensitive lithographic printing plate as described in any one of 1. 17. A photosensitive lithographic printing plate according to any one of claims 1 to 16 is imagewise exposed to a laser beam to photocur the photosensitive layer in an imagewise manner. A method of forming a photocurable photosensitive image by removing an exposed portion from a support, which comprises developing an alkali developing solution after image exposure to remove an unexposed portion of a photosensitive layer from the support. How to make a printing plate.