JP2003066592A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate having high sensitivity and excellent printing durability. SOLUTION: In the photosensitive planographic printing plate having a photopolymerizable photosensitive layer comprising a monomer containing an addition polymerizable ethylenic double bond, a photopolymerization initiator and a polymeric binder on a support having a hydrophilic surface, it is characterized in that the polymeric binder is a polymer having a polymerized component formed by polymerizing a monomer of formula (1) as repeating units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Many photosensitive lithographic printing plates utilizing a photopolymerization system have been known. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and an organic polymer binder optionally used is prepared, and the photopolymerizable composition is supported. A photosensitive material having a layer of the photopolymerizable composition applied on the body is prepared, and a desired image is exposed to polymerize and cure the exposed portion, and the unexposed portion is dissolved and removed to form a cured relief image. Method, the above-mentioned light-sensitive material is one in which a layer of a photopolymerizable composition is provided between two supports at least one of which is transparent, and exposed from the transparent support side to cause a change in adhesive strength by light, There is a method of forming an image by peeling the body, and an image forming method utilizing a change in toner adhesion of the photopolymerizable composition layer due to light.

Further, in recent years, a high-sensitivity light-sensitive material using a photopolymerizable photosensitive material has been studied in various fields of application. For laser direct plate making, a laser oscillation wavelength, for example, 488 nm of an argon ion laser, FD Various types of high-sensitivity photopolymerization type photosensitive materials have been proposed which are capable of being exposed to the light of 532 nm of -YAG laser.

One of these biggest problems is the compatibility of the alkali developability and the obtained image strength.

Usually, when the uncured portion is removed by the alkali developing treatment, even the cured portion is swollen or partially dissolved by the alkali developing treatment, and the strength of the obtained image portion is significantly weakened. was there. Therefore, if the alkali developability is sacrificed, there is a problem that the uncured portion is insufficiently removed, resulting in various problems such as stains on non-image areas in the case of a printing plate. It was

For the purpose of improving the alkali developability, a developer is used.
It is well known and widely practiced to add various surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants) as development accelerators.

However, the adjustment of the developing solution has a limit in achieving both the alkali developability and the image strength. On the other hand, it is also known to add a certain surfactant to the photopolymerizable composition, the purpose is to improve the coating properties,
Among them, fluorine-based surfactants which are excellent in coating property improving effect are widely used, but conventionally known fluorine-containing surfactants have improved coating properties, but the problem that the developability of the photopolymerizable composition is lowered. There was a point.

Therefore, in order to improve the above problems,
In JP-A-2000-275830, in place of a conventional fluorine-containing surfactant, a non-fluorine-containing surfactant is added to a photopolymerizable composition to improve both alkali developability and plate-making sensitivity. The technology is disclosed.

However, the technique described above still has a problem that the sensitivity and printing durability of the photosensitive lithographic printing plate, particularly the effect of improving the printing durability after post-baking (heating treatment) are insufficient. It was

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive lithographic printing plate having high sensitivity and excellent printing durability.

[0011]

The above objects of the present invention have been achieved by the following constitutions 1 to 4.

1. In a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator, and a polymer binder on a support having a hydrophilic surface A photosensitive lithographic printing plate, wherein the polymer binder is a polymer having as a repeating unit a polymerization component formed by polymerizing a monomer represented by the general formula (1).

2. 2. The photosensitivity as described in 1 above, wherein the polymer binder contains a carboxyl group-containing monomer and a copolymer having a methacrylic acid alkyl ester or an acrylic acid alkyl ester as a constituent component during the polymerization reaction. Planographic printing plate.

3. The polymer binder contains a copolymer (A) having an unsaturated bond, which is obtained by reacting a carboxyl group of the copolymer with a compound having both an unsaturated bond and an epoxy group in the molecule. 3. The photosensitive lithographic printing plate as described in 2 above.

4. 4. The photosensitive lithographic printing plate as described in 3 above, wherein the compound having both an unsaturated bond and an epoxy group in the molecule is represented by the general formula (2).

The present invention will be described in detail below. As a result of various studies on the above problems, the present inventors have found that an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator, and a polymer binder are provided on a support having a hydrophilic surface. In a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing
When the polymer binder contains a polymer having as a repeating unit a polymerization component formed by polymerizing the monomer represented by the general formula (1), the effects described in the present invention can be obtained. I found what I could get.

The polymer binder according to the present invention will be described. The polymer binder according to the present invention is characterized by containing a polymer formed by polymerizing the monomer represented by the general formula (1) as a repeating unit. Here, the monomer represented by the general formula (1) will be described.

In the general formula (1), the alkyl group represented by R ₁ and R ₂ has, for example, 1 to 4 carbon atoms.
A branched or straight chain alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.).

In the general formula (1), examples of the aryl group represented by R ₁ and R ₂ include phenyl group, m-chlorophenyl group, p-tolyl group and naphthyl group.

In the general formula (1), examples of the aromatic heterocyclic group represented by R ₁ and R ₂ include a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, 1, 2,3-oxadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, s- Examples thereof include triazine ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, purine ring, quinoline ring and isoquinoline ring.

In the general formula (1), examples of the alkyl group represented by R ₄ include the same groups as the alkyl groups described above for R ₁ and R ₂ .

In the general formula (1), examples of the alkyl group represented by R ₅ include the same groups as the alkyl groups described above for R ₁ and R ₂ .

In the general formula (1), examples of the aryl group represented by R ₅ include the same groups as the aryl groups described above for R ₁ and R ₂ .

In the general formula (1), examples of the aromatic heterocyclic group represented by R ₅ include the same groups as the aromatic heterocyclic groups described above for R ₁ and R ₂ .

In the general formula (1), the divalent linking group represented by X is —O—, the following general formula (3), the following general formula (4), the following general formula (5) or the following. The group represented by the general formula (6) and the like are preferably used.

General formula (3) -C (= O) -A- (CBZ) _m -D- General formula (4) -C (= O)-(A- (CBZ) _p ) _m -D- , A and D each represent -O- or -NH-,
B and Z are each a hydrogen atom, an alkyl group, an aryl group,
It represents an aromatic heterocyclic group or a halogen atom (chlorine atom, fluorine atom, bromine atom, iodine atom, etc.). m and p are 1-8
Represents the integer.

Here, the alkyl group, aryl group, aromatic heterocyclic group and the like represented by B and Z are the alkyl group, aryl group and aromatic heterocyclic group described above for R ₁ and R ₂ , respectively. Similar groups may be mentioned. Further, when there are a plurality of A, B, and Z, each may be the same or different.

[0028]

[Chemical 3]

In the formula, R ₆ represents a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom. Examples of the alkoxyl group represented by R ₆ include a methoxy group and an ethoxy group. The alkyl group represented by R ₆ has the same meaning as the alkyl group described above for R ₁ and R ₂ . s represents an integer of 1 to 4.

[0030]

[Chemical 4]

In the formula, B and Z have the same meanings as B and Z described in the above general formulas (3) and (4), respectively.
q and r each represent an integer of 1 to 8. F is-(CB
Z) _v − or the following general formula (7) is represented. Where B,
Z has the same meaning as B and Z represented by the general formulas (3) and (4), respectively, and v represents an integer of 1 to 8. R ₇ represents a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, and the alkyl group, the alkoxyl group, the halogen atom and the like represented by R ₇ have the same meanings as R _{6 in the} above general formula (5). . t represents an integer of 1 to 4.

[0032]

[Chemical 5]

In the above general formulas (3), (4) and (6), when a plurality of A, B and Z are present in the formula, they may be the same or different.

Specific examples of the monomer represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0035]

[Chemical 6]

[0036]

[Chemical 7]

As the monomer represented by the general formula (1) according to the present invention, a commercially available product may be used, and examples of other useful monomers include acetoacetoxyethyl acrylate and acetoacetoxyethyl acrylate. Examples thereof include acetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate, and 2,3-di (acetoacetoxy) propyl methacrylate.

The monomer represented by the above general formula (1) according to the present invention is obtained by reacting a monomer having a polymerizable hydroxyl group with a diketone or other suitable acetoacetylating agent. Converted to the corresponding acetoacetate,
Can be synthesized.

The synthesis of the monomer is carried out, for example, by Bitzmann,
J. S. (Witzeman, JS), Dell Nottingham, W (Dell Nottingham,
W), Delrector, F.M. J. (Dell Recto
r, F. J. ) 'S coating technology (Coatings Tec)
hology), vol. 62, page 101 (1990)
Year), comparison of methods for producing resins for acetoacetylated paints (C
omparison ofMethods for t
he Preparation of Acetoac
It can be synthesized by referring to Eatated Coating Resins) and the documents contained therein.

The content of the polymer having the polymerization component formed by polymerizing the monomer represented by the general formula (1) as a repeating unit in the polymer binder according to the present invention is 1 mass. % Or more, more preferably 2% by mass to 25% by mass, and particularly preferably 2% by mass to 1% by mass.
It is 5% by mass.

Examples of the carboxyl group-containing monomer used for forming the copolymer constituting the polymer binder according to the present invention include α, β-unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid). , Maleic anhydride, itaconic acid, itaconic anhydride, etc.).

Examples of the alkyl acrylate used for forming the copolymer constituting the polymer binder according to the present invention include substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate and propyl acrylate. Butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate , N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.

Examples of the methacrylic acid alkyl ester used for forming the copolymer constituting the polymer binder according to the present invention include substituted or unsubstituted alkyl methacrylate,
For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methacrylate. Benzyl acid, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N
-Dimethylaminoethyl methacrylate and the like can be mentioned.

The polymer binder according to the present invention is obtained by subjecting the carboxyl group of the copolymer to a compound having both an unsaturated bond and an epoxy group in the molecule to undergo an addition reaction.
It is preferable to contain a copolymer having an unsaturated bond, but as the compound having both an unsaturated bond and an epoxy group in the molecule, the compound represented by the general formula (2) is preferably used.

In the general formula (2), the alkyl group represented by R ₇ and R ₈ has the same meaning as the alkyl group represented by R ₁ and R ₂ above, provided that R ₇ and R ₈ are the same. You may disregard the ring by connecting them.

In the general formula (2), the divalent linking group represented by Z may be an alkylene group (eg, a methylene group, an ethylene group, which may be unsubstituted or substituted).
Trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, ethylethylene group, propylene group, etc.) and alkenylene groups (eg, propenylene group, vinylene group, etc.).

Specific examples of the compound represented by the above general formula (2) include glycidyl methacrylate and glycidyl acrylate, but the present invention is not limited thereto.

The polymer binder according to the present invention may contain a vinyl-based copolymer formed from monomers as described below.

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

(B) Monomers having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5 -Hydroxypentyl methacrylate, 6-
Hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(C) A monomer having an aminosulfonyl group, for example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

(D) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

(E) Acrylamide or methacrylamide, such as acrylamide, methacrylamide, N-
Ethyl acrylamide, N-hexyl acrylamide,
N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenylacrylamide, N-
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide and the like.

(F) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl Methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

(G) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(H) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(I) Styrenes such as styrene, methylstyrene, chloromethylstyrene and the like.

(J) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(K) Olefins such as ethylene, propylene, i-butylene, butadiene and isoprene.

(L) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

(M) Monomers having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene. etc.

(N) A monomer having an amino group, for example, N, N-diethylaminoethyl methacrylate, N, N
-Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, acryloylmorpholine, Ni-propyl acrylamide,
N, N-diethylacrylamide and the like.

The polymer binder according to the present invention preferably has a weight average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but is not limited to this range. In addition, the polymer binder may be combined with any other polymer binder such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, or natural resin, if necessary. Good.

The content of the polymer binder in the photopolymerizable photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and used in the range of 20 to 50% by mass. It is particularly preferable to do so from the viewpoint of sensitivity.

Further, from the viewpoint of balancing the polarities of the entire photosensitive layer and preventing the aggregation of the pigment in the photosensitive layer coating liquid, the acid value of the polymer contained in the polymer binder according to the present invention is 10 It is preferably used in the range of 150 to 3
The range of 0 to 120 is more preferable, and further preferably 5
It is in the range of 0 to 90.

The addition-polymerizable ethylenically unsaturated double bond-containing monomer according to the present invention will be described.

The addition-polymerizable ethylenically unsaturated double bond-containing monomer according to the present invention may be a known monomer. Specific compounds include, for example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3-
Acrylate of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid, in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate, Maleic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalin. Acid neopentyl glycol diacrylate, neopentyl glycol adipate diacrylate, Diacrylate ε- caprolactone adduct of Dorokishipibarin neopentyl glycol, 2- (2-hydroxy-1,1-dimethylethyl)
-5-Hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl ether of 1,6-hexanediol Bifunctional acrylic acid esters such as acrylates, or methacrylic acid obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, itaconic acid, crotonic acid, maleic acid ester such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate , Trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalyl Aldehyde-modified dimethylol propane triacrylate and other polyfunctional acrylic acid ester acid, or these acrylates methacrylate, itaconate, crotonate, methacrylic acid in place of maleate, itaconic acid, crotonic acid, maleic acid ester and the like, These oligomers can also be used.

A prepolymer can also be used in the same manner as above. Examples of the prepolymer include the compounds described below, and a prepolymer obtained by introducing photopolymerizability by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight can also be preferably used. These prepolymers may be used alone or in combination of two or more, or may be used as a mixture with the above-mentioned monomer and / or oligomer.

As the prepolymer, for example, adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, Polybasic acids such as pimelic acid, sebacic acid, dodecanoic acid and tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin (Meth) acrylic acid was introduced into a polyester obtained by binding a polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol. Li ester acrylates, such as bisphenol A · epichlorhydrin · (meth)
Epoxy acrylates such as acrylic acid, phenol novolac, epichlorohydrin, and (meth) acrylic acid in which (meth) acrylic acid is introduced into an epoxy resin, such as ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, and polyethylene. Glycol Tolylene Diisocyanate / 2
-Hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate / xylene diisocyanate,
Urethane acrylate obtained by introducing (meth) acrylic acid into urethane resin, such as 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate and trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate. , For example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate and 2-hydroxyethyl acrylate, and other alkyd-modified acrylates obtained by introducing a (meth) acryloyl group into an oil-modified alkyd resin,
Examples include prepolymers such as spirane resin acrylates.

For the photopolymerizable photosensitive layer according to the present invention, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO.
Monomers such as modified triacrylate, dimethyloltricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, alkylene glycol type acrylic acid modified, urethane modified acrylate, etc. and addition having a structural unit formed from the monomer It may contain polymerizable oligomers and prepolymers.

Further, as the monomer used in the present invention,
Mention may be made of phosphoric acid ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least a part of the hydroxyl groups of phosphoric acid is esterified and has a (meth) acryloyl group.

In addition to these, Japanese Patent Laid-Open Nos. 58-212994, 61-6649, 62-46688, 62-48589 and 62-173295.
No. 62-187092 and No. 63-671.
89, Japanese Patent Application Laid-Open No. 1-244891, and the like, and the like. Further, "11290 chemical products", Chemical Industry Daily, p. 286-p. 294, the compound described in "UV / EB curing handbook (raw material)", Polymer Publishing Association, p. The compounds described in 11 to 65 and the like can also be preferably used in the present invention. Among these, compounds having two or more acryl groups or methacryl groups in the molecule are preferable in the present invention, and the molecular weight is 10,000 or less, more preferably 5,000.
The following are preferred.

In the photopolymerizable photosensitive layer according to the present invention, the above-mentioned addition-polymerizable ethylenic double bond-containing monomer according to the present invention is applied to the photopolymerizable photosensitive layer.
The content is preferably in the range of 0 to 80.0 mass%, more preferably in the range of 3.0 to 70.0 mass%.

The polymer produced from the addition-polymerizable ethylenic double bond-containing monomer according to the present invention is 10% by mass to 70% by mass based on the solid content of the photopolymerizable photosensitive layer according to the present invention.
Mass% is preferable, More preferably, it is 20 mass% -60.
It is% by mass.

The photopolymerization initiator according to the present invention will be described. What can be preferably used as the photopolymerization initiator according to the present invention is described in, for example, J. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreduction as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar. And the like, and compounds disclosed in British Patent 1,459,563 are also preferable.

Specifically, the following examples can be given, but the invention is not limited thereto. That is, benzoin methyl ether, benzoin-i-propyl ether, α, α
Benzoin derivatives such as -dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-
Benzophenone derivatives such as bis (dimethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butyl Acridone derivatives such as acridone; α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, as well as JP-B-59-1281, JP-A-61-9621 and JP-A-60-60.
The triazine derivative described in JP-A-104-104; JP-A-59-
1504 and 61-243807; organic peroxides; JP-B-43-23684 and 44;
No. 6413, No. 44-6413, No. 47-
1604 and U.S. Pat. No. 3,567,453.
Diazonium compounds described in U.S. Pat.
No. 8,328, No. 2,852,379 and No. 2,
Organic azide compounds described in 940,853; Japanese Patent Publication Sho 3
6-22062, 37-13109, 38-18015 and 45-9610, o-quinone diazides; JP-B-55-391.
62, JP-A-59-14023, and "Macromolecules".
s) ”, various onium compounds described in Vol. 10, p. 1307 (1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109, 851 and 126. , 712 and "Journal of Imaging Science (J.Imag.Sci.)", Vol. 30, p. 174 (19).
1986) metal allene complex; Japanese Patent Application No. 4-56831.
(Oxo) sulfonium organic boron complexes described in JP-A No. 4-89535 and JP-A No. 4-89535; titanocenes described in JP-A-59-152396 and JP-A-61-151197;
"Coordination Chemistry Review (Co
coordination Chemistry Revi
ew) ”84, 85-277 (1988) and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; JP-A-3-209.
2,4,5-Triarylimidazole dimers described in Japanese Patent No. 477; carbon tetrabromide, JP-A-59-107344.
Organic halogen compounds and the like described in Japanese Patent Publication No.

Among them, titanocenes are preferable. Specific examples of titanocenes include 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-tetrafluorophenyl-1-
Il, di-cyclopentadienyl-Ti-bis-2,
4,6-Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals) and the like can be mentioned. However, the present invention is not limited to this.

When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.

Examples of the compound for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, flugide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane. , Triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds,
Examples thereof include pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, and thiobarbituric acid derivatives, and further, European Patent 568,993, US Patents 4,508,811, 5,227,227, and Japanese Unexamined Patent Publication No. 2001-125255, JP-A-11-271
The compounds described in Japanese Patent No. 969 etc. are also used.

In the present invention, a preferable specific example of the combination of the photopolymerization initiator and the sensitizing dye is described in JP-A-200
The combinations described in 1-125255 and JP-A No. 11-271969 are mentioned.

The blending amount of these polymerization initiators is not particularly limited, but preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the addition-polymerizable ethylenically unsaturated double bond-containing monomer according to the present invention. It is a department. The molar ratio of the photopolymerization initiator to the sensitizing dye is preferably 1: 100 to 100: 1.

Various additives used in the present invention will be described. The coating composition for the photopolymerizable photosensitive layer according to the present invention contains, in addition to the above-mentioned components, an ethylenically unsaturated double bond monomer which is polymerizable during the production or storage of the photosensitive lithographic printing plate material. In order to prevent unnecessary polymerization, it is desirable to add a polymerization inhibitor. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t
-Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol),
N-nitrosophenyl hydroxylamine primary cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and the like can be mentioned.

The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% based on the total solid content of the composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

A colorant can also be used, and as the colorant, conventionally known ones including commercially available ones can be preferably used. For example, those described in the revised new edition "Pigment Handbook", edited by Japan Pigment Technology Association (Seibundo Shinkosha), Color Index Handbook, etc. may be mentioned.

Examples of pigments include black pigments, yellow pigments, red pigments, brown pigments, violet pigments, blue pigments, green pigments, fluorescent pigments and metal powder pigments. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium and calcium) and organic pigments (azo, thioindigo). Pigments, anthraquinone pigments, anthanthrone pigments, triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and their derivatives, quinacridone pigments, etc.).

Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength range of the spectral sensitizing dye corresponding to the exposure laser used. The reflection absorption of the pigment using the integrating sphere is preferably 0.05 or less. The amount of the pigment added is 0.1 to the solid content of the composition.
It is preferably 10% by mass, more preferably 0.2 to 5% by mass.

As an exposure light source, an argon laser (48
(8 nm) or SHG-YAG laser (532 nm), it is preferable to use a violet pigment or a blue pigment from the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visibility after development. Examples of such materials include cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue farst sky blue, indanthrene blue, indico, dioxane violet, iso Examples thereof include biolanthrone violet, indanthrone blue, and indanthrone BC. Among these, phthalocyanine blue and dioxane violet are more preferable.

Further, the above composition may contain a surfactant as a coatability improving agent within a range not impairing the performance of the present invention. Among them, the fluorine-based surfactant is preferable.

In order to improve the physical properties of the cured film,
Additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added. The addition amount of these is preferably 10% or less of the total solid content.

Coating of the photopolymerizable photosensitive layer according to the present invention will be described. Examples of the solvent used when preparing the photosensitive composition of the photopolymerizable photosensitive layer according to the present invention include alcohol: polyhydric alcohol derivatives, sec-butanol, isobutanol, n-hexanol, and benzyl alcohol. , Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, or ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether,
Further, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like are preferable.

Prepared Photosensitive Composition (Photosensitive Layer Coating Solution)
Can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. As a coating method of the coating liquid, for example, air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method,
Cast coating method, curtain coater method, extrusion coater method and the like can be mentioned.

When the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained, and when it is too high, not only Marangoni occurs but also fog in non-image area occurs.
As a preferable drying temperature range, a range of 60 to 160 ° C is preferable, a range of 80 to 140 ° C is more preferable, and a range of 90 to 120 ° C is particularly preferable.

The protective layer used in the present invention will be described. A protective layer is preferably provided on the upper side of the photopolymerizable photosensitive layer according to the present invention. The protective layer (oxygen barrier layer) preferably has high solubility in a developer (generally an alkaline aqueous solution) described later.

Preferred examples of the material forming the protective layer are polybiyl alcohol, polysaccharides, polyvinylpyrrolidone, polyethylene glycol, gelatin,
Glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate,
Examples thereof include polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide and the like. These compounds may be used alone or in combination of two or more to form a coating composition. A particularly preferable compound is polyvinyl alcohol.

To prepare the protective layer coating composition, the above materials can be dissolved in a suitable solvent to prepare a coating solution.
This coating solution is coated on the photopolymerizable photosensitive layer according to the present invention,
The protective layer can be formed by drying. The thickness of the protective layer is preferably 0.1 to 5.0 μm, particularly preferably 0.
It is 5 to 3.0 μm. The protective layer may further contain a surfactant, a matting agent, etc., if necessary.

As the coating method of the protective layer, the known methods mentioned in the above examples can be preferably used. The drying temperature of the protective layer is more preferably lower than the drying temperature of the photosensitive layer. The difference from the drying temperature of the photosensitive layer is preferably 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit in that case is preferably about 95 ° C. at most.

The image forming method used in the present invention will be described. Examples of the light source for imagewise exposing the lithographic printing plate material of the present invention include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, and an electrodeless light source. it can. A xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, an electrodeless light source, etc. can be used.

In the case of collective exposure, a mask material having a negative pattern of a desired exposure image formed of a light-shielding material may be superposed on the photopolymerizable photosensitive layer and exposed.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp or a tungsten lamp is exposed and controlled by an optical shutter material such as liquid crystal or PLZT, an image signal is used. It is possible and preferable to perform appropriate digital exposure. In this case, direct writing can be performed without using a mask material.

The laser exposure is suitable for direct writing without using a mask material, because light can be focused into a beam and scanning exposure can be performed according to image data.
Further, when a laser is used as a light source, it is easy to reduce the exposure area to a minute size, and high-resolution image formation becomes possible.

As the laser light source, any of an argon laser, a He-Ne gas laser, a YAG laser, a semiconductor laser and the like can be preferably used. Laser scanning methods include cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum having a recording material wound on the outer surface, and rotation of the drum is main scanning and movement of laser light is sub scanning. In the cylindrical inner surface scanning, the recording material is fixed to the inner surface of the drum, the laser beam is irradiated from the inner side, and the main scanning is performed in the circumferential direction by rotating a part or the whole of the optical system, and a part of the optical system or Sub-scanning is performed in the axial direction by linearly moving the whole body in parallel with the axis of the drum.
In plane scanning, a polygon mirror or galvanometer mirror and fθ
Main scanning of laser light is performed by combining a lens and the like, and sub-scanning is performed by moving the recording medium. The scanning of the outer surface of the cylinder and the scanning of the inner surface of the cylinder make it easier to increase the accuracy of the optical system and are suitable for high-density recording.

The developing solution used in the present invention will be described. The image-exposed photopolymerizable photosensitive layer is cured in the exposed area.
By developing this with an alkaline developing solution, the unexposed portion is removed and image formation becomes possible. As such a developing solution, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; sodium diphosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; Examples thereof include alkaline developers using inorganic alkaline agents such as sodium borate, potassium borate, and ammonium borate; sodium hydroxide, potassium, ammonium borate, and lithium.

Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine,
Di-i-propylamine, tri-i-propylamine,
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used.

These alkaline agents may be used alone or in combination of two or more. If necessary, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer.

In the development used in the present invention, it is preferable to develop with a developer containing an alkali silicate and having a pH of less than 12.5, more preferably in the range of pH 10 to 12.5. The effect of the present invention is specifically exhibited by such development. That is, while not only exploiting the developability and sensitivity that were conventionally insufficient as sufficient performance,
Performances such as improvement of development sludge performance and printing durability can be improved at the same time.

The support according to the present invention will be described. The support for the photosensitive lithographic printing plate material of the present invention is, for example, a metal plate such as aluminum, stainless steel, chromium or nickel, or a plastic film such as a polyester film, a polyethylene film or a polypropylene film laminated with the above metal thin film or A vapor-deposited product, or a product such as a polyester film, a vinyl chloride film, or a nylon film whose surface has been hydrophilized can be used, but an aluminum plate is preferably used. In this case, a pure aluminum plate and an aluminum alloy plate, etc. It doesn't matter.

As the aluminum alloy for the support, various materials can be used. For example, alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron. Is used.

The support according to the present invention is preferably subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene and thinner, an emulsion degreasing treatment using an emulsion such as kesilon, triethanol and the like are used. An aqueous solution of alkali such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for degreasing treatment,
It is also possible to remove stains and oxide films that cannot be removed only by the above degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support. In this case, dip it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to desmut it. It is preferable to apply a treatment.

Examples of the surface roughening method include a mechanical method and an electrolytic etching method.

The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. For the roughening by the brush polishing method, for example, a rotating brush using brush bristles having a diameter of 0.2 μm to 0.8 mm is rotated, and the surface of the support has, for example, a particle diameter of 10 μm to 1 μm.
It can be performed by pressing a brush while supplying a slurry in which particles of volcanic ash of 00 μm are evenly dispersed in water. Roughening by honing polishing can be performed with a grain size of 10
Particles of volcanic ash of 100 μm to 100 μm are uniformly dispersed in water, pressure is applied from a nozzle to eject, and the surface of the support can be obliquely collided for roughening. Also, for example,
Abrasive particles having a particle size of 10 μm to 100 μm are provided on the surface of the support at 2.5 × 10 ³ at intervals of 100 μm to 200 μm.
Roughening can also be performed by laminating sheets coated so as to have a density of 10 pieces / cm ² to 10 × 10 ³ pieces / cm ² and applying a pressure to transfer the rough surface pattern of the sheets.

After the surface is roughened by the above-mentioned mechanical surface roughening method, it is preferable to immerse it in an aqueous solution of an acid or an alkali in order to remove the abrasive, the aluminum scraps and the like formed on the surface of the support. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the base include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an alkaline aqueous solution such as sodium hydroxide. The dissolution amount of aluminum in the plate ^{surface, 0.5g / m 2 ~5g / m} 2 is preferred. It is preferable to carry out the neutralization treatment by immersing in an alkaline aqueous solution and then immersing it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The electrochemical surface roughening method is not particularly limited, but a method of electrochemically surface roughening in an acidic electrolytic solution is preferable. As the acidic electrolytic solution, an acidic electrolytic solution which is usually used in an electrochemical roughening method can be used,
It is preferable to use a hydrochloric acid-based or nitric acid-based electrolyte. For the electrochemical roughening method, for example, Japanese Patent Publication No. 48-2
8123, British Patent No. 896,563, JP-A-53.
The method described in No. 67507 can be used. This roughening method can generally be carried out by applying a voltage in the range of 1 to 50 volts,
It is preferable to select from the range of 10 to 30 volts.
The current density may be in the range of 10 A / dm ^{2 to} 200 A / dm ² , but 50 A / dm ^{2 to} 150 A / d.
It is preferable to select from the range of m ² . Electricity is 100c
/ Dm ² may be in the range of ~5000c / dm ^2, but preferably selected from the range of ^{100c / dm 2 ~2000c / dm 2} . The temperature for performing this surface roughening method is 10 ° C.
The range of -50 to 50 ° C can be used, but the range of 15 to 45 ° C
It is preferable to select from the range of ° C.

When electrochemical surface roughening is carried out using a nitric acid-based electrolytic solution as the electrolytic solution, it can be generally carried out by applying a voltage in the range of 1 to 50 volts.
It is preferable to select from the range of 10 to 30 volts. The current density may be in the range of 10 A / dm ^{2 to} 200 A / dm ² , but is preferably selected from the range of 20 A / dm ^{2 to} 100 A / dm ² . Electricity is 100c / dm ²
A range of up to 5000 c / dm ² can be used,
It is preferable to select from the range of 100 c / dm ^{2 to} 2000 c / dm ² . The temperature at which the electrochemical graining method is performed is 10 ° C.
~ 50 ° C range can be used, but 15 ° C-45
It is preferable to select from the range of ° C. The nitric acid concentration in the electrolytic solution is preferably 0.1% by mass to 5% by mass. The electrolyte contains
If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added.

When a hydrochloric acid-based electrolytic solution is used as the electrolytic solution,
Generally, a voltage in the range of 1 V to 50 V is applied.
It can be done by
It is preferable to select from the range of lt. Current density is 10A
/ Dm²~ 200A / dm²A range of can be used
But 50A / dm²~ 150A / dm²Choose from a range of
Is preferred. Electricity is 100c / dm²~ 5000c
/ Dm²Can be used, but 100 c / d
m²~ 2000c / dm², And even 200c / dm ²~ 1
000c / dm²It is preferable to select from the range. Electrification
The temperature for performing the surface roughening method is in the range of 10 ° C to 50 ° C.
You can choose from the range of 15 to 45 ° C
preferable. Hydrochloric acid concentration in the electrolyte is 0.1-5% by mass
Is preferred. If necessary, use nitrates or chlorides in the electrolyte.
Compounds, amines, aldehydes, phosphoric acid, chromic acid, borates
Acids, acetic acid, oxalic acid, etc. can be added.

After the surface is roughened by the above-mentioned electrochemical surface roughening method, it is preferable to immerse it in an aqueous solution of acid or alkali in order to remove aluminum scraps and the like on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the base include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an aqueous solution of alkali. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . Further, it is preferable that after the dipping treatment with an aqueous alkali solution, the dipping treatment is carried out by dipping in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The mechanical surface-roughening treatment method and the electrochemical surface-roughening method may be used alone for surface-roughening, or the mechanical surface-roughening treatment method may be followed by an electrochemical surface-roughening method. You may carry out and roughen.

After the surface roughening treatment, anodizing treatment can be performed. The method of anodizing treatment that can be used in the present invention is not particularly limited, and a known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. The anodizing treatment includes
Using an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10% to 50% as an electrolytic solution, a current density of 1 A / dm ^{2 to} 10 A /
A method of electrolyzing with dm ² is preferably used, but in addition,
US Pat. No. 1,412,768, a method of electrolyzing in sulfuric acid at a high current density, and US Pat. No. 3,511,6
No. 61, a method of electrolyzing using phosphoric acid, a method of using a solution containing one or more kinds of chromic acid, oxalic acid, malonic acid and the like can be mentioned. Anodized coating amount of the ^{formed, 1mg / dm 2 ~50mg / dm} 2 is is suitable, preferably ^{10mg / dm 2 ~40mg / dm 2} . The amount of anodic oxide coating is, for example, an aluminum plate containing a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 ml, chromium oxide (I
V): 20 g is dissolved in 1 liter of water to prepare), the oxide film is dissolved, and the weight change of the plate before and after the coating is dissolved is measured.

The anodized support may be sealed if necessary. These sealing treatments can be performed by using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chains, polyacrylic acid, water-soluble metal salts (eg boric acid). Zinc), a yellow dye, an amine salt or the like as an undercoat is also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently bonded as disclosed in JP-A-5-304358 is also suitably used.

As the support, various materials can be used as described above. Further, for example, a metal plate such as stainless steel, chromium or nickel, or a plastic film such as a polyester film, a polyethylene film or a polypropylene film, and the above metal thin film can be used. It is also possible to use a laminated or vapor-deposited product, and further, for example, a polyester film, a vinyl chloride film, a nylon film or the like having its surface subjected to a hydrophilic treatment, or the like. As a hydrophilic treatment method for the plastic film, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, provision of a water-soluble resin layer coating layer and the like are preferably used. In the practice of the present invention, the surface is roughened, anodized, sealed,
And an aluminum plate subjected to a subbing treatment is particularly preferable.

The support according to the present invention has hydrophilicity,
Here, hydrophilicity is defined by measuring the contact angle.

<< Measurement of Contact Angle: Evaluation of Hydrophilicity >> The contact angle used in the present invention is 30 μs after dropping 1 μl of pure water at 25 ° C. with a microburet on a horizontal support. What has an average value of 30 degrees or less measured three times is defined as having hydrophilicity. In the present invention, the contact angle is preferably 20 degrees or less, more preferably 10 degrees or less, and most preferably 5 degrees or less.

The contact angle is measured, for example, by using a contact angle meter CA-P manufactured by Kyowa Chemical Co., Ltd., but during the measurement, be careful not to evaporate the water droplets dropped by filling the sample chamber with saturated steam. To do.

[0124]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition, "part" in an Example represents a "mass part" unless there is particular notice.

Example 1 <Preparation of Polymer Binder> (Preparation of Polymer Binder 1) 12 parts of methacrylic acid and 70 parts of methyl methacrylate were placed in a three-necked flask under a nitrogen stream.
Add 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α′-azobisisobutyronitrile, and add 6 parts in an oil bath at 80 ° C. in a nitrogen stream.
After reacting for a time, a polymer binder 1 was obtained. The weight average molecular weight measured by GPC was about 45,000.

(Preparation of Polymer Binder 2) In a three-necked flask under a nitrogen stream, 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and α, α'-. 3 parts of azobisisobutyronitrile was added, and the mixture was reacted in a nitrogen stream in an oil bath at 80 ° C. for 6 hours. Then, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain a polymer binder 2.
The weight average molecular weight measured by GPC is about 50,000.
0, the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Preparation of Polymer Binder 3) In a three-necked flask under a nitrogen stream, 8 parts of 2-acetoacetoxyethyl methacrylate (M-1), 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 10 parts of ethyl methacrylate. , 500 parts of ethanol and 3 parts of α, α′-azobisisobutyronitrile were put therein, and the mixture was reacted in a nitrogen stream in an oil bath at 80 ° C. for 6 hours to obtain a polymer binder 3.

The weight average molecular weight measured by GPC was about 55,000. (Preparation of Polymer Binder 4) 2-acetoacetoxyethyl methacrylate (M-
1) 8 parts, 12 parts methacrylic acid, 6 methyl methacrylate
2 parts, acrylonitrile 8 parts, ethyl methacrylate 10
Parts, 500 parts of ethanol and 3 parts of α, α′-azobisisobutyronitrile were added, and the mixture was reacted in an oil bath at 80 ° C. for 6 hours in a nitrogen stream to obtain a polymer binder 4. The weight average molecular weight measured by GPC was about 45,000.

(Preparation of Polymer Binder 5) In a three-necked flask under a nitrogen stream, 8 parts of 2-acetoacetoxyethyl methacrylate (M-1), 12 parts of methacrylic acid, 62 parts of methyl methacrylate, 8 parts of acrylonitrile and methacryl. 10 parts of ethyl acidate, 500 parts of ethanol and 3 parts of α, α′-azobisisobutyronitrile were added, and the mixture was put in a nitrogen stream at 80
The reaction was carried out in an oil bath at ℃ for 6 hours. Then, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain a polymer binder 5. The weight average molecular weight measured by GPC is about 5
It was 10,000.

<< Preparation of Support >> An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C., and degreasing treatment was carried out for 1 minute. Then, it was washed with water. This degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and then washed with water. Next, this aluminum plate was electrolytically surface-roughened with an alternating current for 60 seconds in a 0.3% by mass aqueous nitric acid solution at a temperature of 25 ° C. and a current density of 100 A / dm ² , and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a dripped 5% aqueous sodium hydroxide solution. The desmutted roughened aluminum plate is placed in a 15% sulfuric acid solution at 25 ° C. and a current density of 10 A / d.
Anodizing treatment was carried out for 1 minute under the condition of m ² and voltage of 15 V, and further, sealing treatment was carried out with 3% sodium silicate at 90 ° C. to prepare a support.

At this time, the center line average roughness (Ra) of the surface was 0.65 μm. Here, the center line average roughness (Ra) of the surface is a value defined by JIS B 0601.

<< Installation of Undercoat Layer on Support >> On the above support, a coating solution for the undercoat layer having the following composition was dried at 0.1 g / m ²
Was applied with a wire bar so as to obtain the above composition, dried at 90 ° C. for 1 minute, and further heat-treated at 110 ° C. for 3 minutes to prepare an undercoated support.

(Preparation of Coating Liquid for Undercoat Layer) γ-methacryloxypropyltrimethoxysilane 1 part Methyl ethyl ketone 80 parts Cyclohexanone 19 parts << Preparation of planographic printing plate material >> On the above-mentioned undercoated support,
1.4 g / m of the photopolymerizable photosensitive layer coating liquid having the following composition when dried
^It was applied with a wire bar so as to be ^2, and dried at 95 ° C for 1.5 minutes. After that, an overcoat layer coating solution having the following composition was applied onto the photosensitive layer with an applicator so that the dryness was 2.0 g / m ² , and dried at 75 ° C. for 1.5 minutes to form a coating on the photosensitive layer. A lithographic printing plate material having an overcoat layer was prepared.

[0134]   (Preparation of photopolymerizable photosensitive layer coating liquid)   Acrylic copolymer (shown in Table 1 below) 35.0 parts   Spectral sensitizing dye 1 2.0 parts   Spectral sensitizing dye 2 2.0 parts   IRGACURE 784 (manufactured by Ciba Specialty Chemicals) 4.0 parts   EO-modified tris (acryloxyethyl) isocyanuric acid   (Aronix M-315: manufactured by Toagosei Co., Ltd.) 20.0 parts   Polytetramethylene glycol diacrylate (PTMGA   -250: Kyoeisha Chemical Co., Ltd.) 10.0 parts   Polyfunctional urethane acrylate (U-4HA: Shin-Nakamura Chemical Co., Ltd.)                                                           20.0 parts   Phthalocyanine pigment (MHI454: manufactured by Mikuni dye company) 6.0 parts   2-t-butyl-6- (3-t-butyl-2-hydroxy   -5-Methylbenzyl) -4-methylphenyl acrylate   (Sumilizer GS: Sumitomo 3M) 0.5 parts   Fluorine-based surfactant (FC-431; manufactured by Sumitomo 3M Limited) 0.5 part   Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts   Cyclopentanone (boiling point = 129 ° C.) 820 parts

[0135]

[Chemical 8]

(Preparation of coating liquid for overcoat layer) Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Industry) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries) 10 parts Surfactant (F142D: Dainippon Daini) Ink Kogyo Co., Ltd.) 0.5 part Water 900 parts << Image formation >> The photopolymerization type lithographic printing plate material thus prepared was equipped with a FD-YAG laser light source C
Using a TP exposure device (Tigercat: ECRM), 2540 dpi (dpi is 1 inch, that is, 2.5)
Image exposure was performed at a resolution of (representing the number of dots per 4 cm). Then, a pre-washing part for removing the overcoat layer before development, a developing part filled with a developer having the following composition, a washing part for removing the developer adhering to the plate surface, and a gum solution (GW-3 for protecting the image area) : Mitsubishi Chemical's 2-fold dilution)
CTP automatic processor equipped with (PHW23-V: Tech
(manufactured by Nigraph) was developed to obtain a lithographic printing plate.

(Developer Composition (Aqueous Solution Containing Additives Below)) A Potassium Silicate 8.0% by Mass Perex NBL: Kao Corporation 3.0% by Mass Caustic Potassium pH = 12.3 Evaluation of lithographic printing plate >> The lithographic printing plate obtained as described above was evaluated as follows.

<Sensitivity> An appropriate exposure amount is defined as an exposure amount at which no film loss in the image area is observed and a halftone dot exposure area of 175 lines / 50% can reproduce 50% on the prepared lithographic printing plate surface. The exposure amount was defined as the sensitivity.

<< Evaluation of Printing Durability and Evaluation of Printing Durability During Heat Treatment >> A lithographic printing plate produced by exposing and developing an image of 175 lines with an appropriate exposure amount was used as a printing machine (manufactured by Mitsubishi Heavy Industries Ltd. DAI).
YA1F-1) using coated paper, printing ink (Toyo Ink Co., Ltd., Toyo King High Echo M Beni), and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%). Printing was carried out, and the number of printed sheets where dot highlighting occurred was used as an index of printing durability.

Further, after washing the planographic printing plate sample after development, RC-510 baking gum (manufactured by Agfa Co.)
Was applied to the plate surface, dried, and heat-treated at 270 ° C. for 1 minute (post-baking treatment). The printing durability of the heat-treated lithographic printing plate sample was evaluated by the above method.

The results obtained are shown in Table 1.

[0142]

[Table 1]

From Table 1, the samples of the present invention are
It is clear that the sensitivity, printing durability, and printing durability during heat treatment (after post-baking) are extremely excellent.

[0144]

According to the present invention, it was possible to provide a photosensitive lithographic printing plate having high sensitivity and excellent printing durability.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/038 501 G03F 7/038 501 F term (reference) 2H025 AA01 AA12 AB03 AC01 AC08 AD01 BC13 BC42 BC52 BD23 BD43 CA00 CB13 CB14 CB43 FA17 2H096 AA06 BA05 BA06 CA03 EA04 GA08 4J011 CA05 CA08 CC04 CC10 PA65 PA68 PA69 PC02 PC08 4J026 AA20 AA37 AA48 BA27 BA28 BA30 BA50 DB06 DB36 FA05 GA07

Claims (4)

[Claims] 1. A photosensitive having a photopolymerizable photosensitive layer containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator, and a polymer binder on a support having a hydrophilic surface. In a lithographic printing plate, the polymer binder is a polymer having as a repeating unit a polymer component formed by polymerizing a monomer represented by the following general formula (1). Sex lithographic printing plate. [Chemical 1] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, and R ₃ represents a hydrogen atom, a methyl group, a cyano group, or a methoxycarbonyl group. R ₄ represents a hydrogen atom or an alkyl group, and R ₅ is
It represents an alkyl group, an aryl group, or an aromatic heterocyclic group. X represents a divalent linking group, and Y represents -O- or -NH-. n represents 0 or 1. ] 2. The polymer binder contains a carboxyl group-containing monomer and a copolymer having a methacrylic acid alkyl ester or an acrylic acid alkyl ester as a constituent component during the polymerization reaction. 1. The photosensitive lithographic printing plate described in 1. 3. A copolymer having an unsaturated bond (A) obtained by reacting a carboxyl group of the copolymer with a compound having both an unsaturated bond and an epoxy group in the molecule as a polymer binder. ) Is contained, The photosensitive lithographic printing plate of Claim 2 characterized by the above-mentioned. 4. The photosensitive lithographic printing plate according to claim 3, wherein the compound having both an unsaturated bond and an epoxy group in the molecule is represented by the following general formula (2). [Chemical 2] [In the formula, R ₆ represents a hydrogen atom or a methyl group, and R ₇ , R
Each ₈ represents a hydrogen atom, an alkyl group, or a group capable of forming a ring by R ₇ and R ₈ . Z represents a divalent linking group. ]