JP2003315990A - Image forming material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming material which minimizes the effect of inhibition of polymerization due to water, oxygen, carbon dioxide, and temperature even when it has no oxygen intercepting layer, ensures little variation of sensitivity with time change, and has excellent storage stability. <P>SOLUTION: In the image forming material having on a support a photosensitive layer comprising a photopolymerizable composition containing A) a monomer containing an addition-polymerizable ethylenic double bond, B) a photopolymerization initiator system, and C) a polymeric binder, the composition contains a fluorine-free nonionic surfactant having an HLB (hydrophile-lipophile balance) of ≤10 and an oxygen intercepting layer is not present on the photosensitive layer. <P>COPYRIGHT: (C)2004,JPO

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 high-sensitivity image forming material such as a photosensitive lithographic printing plate which can be used for various pattern forming materials such as a pigment-dispersed resist for a display, and an image forming method.

[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. There is known a method of forming a cured relief image by exposing a desired image on a provided light-sensitive material to polymerize and cure the exposed portion and dissolving and removing the unexposed portion. Further, a photosensitive material provided with a layer of a photopolymerizable composition between two supports, at least one of which is transparent, is exposed from the transparent support side to cause a change in adhesive strength by light, and the support is peeled off. Thus, there is a method of forming an image, and an image forming method utilizing a change in toner adhesion of the photopolymerizable composition layer 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-mentioned photopolymerizable compositions is desired to be further improved in terms of sensitivity, and 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. It should be a composition.

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). Further, in JP-A-2000-275830, the photopolymerizable composition is excellent in developability and has good sensitivity because it contains a non-fluorine-containing nonionic surfactant having an HLB value of 3 to 20. However, the oxygen barrier layer is limited to an essential system here.

[0005]

However, it has been practically necessary for such a photopolymerizable composition to block oxygen during conventional 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 layer for the purpose of blocking oxygen. On the other hand, an image forming material having no oxygen barrier layer has been demanded in order to simplify the manufacturing process and the developing process and shorten the working time. The present invention relates to a photosensitive lithographic printing plate having no oxygen barrier layer, which suppresses the effects of oxygen, water, and temperature, and is an image forming material such as a photosensitive lithographic printing plate which has excellent sensitivity and stability over time. And an image forming method.

[0006]

According to the study of the present inventor, the use of a non-fluorine-containing nonionic surfactant having an HLB value of 10 or less makes it possible to use an oxygen barrier layer which has been conventionally required. The inventors have found that even when it is not present, the effects of oxygen, water, carbon dioxide, and temperature can be suppressed, and an image having storage stability with little change in sensitivity with time is formed, and the present invention has been reached. That is, the gist of the present invention is a photosensitive layer comprising a photopolymerizable composition containing A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiation system, and C) a polymer binder. An image forming material having a support on the support, wherein the composition contains a non-fluorine-containing nonionic surfactant having an HLB value of 10 or less, and does not have an oxygen barrier layer on the photosensitive layer. Image forming material.
Another gist of the present invention is to subject the image-forming material according to any one of claims 1 to 13 to imagewise exposure with a laser beam to photo-cur the photosensitive layer, and then to expose the unexposed portion of the photosensitive layer with an alkali. An image forming method is characterized in that it is developed with a developing solution and removed from the support.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (Ethylene Monomer) A) an addition-polymerizable ethylenic double bond-containing compound (hereinafter abbreviated as “ethylenic monomer”), which is a component in the photopolymerizable composition of the present invention, means photopolymerization. When the photosensitive layer composed of the photosensitive composition is exposed to actinic rays, it is added with the second essential component B) by the action of the photopolymerization initiator to undergo addition polymerization and cure. It is a quantity. 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.

Examples of the ethylenic monomer include compounds having one ethylenic double bond in one molecule and polyfunctional ethylenic monomers having two or more ethylenic double bonds in one molecule. As the former, specifically, (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, a monoester of a carboxylic acid compound having one ethylenically unsaturated bond and a poly (mono) hydric alcohol. Etc. As the ethylenic monomer, 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 hexaacrylate, 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 compounds 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. Furthermore, a urethane compound having 4 or more urethane bonds and 4 or more addition-polymerizable double bonds in one molecule is preferable. As the ethylenic monomer used in combination with the urethane compound in the present invention, 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 (I) and (II).

[0012]

[Chemical 1]

(In the general formulas (I) and (II), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 25, m
Represents an integer of 1 to 3. ) In the compounds represented by the general formulas (I) and (II), n is 1 to
A value of 10 is preferable in terms of improving printing durability and the non-image area removal property. Among the compounds represented by the general formulas (I) and (II), 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.

(Photopolymerization Initiation System) Next, the photopolymerization initiation system B) used as a component of the photopolymerizable composition will be described. The photopolymerization initiator 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, as a preferable radical generator that generates an active radical by interacting with a photoexcited sensitizer,
For example, titanocenes, hexaarylbiimidazoles, organic boron anions (borate), halogenated hydrocarbon derivatives (halomethyl group-containing compounds), diaryl iodonium salts, organic peroxides and the like can be mentioned.

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.
No. 9, etc., and Kunz, Martin “Rad Tech'98.Pr.
Oceeding April 19-22, 1998, Chicago ”and the like, but those represented by the following general formula (III) are particularly preferable.

[0019]

[Chemical 2]

[In the formula (III), 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 (III) are alkyl groups, the number of carbon atoms is usually 1 to 15,
Preferably, the number of carbon atoms when it is an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5, and the number of carbon atoms when it is an aryl group is usually 6 to 20, preferably 6 to 15, hetero. When it is a cyclic group, it usually has 4 to 2 carbon atoms.
0, preferably 4 to 15, and as the substituents therefor, a halogen atom, an alkyl group, an alkoxy group,
Examples thereof include trifluoromethyl group and trimethylsilyl group. Among them, R ^{2 to} R ⁴ are independently a phenyl group which may be substituted with a halogen atom, and R ⁵ is 1 to 6 carbon atoms.
Is preferably an alkyl group.

Specific examples of these organic boron anions include n-butyl-methyl-diphenylboron anion, n-butyl-triphenylboron anion and n.
-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, and 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.

[0025]

[Chemical 3]

[In the formula (IV), 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. ]

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 a compound which, when coexisting with the above-mentioned activator, can effectively generate an active radical upon irradiation with light. Examples of typical sensitizers include triphenylmethane-based leuco dyes such as leuco crystal violet and leucomalachite green disclosed in US Pat. No. 3,479,185, erythrosine and eosin Y. Such as photoreducible dyes, aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat. No. 3,549,367, US Pat. No. 3,652,275, and the like, Β-diketones shown in US Pat. No. 3,844,790, US Pat. No. 4,16
Indanones found in Japanese Patent 2,162, JP-A-5
No. 2-112681, ketocoumarins, aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in JP-A-59-56403, aminophenyl complex found in US Pat. No. 4,594,310. Rings, julolidine heterocycles described in U.S. Pat. No. 4,966,830, JP-A-5-241
Pyrromethene-based dyes, other cyanine dyes, dialkylbenzene-based compounds and the like, which are disclosed in Japanese Patent No. 338, can be used.

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-based compound has a dialkylaminobenzene structure and may have any substituent. Among them, the dialkylaminobenzophenone-based compound and p- with respect to the amino group on the benzene ring are 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.

Among them, the preferable dialkylaminobenzene compounds are represented by the following general formulas (V) and (VI).

[0033]

[Chemical 4]

(In the formula (V), R ^{7 to} R ¹⁰ are each independently an alkyl group having 1 to 6 carbon atoms, and R ^{11 to} R ¹⁴ are
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
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. )

[0035]

[Chemical 5]

(In the formula (VI), R¹⁵, R¹⁶Are independent
To give an alkyl group having 1 to 6 carbon atoms to R¹⁷And R¹⁸Is independent
And a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is
Oxygen atom, sulfur atom, dialkylmethine group, or -N
(R¹⁹) -Indicates R¹⁹Is a hydrogen atom or carbon 1-6
Indicates an alkyl group. However, R¹⁵And R¹⁶, R¹⁵And R¹⁷Or R
¹⁶And R¹⁸May independently bond to form a ring.
Yes. ) The number of carbon atoms in the alkyl group of dialkylmethylene is
It is 1 to 6, preferably 1. In formulas (V) and (VI)
And R⁷~ R¹⁸When any of the above combine to form a ring
A 5- or 6-membered ring is preferred, and a 6-membered ring is particularly preferred.
Good Examples of the compound represented by the formula (V) include 4,4 '
-Dimethylaminobenzophenone, 4,4'-diethyl
Aminobenzophenone and compounds of the following structure
It

[0037]

[Chemical 6]

The compounds represented by the general formula (IV) 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.

[0039]

[Chemical 7]

The cyanine dye has a basic 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 and benzothiazole dyes, those represented by the following general formula (VI) are particularly preferable.

[0041]

[Chemical 8]

[In the formula (VII), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ²⁰ and R ²¹ each independently may have a substituent. An alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent, and which has an L1 substituent Also shows good penta, hepta, nona, or undecamethine groups. Two substituents on the penta, hepta, nona, or undecamethine group are linked to each other to form a cycloalkene ring, cycloalkeneone ring, cycloalkenedione ring, or cycloalkenethione ring having 5 to 7 carbon atoms. Also, the condensed benzene ring may have a substituent,
In that case, two adjacent substituents may be linked to each other to form a condensed benzene ring. Xa-represents a counter anion. ]

Here, the number of carbon atoms when R ²⁰ and R ²¹ in the formula (VII) are alkyl groups is usually 1 to 15, preferably 1 to 10 and the number of carbon atoms when they are alkenyl groups and alkynyl groups. Is usually 2 to 15, preferably 2 to 10, and the substituents thereof, including the phenyl group, usually have 1 to 15 carbon atoms, preferably 1 to 10 alkoxy groups, phenoxy groups, hydroxy groups, Or a phenyl group and the like, and the substituent in L1 includes an aromatic ring or a heterocycle directly or through an ether or thioether bond, an alkyl group, an amino group, a halogen atom, etc., and a substitution in the condensed benzene ring. As a basis,
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.

Furthermore, the photopolymerization initiator used in the present invention may optionally contain, as a polymerization accelerator, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzimidazole
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.

(Polymer Binder) The photopolymerizable composition of the present invention generally contains a polymer binder capable of forming a film. Specific preferred 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,
Examples include homo- or copolymers such as maleimide, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, and polyvinyl butyral. Among them, methyl (meth) acrylate, ethyl (meth) acrylate,
Optionally substituted (meth) acrylic acid ester such as propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, benzyl (meth) acrylate A copolymer containing a carboxyl group in the molecule containing at least one of the above and (meth) acrylic acid as a copolymerization component (hereinafter, "carboxyl group-containing copolymer").
Referred to)) is preferred. In addition, in this specification, (meth) acryl means methacryl or acryl.

The preferred acid value of the carboxyl group-containing polymer binder is 10 to 250 KOH.mg/g, and the preferred 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.

(Nonionic Surfactant) The non-fluorine-containing nonionic surfactant of the present invention will be described. Fluorine-based surfactants that have been conventionally used for the purpose of improving coatability have both water-repellent and oil-repellent functions. The non-fluorine-containing nonionic surfactant of the present invention has an HLB value of 10 or less, specifically, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether. , Polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan Distearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, poly Xyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbit tetraoleate, glycerol monostearate, monogreceride stearin system, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate , Polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, sorbitan fatty acid ester such as alkylalkanolamide, aliphatic monoglyceride, polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester and the like. Among them, a polyoxyethylene derivative having a polyoxyethylene structure is particularly preferable. Also preferred HLB
The value range is 9.5 or less, and particularly preferably 9 or less. The lower limit is preferably 3.0 or more.

The amount of the non-fluorine type nonionic surfactant used is usually 0.01 to 20 parts by weight, preferably 0.05 parts by weight or more, based on 100 parts by weight of the polymerizable ethylenic monomer. It is preferably 0.5 part by weight or more, and preferably 15 parts by weight or less. The amount of non-fluorine-containing nonionic surfactant used is 10 in total of the photopolymerizable composition.
It is preferable to contain 0.01 to 15 parts by weight with respect to 0 parts by weight, preferably 10 parts by weight or less, and more preferably 0.1 parts by weight or more. If the amount used is too large, problems such as foaming of the coating liquid tend to occur, and if it is too small, sufficient curing tends not to be obtained. Further, these non-fluorine-containing nonionic surfactants may be used alone or in combination of two or more. Above all, it is preferable to use a substance having HLB of 9.5 or less and a substance having HLB of 9.6 to 10 because the storage stability is further improved.

(Amine Compound) The photopolymerizable composition of the present invention contains 2 parts of the photopolymerizable composition for the purpose of improving sensitivity.
It preferably contains an amine compound having a pKb (dissociation constant) of 7 or less at 5 ° C., or an amine compound having a primitive group [N—CH 2]. More preferably, it is an amine compound having a pKb at 25 ° C of 7 or less in the photosensitive layer and having an atomic group [N-CH2] in the molecule. As the amine compound, an aliphatic compound, as long as the above conditions are satisfied,
It may be either an alicyclic or aromatic amine, and the hydrocarbon group in the amine compound 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. The pKb of the amine compound is preferably 5 or less. The lower limit of pKb is preferably 3 or more. Further, the amine compound more preferably has an atomic group [CH2-N-CH2] in the molecule.

Preferred amine compounds include aliphatic amines having a hydrocarbon group which may have a substituent from the viewpoint of pKb. Specifically, butylamine, dibutylamine, tributylamine, amylamine, diamylamine, Fats optionally substituted with a hydroxyl group or a phenyl group, such as triamylamine, hexylamine, dihexylamine, trihexylamine aminebenzylamine, dibenzylamine, tribenzylamine, triethanolamine, allylamine, diallylamine, triallylamine, etc. Group amines.

(Additive) The photopolymerizable composition of the present invention may further contain other substances in addition to the above-mentioned essential components A) to C) depending on its 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.

The above-mentioned additives are preferably added in an amount of not more than 2 parts by weight of the thermal polymerization inhibitor, not more than 20 parts by weight of the colorant, not more than 40 parts by weight of the plasticizer, and not more than 40 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. (Solvent) 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. (Layer constitution) In the present invention, an oxygen barrier layer is not provided on the photosensitive layer formed on the support. If the purpose is not to block oxygen, a film or layer may be provided on the photosensitive layer. The type thereof is not particularly limited, and examples thereof include a protective film for protecting the photopolymerizable composition from scratches, a slipping layer for improving sliding, and mat attachment.

(Support) 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 its thickness is usually 0. 01-
It is about 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. According to JIS B06
The average roughness Ra defined by 01 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, and 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 / dm2 for about 5 to 60 seconds. The amount of oxide film formed by this is 1 to 100 mg / dm
2, especially 10 to 50 mg / dm @ 2 is preferred. Also,
Further, if necessary, by treatment with alkali silicate such as sodium silicate treatment or hot water, or by 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. Surface treatment can be performed.

(Coating) As a coating method of the photosensitive composition, a known method such as dip coating, coating rod, spinner coating, spray coating or roll coating can be applied. The coating amount varies depending on the use, but the dry film thickness is preferably in the range of 0.5 to 100 g / m @ 2, for example, lithographic printing plate is 0.5 to 5 g / m @ 2.
Is preferred. The drying temperature is, for example, 30 to 150.
5 seconds to 60 at about 40 ° C, preferably about 40 to 110 ° C
It is about minutes, preferably about 10 seconds to 30 minutes. (Exposure) The exposure light source applicable to the composition of the present invention is not particularly limited, and examples thereof include carbon arc, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, helium cadmium laser, and violet laser. , Blue laser, argon ion laser, FD-YAG laser, semiconductor infrared laser, YAG laser, and helium neon laser 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, FD-
Near 532 nm of YAG laser, 7 of semiconductor laser
Around 80 nm, around 830 nm of semiconductor laser, YA
A specific example is a laser that oscillates each wavelength in the vicinity of 1064 nm of the G laser.

(Development) In the image forming method of the present invention, after imagewise exposing the image forming material with such a laser exposure machine, development is performed using an aqueous solution containing a surfactant and an alkali and / or an organic solvent. For example, an image can be formed on the support. The developing solution further includes an organic solvent, a buffer,
It may contain dyes or pigments. 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 Salts, alkylnaphthalene sulfonates, alkyl sulfates,
The pH of anionic surface active image liquids such as alkyl sulfonates and sulfosuccinic acid ester 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 may be 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 by a 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 by the method for measuring peel strength with 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.

(Post-Exposure) In the present invention, the image intensity can be further enhanced by performing the whole surface exposure after the above-mentioned development processing. The light source for the overall post-exposure is not particularly limited, but for example, carbon arc, high pressure mercury lamp,
Examples include ultra-high pressure mercury lamps, low pressure mercury lamps, Deep UV lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, halogen lamps and excimer UV lamps. 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 are particularly preferable.
Examples include lamps, high-pressure mercury lamps, and low-pressure mercury lamps.

Although not particularly limited, the plate surface arrival 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. Although not particularly limited, the preferable light intensity is 5 mW / cm2 to 1 W / cm2 or less, and more preferably 10 mW / cm2 to 500 mW / cm2.
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 the post-exposure is 200 to 1100n
Light of wavelength m can be used.

The post-exposure method may be carried out while the image is stopped or while the image is continuously conveyed in the processing direction. Further, the exposure amount is not particularly limited, and the larger the amount, the more the effect can be expected, but 10 mJ / cm 2 is used in order to rationalize the image forming process.
Or more, preferably 50 mJ / cm 2 or more, 10 J / c
m2 or less, preferably 8 J / cm2 or less is desirable. The temperature of the image forming material during the post-exposure is 40 ° C to 300 ° C.
The heating or holding is particularly effective in improving the strength of the image unless other problems occur. The conditions and method are not particularly limited, and examples thereof include warm air such as a hot plate and a dryer, radiant heat such as a ceramic heater and a powerful light source. Particularly preferably, it is simple and preferable to use the radiant heat of the light source used for the post-exposure. If the temperature becomes too high, a problem such as deformation of the support may occur. Therefore, it is desirable to appropriately use a cooling device, a cold mirror or IR cut filter for reducing IR radiant heat so that the temperature falls within an appropriate temperature range.

Further, in the present invention, the image strength can be further enhanced by performing a post-heating treatment on the entire surface after the development processing. 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. The post-heating may be performed while the plate is 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, a heating step may be added immediately after laser exposure (before development).
In some cases, it is effective in improving the image strength.
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.

[0065]

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> In a four-necked flask, 100 ml of ethyl acetate, 180 mg of n-butyltin dilaurate, 60 mg of paramethoxyphenol, A-9530 (manufactured by Shin-Nakamura Chemical Co., Ltd .: one hydroxyl group) And a compound mainly containing dipentaerythritol pentaacrylate containing 5 addition-polymerizable double bonds and having a molecular weight of about 530 (theoretical value). 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 “ethylenic monomer-1”. (Weight average molecular weight is about 10,000.)

Synthesis Example 2 <Synthesis of polymer binder-1> Methyl methacrylate / methacrylic acid = 80/20 mol
% (Preparation ratio) of a copolymer, Mw = 70,000 (hereinafter abbreviated as “polymer binder-1”) was synthesized. A-200 (manufactured by Daicel Chemical Industries Ltd .; alicyclic epoxy group- and acryloyl group-containing compound.) Is reacted with 50% of the whole methacrylic acid component of this binder-1 to give a polymer binder having a weight average molecular weight of about 80,000. -1 was obtained.

<Production of Aluminum Support> Support-1 A 0.2 mm-thick aluminum plate was degreased with 3% sodium hydroxide, and this was degreased in a 18.0 g / l hydrochloric acid bath for 25 hours.
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,
Aluminum plate for lithographic printing plate (hereinafter referred to as "support-
Abbreviated as 1 ”. ) Got. The anodic oxide film formed is 2.
It is 1 g / m2.

On the above-mentioned support-1, the following photopolymerizable composition coating liquid-1 was prepared, 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.

[0070]

[Table 1] (Photopolymerizable composition coating liquid-1) Surfactant Types and parts by weight shown in Table-1 Polymer binder-1 45 parts by weight Ethylenic monomer-1 35 parts by weight Ethylenic monomer Body-2 10 parts by weight Sensitizer-A 2.4 parts by weight Radical generator-A 15 parts by weight S-381 (Asahi Glass Fluorosurfactant) 0.3 parts by weight Phthalocyanine pigment (P.B. 15: 6) ) 10 parts by weight Disperbyk 161 (manufactured by BYK Chemie) 5 parts by weight tribenzylamine (pKb: 4.6) 10 parts by weight The total solid content is mixed with a coating solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether) in a weight ratio. 30:70).
Adjusted to 0% by weight.

<Evaluation of Sensitivity> Using a near-infrared exposure device (Trendsetter 3224-T: oscillation wavelength 830 nm) manufactured by Creo Co., Ltd. with a step tablet (manufactured by Fuji Co.) attached on a photosensitive lithographic printing plate, Image exposure was performed according to the exposure amount. 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. <Evaluation of storability> Wrapping the photosensitive lithographic printing plate with moisture-proof paper, 2
After storage at room temperature in the dark for a month, the above exposure and development processing was performed. As a result, the case where there was no change in sensitivity compared with the sensitivity before storage was marked with ⊚, and the case where the change in sensitivity was within 0.5 steps of step sensitivity was marked with ◯.

[0072]

[Table 2]

<Surfactant> -Surfactant-1 Trade name Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether nonionic surfactant HLB value = 9.6) -Surfactant-2 Trade name MYO-2 (Nikko Chemicals Co., Ltd .: Polyethylene glycol monooleate Nonionic surfactant HLB
Value = 4.5) ・ Surfactant-3 Brand name BPS-5 (manufactured by Nikko Chemicals Co., Ltd.) (Polyoxyethylene phytosterol nonionic surfactant HLB
Value = 9.5) ・ Surfactant-4 Product name BS-2 (manufactured by Nikko Chemicals Co., Ltd.) (polyoxyethylene stearyl ether nonionic surfactant HLB
(Value = 8.0)

[0074]

The image-forming material of the present invention has a specific HLB.
By containing a non-fluorine-containing nonionic surfactant with a value, in particular, the sensitivity does not change over time even without an oxygen barrier layer, and storage stability is excellent, and the effects of water, oxygen, carbon dioxide, and temperature are also high. The image forming material such as a lithographic printing plate having good sensitivity can be provided by suppressing the above.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/038 501 G03F 7/038 501 7/11 501 7/11 501 F term (reference) 2H025 AA01 AB03 AB05 AB11 AB15 AB17 AC01 AC08 AD01 BC14 BC32 BC51 BC66 BC84 CA14 CA42 CA50 CC04 CC20 FA03 FA17 2H096 AA07 AA26 AA27 AA28 BA05 BA06 BA20 EA02 EA04 GA08 LA16 4J027 AC02 AC03 AC04 AC06 AC09 AE04 AE07 AG12 BA24 BA25 BA20 BA20 BA06 BA20 BA06 BA20 BA20 BA06 BA20 BA06 BA28 CA02 CA03 CA05 CA06 CA07 CA10 CA34 CB10 CC05 CC07 CD10

Claims (14)

[Claims] 1. A photosensitive layer comprising a photopolymerizable composition containing A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiation system, and C) a polymer binder. In the image forming material on the body, the composition contains a non-fluorine-containing nonionic surfactant having an HLB value of 10 or less,
An image-forming material having no oxygen barrier layer on the photosensitive layer. 2. The non-fluorine-containing nonionic surfactant according to claim 1, wherein a surfactant having an HLB value of 9.5 or less and a surfactant having an HLB value of 9.6 to 10 are used in combination. Image forming material. 3. The image forming material according to claim 1, wherein the non-fluorine-containing nonionic surfactant is contained in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the photopolymerizable composition. 4. The polymer binder c) has an addition-polymerizable ethylenic double bond in at least a side chain.
The image forming material according to any one of 3 above. 5. The image formation according to claim 1, wherein the addition-polymerizable ethylenic double bond monomer A) is a phosphate compound having at least one (meth) acryloyl group. material. 6. The addition-polymerizable ethylenic double bond monomer A) is a urethane compound having 4 or more urethane bonds and 4 or more addition-polymerizable double bonds in one molecule. Item 6. The image forming material according to any one of items 1 to 5. 7. The image forming material according to claim 1, wherein the photopolymerization initiator B) contains a sensitizer having absorption in the infrared region. 8. The image forming material according to claim 7, wherein the sensitizer is a cyanine dye. 9. The method according to claim 1, which is for laser scanning exposure.
The image forming material as described in any one of 1. 10. The photopolymerization initiation system B) contains an organic boron anion and / or a halomethyl group-containing compound.
10. The image forming material according to any one of 9 to 10. 11. The photopolymerizable composition is an atomic group [N—CH ₂ ].
The image-forming material according to claim 1, further comprising an amine compound having 12. The photopolymerizable composition has a pK at 25 ° C.
The image forming material according to any one of claims 1 to 11, wherein b contains an amine compound having 7 or less. 13. The image forming material according to claim 1, which is a photosensitive lithographic printing plate. 14. The image forming material according to claim 1 is imagewise exposed to a laser beam to photo-cur the photosensitive layer imagewise, and then the unexposed portion of the photosensitive layer is treated with an alkaline developer. An image forming method comprising developing and removing from a support.