JP2003066606A - Photosensitive planographic printing plate material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate material having good developability and ensuring a small amount of development sludge particularly even when a developing solution of <pH 12.5 is used in relation to improvement of high sensitivity, printing resistance, ink receptivity, etc. SOLUTION: In the photosensitive planographic printing plate material having a photopolymerizable photosensitive layer comprising a polymeric binder on a support, the polymeric binder comprises a vinyl copolymer having a monomer unit of formula (I) (where R1 and R2 are each alkyl or the like; R3 is methyl or the like; and (n) is an integer of 2-6) as a constituent element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate material, which is excellent in sensitivity, developability, ink receptivity and printing durability, and is also good in alkali development treatment having a pH lower than conventional ones. The present invention relates to an improved photosensitive lithographic printing plate material having excellent sensitivity, developability, ink receptivity, printing durability, and development sludge performance.

[0002]

2. Description of the Related Art Conventionally, a photosensitive lithographic printing plate material is known in which a photopolymerizable layer and a protective layer are laminated on a support which has been subjected to a hydrophilic surface treatment. In addition, particularly in recent years, in order to quickly obtain a high-resolution lithographic printing plate material, and for the purpose of filmless, digital exposure based on image information using a laser is performed, and this is developed to obtain a lithographic printing plate. The manufacturing method is generalized.

As an example, for example, an output signal from an electronic plate making system or an image processing system or an image signal transmitted through a communication line modulates a light source to directly scan and expose a photosensitive material for printing. Systems for forming plates are known.

The photopolymerizable layer is generally composed of an acrylic monomer, an alkali-soluble resin and a photopolymerizable initiator, and optionally a sensitizing dye for adjusting the wavelength (especially when laser writing). Is known to contain.

It is also known to provide a protective layer for the purpose of preventing polymerization inhibition by oxygen.

Exposure of a photopolymerizable photosensitive lithographic printing plate material
As a light source for plate making, a long-wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) is used. More recently, for example, I
A semiconductor laser that uses nGaN-based or ZnSe-based materials and is capable of continuous oscillation in the 350 nm to 450 nm region is in the practical stage. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because the semiconductor laser can be manufactured inexpensively due to its structure. Furthermore, conventional FD-
Compared to systems that use YAG or Ar lasers,
There is a possibility that a photosensitive material with a short photosensitive area that can be operated under a brighter safe light can be used.

In the case of a photopolymerizable photosensitive lithographic printing plate material, it is usually subjected to image exposure and, if necessary, heat treatment, followed by washing with water for removing the protective layer, developing treatment for dissolving and removing unexposed portions, and washing with water. Treatment and finisher gum treatment for making the non-image area hydrophilic are performed to obtain a lithographic printing plate. At this time, if the protective layer component is not sufficiently removed from the exposed portion of the photosensitive layer, or if the finisher gum component is firmly formed in the image portion, ink inking is poor at the start of printing and the amount of damaged paper increases. There is a possibility that it will occur.
Japanese Patent No. 15598 discloses a technique of controlling the amount of residual solvent in the photosensitive layer before applying the protective layer, but these methods have been insufficient.

On the other hand, as a developer for the photosensitive lithographic printing plate material, in order to completely remove the photosensitive layer in the non-image area, that is, to perform development, it is usually used as an aqueous alkaline developer at pH 1
It was generally used at 2.5 or higher. However, in recent years, treatment with an alkaline developer having a lower pH has been desired from the viewpoint of workability, safety, environmental suitability and the like.

Under these circumstances, in the conventional photopolymerizable photosensitive lithographic printing plate material, problems such as an increase in the developability and the amount of development sludge are clarified in the development with the alkaline developer having such a low pH. On the other hand, if an attempt is made to enhance the developability of the photosensitive polymer layer by developing with a low pH developer,
There is a problem that the printing durability and the ink receptivity deteriorate.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems. That is, the first aspect of the present invention
The purpose of is to provide a photosensitive lithographic printing plate material excellent in sensitivity, developability, printing durability, and ink receptivity. A second object of the present invention is to provide an excellent photosensitive lithographic printing plate material having good sensitivity, developability, printing durability, ink receptivity, and development sludge performance even in a low pH alkaline developing treatment.

[0011]

The above objects of the present invention have been achieved by the following.

A. At least one layer of a photopolymerizable film containing (1) an addition-polymerizable ethylenically unsaturated double bond-containing monomer, (2) a photopolymerization initiator and (3) a polymer binder on a support. In the photosensitive lithographic printing plate material having a light layer, the (3) polymer binder is a vinyl-based copolymer having a monomer unit represented by the general formula (I) as a constituent element. Photosensitive planographic printing plate material.

B. The photosensitive lithographic printing plate material as described in a above, wherein the vinyl copolymer contains 3 to 40 mol% of the monomer unit represented by the general formula (I).

C. The vinyl copolymer contains 3 to 40 mol% of the monomer unit represented by the general formula (I), and the carboxyl group of the monomer unit contains an epoxy group-containing unsaturated compound in a reaction rate of 20 to 60 mol. The photosensitive lithographic printing plate material as described in the above item a, which is a reaction product bonded in%.

D. PH containing alkali silicate 12.
The photosensitive lithographic printing plate material as described in any one of a to c above, which is developed with a developing solution of less than 5.

E. The photosensitive lithographic printing plate material as described in any of a to d above, further comprising an oxygen barrier layer on the photopolymerizable photosensitive layer.

F. The photosensitive lithographic printing plate material as described in any one of a to e above, wherein the support is an aluminum support that has been at least roughened and anodized.

G. The photosensitive lithographic printing plate material according to the above item f, wherein the support is an aluminum support that has been subjected to surface roughening and anodization, and further subjected to a hydrophilic treatment or an undercoating treatment.

The present invention will be described in more detail below. (Support) The support relating to the photosensitive lithographic printing plate material of the present invention is 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 and the above-mentioned metal. A thin film laminated or vapor-deposited, or a polyester film, a vinyl chloride film, a nylon film or the like which has been subjected to a hydrophilic treatment on the surface can be used, but an aluminum plate is preferably used, and in this case, a pure aluminum plate and It may be an aluminum alloy plate or the like.

As the aluminum alloy for the support, various materials can be used. For example, an alloy of aluminum with a metal 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 the rolling oil on the surface before 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.

The surface roughening method includes, for example, 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. The roughening by the brush polishing method is performed by, for example, rotating a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm, and, for example, a particle diameter of 10 to 100 μm on the support surface.
It can be carried out by pressing a brush while supplying a slurry in which the particles of the volcanic ash are uniformly dispersed in water. Roughening by honing polishing is performed, for example, with a particle size of 10 to 100.
Particles of μm volcanic ash can be evenly 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, on the surface of the support,
Abrasive particles having a particle size of 10 to 100 μm are
2.5 × 10 ³ to 10 × 10 ³ pieces / cm ² at intervals of μm
Laminate the coated sheets so that they exist at the density of
Roughening can also be performed by applying pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the above-described 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 amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . After soaking in an alkaline solution, phosphoric acid, nitric acid, sulfuric acid,
It is preferable to perform a neutralization treatment by immersing in an acid such as chromic acid or a mixed acid thereof.

The electrochemical surface-roughening method is not particularly limited, but the method of electrochemically surface-roughening in an acidic electrolyte 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
The methods described in Japanese Patent No. 8123, British Patent No. 896,563, and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method is generally 1-5.
It can be carried out by applying a voltage in the range of 0 V, but it is preferable to select it in the range of 10 to 30 V. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. Electricity is 100-5000c /
A range of dm ² can be used, but from 100 to 200
It is preferable to select from the range of 0 c / dm ² . The temperature for carrying out this surface roughening method may be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

Electrification using a nitric acid-based electrolyte as the electrolyte
When performing a surface roughening, a range of 1 to 50 volts is generally used.
Can be done by applying a voltage of
It is preferable to select from the range of 10 to 30 volts. Current density
10 to 200 A / dm ²The range of
Can, but 20-100A / dm²It is preferable to choose from the range
Good Electricity is 100-5000c / dm²Range of
Can be used, but 100 to 2000 c / dm²
It is preferable to select from the range. Performs an electrochemical roughening method
The heating temperature may be in the range of 10 to 50 ° C.
Is preferably selected from the range of 15 to 45 ° C. Electrolyte
The nitric acid concentration in is preferably 0.1 to 5 mass%. electrolytic
The solution should contain nitrates, chlorides, amines, and
Luthedes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid
Etc. can be added.

When a hydrochloric acid-based electrolyte is used as the electrolyte,
Generally, it can be performed by applying a voltage in the range of 1 to 50 V, but it is preferable to select from the range of 2 to 30 V. Current density is 10 to 200 A / d
A range of m ² can be used, but 50 to 150 A /
It is preferable to select from the range of dm ² . The amount of electricity is 100
A range of up to 5000 c / dm ² can be used,
100 to 2000 c / dm ² , further 200 to 1000
It is preferable to select from the range of c / dm ² . The temperature for carrying out the electrochemical graining method may be in the range of 10 to 50 ° C, but is preferably selected in the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added to the electrolytic solution.

After the surface is roughened by the 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 dust 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 method may be followed by an electrochemical surface-roughening method. You may carry out and roughen.

After the roughening treatment, an anodic oxidation 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
A method in which an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% is used as an electrolytic solution and electrolysis is performed at a current density of 1 to 10 A / dm ² is preferably used, but in addition, US Pat. No. 1,412,768 is used. The method of electrolyzing in sulfuric acid at a high current density described in Japanese Patent No. 3,511,661, the method of electrolysis using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, oxalic acid, malonic acid, etc. Examples include a method of using a solution containing one kind or two or more kinds. The formed anodic oxide coating amount is appropriately 1 to 50 mg / dm ² , and preferably 10 to 40 mg / dm ² . The anodic oxide coating amount is, for example, an aluminum plate with a phosphoric acid chromic acid solution (phosphoric acid 85%
Liquid: 35 ml, chromium oxide (IV): 20 g is dissolved in 1 L of water) to dissolve the oxide film, and the mass change of the plate before and after dissolution is measured.

The anodized support may be subjected to a sealing treatment 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 are carried out, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, 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, and, for example, a polyester film, a vinyl chloride film, a nylon film or the like whose surface has been hydrophilized can also be used. As a hydrophilic treatment method for the 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.

(Addition-Polymerizable Ethylenically Unsaturated Double Bond-Containing Monomer) The addition-polymerizable ethylenically unsaturated double bond used in the photopolymerizable photosensitive layer of the present invention (hereinafter sometimes referred to as photosensitive layer) The bond-containing monomer (hereinafter sometimes referred to as a monomer) includes a known monomer having a radically polymerizable ethylenically unsaturated bond.

Specific compounds include, for example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryl. Oxyhexanolide 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 Examples thereof include polyfunctional acrylic acid ester acids such as aldehyde-modified dimethylolpropane triacrylate, or methacrylic acid obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, itaconic acid, crotonic acid, maleic acid ester and the like.

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.

Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, 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.

The photopolymerizable photosensitive layer of the present invention comprises a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate and trimethylol. It may contain a monomer such as propane acrylic acid benzoate, an alkylene glycol type acrylic acid-modified or urethane-modified acrylate, and an addition-polymerizable oligomer or prepolymer having a constitutional unit formed from the monomer.

Furthermore, examples of the ethylenic monomer used in the present invention include 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 those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferable.

In the photopolymerizable photosensitive layer of the present invention, the above-mentioned monomer is added in an amount of 1.0 to 8 in the photosensitive composition of the photosensitive layer.
The content is preferably in the range of 0.0% by mass, more preferably in the range of 3.0 to 70.0% by mass.

(Polymer Binder) The polymer binder according to the present invention preferably contains a vinyl-based copolymer having the monomer unit represented by the general formula (I) as a constituent element, and further, It is preferable to contain a vinyl copolymer composed of the monomer represented by the general formula (I) and at least one of the monomers described in (1) to (17) below.

In the general formula (I), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group or a hetero atom-containing aromatic group, and preferably a hydrogen atom.

R ₃ represents a hydrogen atom, a methyl group or a cyano group, preferably a hydrogen atom or a methyl group.

The monomer represented by the above general formula (I) can be prepared by a known method, for example, Zh.
Prikl. Khim. 26, 1953, p410-4
11, Kunstst, 21, 1931, p76, J. Mol.
Chem. Soc. Perkin Trans. Two
5, 1998, p1249-1256, J. Gen. C
hem. USSR, 54, 3, 1984, 1984, p.
It can be prepared according to the method described in the literature such as 610-614 and the like. Further, generally commercially available β-methacryloyloxyethyl hydroftergent and the like can also be used in the present invention.

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

(2) 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.

(3) 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.

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

(5) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride.

(6) Substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate , Decyl acrylate,
Undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, acrylic acid-
2-chloroethyl, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.

(7) 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, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.

(8) 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.

(9) 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.

(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether,
Propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc.

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

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

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

(14) Olefins such as ethylene,
Propylene, i-butylene, butadiene, isoprene and the like.

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

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

(17) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, acryloyl morpholine, N-i-propyl acrylamide, N, N- Diethyl acrylamide etc.

The above vinyl-based copolymer according to the present invention is
It has a monomer represented by the general formula (I) as an essential constituent unit, and preferably contains 3 to 40 mol% of the monomer unit (monomer unit) represented by the general formula (I). It is preferably contained, and more preferably 5 to 30 mol%.

In addition, a vinyl copolymer containing 3 to 40 mol% of the monomer unit represented by the general formula (I) can be used, for example, with allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl ( (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Compounds or epoxy group-containing unsaturated compounds such as 3,4-epoxycyclohexylmethyl (meth) acrylate (preferably alicyclic epoxy group-containing unsaturated compounds)
At a temperature of about 20 to 120 ° C. for about 1 to 50 hours,
A vinyl-based copolymer, which is a reaction product obtained by reacting 20 to 60 mol% of the carboxyl groups of the monomer unit represented by the general formula (I), is preferable.

As a method for synthesizing the vinyl copolymer according to the present invention, a generally known polymerization method can be used. For example, JP-A-10-315598 and 11-271963 can be used. Patent publications such as Japanese patent publications and "Polymer synthesis experimental method" (WR Sorenson
T. W. It can be synthesized according to the method described by Campbell, published by Tokyo Kagaku Dojin, and the like.

These copolymers preferably have a mass average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC),
It is not limited to this range.

If desired, the above-mentioned polymer binder may be any other polymer binder such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin, etc. You may use together with the vinyl-type copolymer which concerns on this invention.

The content of the polymer binder in the composition for coating the photopolymerizable photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 50% by mass. From the viewpoint of sensitivity, it is particularly preferable to use in the range of%. Further, the vinyl-based copolymer according to the present invention preferably accounts for 50 to 100% by mass, and more preferably 100% by mass, in the polymer binder.

The acid value of the polymer contained in the polymer binder according to the present invention is preferably in the range of 10 to 150, more preferably 30 to 120, and more preferably 50.
It is particularly preferable to use in the range of from 90 to 90 from the viewpoint of balancing the polarities of the entire photosensitive layer, and this can prevent aggregation of the pigment in the photosensitive layer coating liquid.

(Photopolymerization Initiator) As the photopolymerization initiator according to the present invention, those which can be preferably used are described, for example, in J. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar.
Azo compounds, diazo compounds, halogen compounds, photoreducible dyes and the like can be mentioned, and the compounds disclosed in British Patent 1,459,563 are also preferable.

Specifically, the following examples can be given, but the present invention is not limited to these. 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 complexes described in JP-A-5-21386.
No. 1 and No. 5-255347 (oxo) sulfonium organic boron complex; titanocenes described in JP-A-59-152396 and JP-A-61-151197; "Coordination Chemistry Review (Coordination Chemistry Review). R
84), pages 85-277 (1988).
And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701;
2,4,5-Triarylimidazole dimers described in JP-A-209477; carbon tetrabromide, JP-A-59-107.
Organic halogen compounds described in Japanese Patent No. 344, etc.

Among them, preferred are titanocenes. 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 sensitizing 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 combination described in JP-A No. 1-125255 and JP-A No. 11-271969 can be 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) 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 capable of being polymerized during the production or storage of the photosensitive lithographic printing plate material. It is desirable to add a polymerization inhibitor to prevent unnecessary polymerization of the bound monomer. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol). , 2, 2 '
-Methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2-t-butyl-6- (3-t-butyl-2)
-Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and the like.

The amount of the polymerization inhibitor added 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, and in this case, the pigment at the laser wavelength used is selected. 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) Examples of the solvent used for preparing the photosensitive composition for the photopolymerizable photosensitive layer according to the present invention include alcohol: polyhydric alcohol derivatives, and
c-butanol, isobutanol, n-hexanol,
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, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, or esters: ethyl lactate, butyl lactate, Preferable examples include diethyl oxalate and methyl benzoate.

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, Marangoni is generated, and fog in non-image area is generated.
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.

(Protective Layer) 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 include polyvinyl 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 50 ° C. at most.

The drying temperature of the protective layer is preferably lower than the glass transition temperature (Tg) of the binder contained in the photosensitive layer. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or more, more preferably 40 ° C. or more, and the upper limit of the difference is at most about 60 ° C. Is preferred.

(Image forming method) As a light source for imagewise exposing the planographic printing plate material of the present invention, for example, laser, light emitting diode, xenon lamp, xenon flash lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure. Examples thereof include a mercury lamp and an electrodeless light source.

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 squeezed 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.

(Developer) In the image-exposed photopolymerizable photosensitive layer, the exposed portion is cured. 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,
Same potassium, same ammonium; dibasic sodium phosphate, same potassium, same ammonium; sodium bicarbonate, same potassium, same ammonium; sodium carbonate, same potassium,
Examples thereof include alkaline developers using inorganic alkali agents such as ammonium ammonium; sodium hydrogen carbonate, potassium hydrogen, ammonium hydroxide; sodium borate, potassium potassium, ammonium hydrogenate; sodium hydroxide, potassium potassium, ammonium hydrogen and lithium.

In addition, 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 according to 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 10.5 to 12.4. The effect of the present invention is specifically exhibited by such development. That is, not only can the developability and sensitivity that were conventionally insufficient be brought out as sufficient performance, but also the performance such as improvement of development sludge performance and improvement of printing durability can be improved at the same time.

[0101]

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.

(Examples 1 to 13 and Comparative Examples 1 to 4) (Synthesis of Binder) In a three-necked flask under a nitrogen stream,
Methyl methacrylate (Compound 1 below) 37.5 parts (0.
375 mol), 34-75 parts of β-methacryloyloxyethyl hydrotergent (compound 2 below) (0.
125 mol), 100 parts of ethanol and 1.23 parts of α, α′-azobisisobutyronitrile were added, and the mixture was reacted for 6 hours in an oil bath at 80 ° C. in a nitrogen stream to give a polymer binder A
Got The mass average molecular weight measured by GPC is about 5
It was 6,000.

Thereafter, 1 part of triethylammonium chloride and 8.875 parts (0.0625 mol) of glycidyl methacrylate (the following epoxy group-containing compound 1) were added and reacted at a temperature of 25 ° C. for 3 hours to give a polymeric binder F. Obtained. The mass average molecular weight measured by GPC is about 6
It was 3,000.

As shown in Table 1 below, the monomer units, the ratio thereof, and the reaction ratio of the epoxy group-containing unsaturated compound were changed by changing the charged amount, and the same operation was carried out. Got

[0105]

[Table 1]

[0106]

[Chemical 2]

[0107]

[Chemical 3]

[0108]

[Chemical 4]

(Production of Support) An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was immersed in a 5% sodium hydroxide aqueous solution kept at 65 ° C., and degreasing treatment was performed 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.

(Undercoat layer on support) On the support,
Apply the undercoat layer coating liquid of the following composition with a wire bar to a dryness of 0.1 g / m ² , and dry at 90 ° C. for 1 minute,
Further, heat treatment was performed at 110 ° C. for 3 minutes to prepare an undercoated support.

Undercoat layer coating liquid 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.

[0112]   Photopolymerizable photosensitive layer coating liquid   Polymer binder (shown in Tables 2 and 3) 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   Polyfunctional urethane acrylate   (U-4HA: manufactured by Shin-Nakamura Chemical Co., Ltd.) 50.0 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 (F178K: manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 part   Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts   Cyclopentanone (boiling point = 129 ° C.) 820 parts   Protective layer (overcoat layer) coating liquid   Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Industry) 89 parts   Water-soluble polyamide (P-70: manufactured by Toray) 10 parts   Surfactant (F142D: manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 part   900 parts of water

[0113]

[Chemical 5]

(Image formation) With respect to the photopolymerization type planographic printing plate material produced as described above, a CTP exposure device (Tigercat: E) equipped with an FD-YAG laser light source was used.
Image exposure was carried out using a CRM) manufactured at a resolution of 2540 dpi (dpi represents the number of dots per inch, that is, 2.54 cm). Next, a pre-washing part for removing the overcoat layer before development, a developing part filled with the following developer composition 1, a washing part for removing the developer adhering to the plate surface, and a gum solution for protecting the image area (GW-3 : 2 made by Mitsubishi Chemical
CTP automatic developing machine (PHW2) equipped with double diluted
3-V: manufactured by Technigraph Co., Ltd.) and subjected to development processing to obtain planographic printing plates of Examples 1 to 13 and Comparative Examples 1 to 4.

[0115]   Developer composition 1 (Aqueous solution containing the following additives)   A potassium silicate (potassium silicate) 8.0 mass%   Perex NBL: 3.0% by mass manufactured by Kao Corporation   Adjust caustic potash pH = 12.8.

(Evaluation of lithographic printing plate) The lithographic printing plate obtained as described above was evaluated as follows. The evaluation results are shown in Table 2.

<< 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.

<< Ink ink receptivity, developability, printing durability >> 175
A lithographic printing plate prepared by exposing and developing a line image with an appropriate exposure amount was used as a printing machine (manufactured by Mitsubishi Heavy Industries, Ltd. DAIYA1F-
In 1), printing was performed using coated paper, printing ink (Toyo Ink Co., Ltd., Toyo King High Echo M Beni) and dampening water (Tokyo Ink, Co., Ltd. H liquid SG-51 concentration 1.5%). The number of sheets until stable printing was performed was used as an index of ink receptivity. The stain resistance of the printed matter in the non-image area (unexposed area) was observed and used as an index of developability. The highlight part is narrowed down,
The number of prints in which the entanglement of the shadow portion occurred was used as an index of printing durability.

[0119]

[Table 2]

(Examples 14 to 26, Comparative Examples 5 to 8) Table 3
Examples 1 to 13 and Comparative Example 1 except that the polymer composition as shown in FIG.
To Examples 4 to 4 and Comparative Examples 5 to 5.
8 lithographic printing plates were obtained.

[0121]   Developer composition 2 (Aqueous solution containing the following additives)   A potassium silicate 3.0 mass%   Perex NBL: 3.0% by mass manufactured by Kao Corporation   Adjust caustic potash pH = 10.8.

(Evaluation of lithographic printing plate) The lithographic printing plate obtained as described above was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 3. The sludge amount was evaluated as follows.

<< Development Sludge Amount >> 100% of developer composition 2
20 cm x 20 cm for each photosensitive lithographic printing plate material per ml
Is developed at 30 ° C. for 30 seconds, and then DT-1 (1 at 55 ° C. and 50% RH is added in order to forcibly deteriorate the developing solution.
After that, the developer was suction filtered with a Kiriyama funnel to collect the sludge remaining on the filter paper (a portion in which the developer was not dissolved), and the mass after drying was measured.

[0124]

[Table 3]

[0125]

INDUSTRIAL APPLICABILITY The present invention is a photosensitive lithographic printing plate material having excellent properties such as high sensitivity of photopolymerization type, which has good developability even when the pH of the developer is less than 12.5, and develops sludge. It is possible to provide a photosensitive lithographic printing plate material which has a small amount and is excellent in printing durability and ink receptivity.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA12 AB03 AC01 AC08                       AD01 BC32 BC42 CA01 CA18                       CA23 CA26 CA28 CA39 CA41                       CB14 CB43 DA04 DA18 DA20                       FA03 FA17                 2H096 AA07 AA08 BA05 CA03 CA20                       EA02 EA04 GA08 GA09 GA13                       LA19                 2H114 AA04 AA14 AA23 AA27 AA30                       BA02 BA10 DA04 DA21 DA34                       DA41 DA51 DA52 DA53 DA55                       DA64 EA01 EA02 EA03 EA08                       FA18 GA09

Claims (7)

[Claims] 1. At least 1 containing (1) an addition-polymerizable ethylenically unsaturated double bond-containing monomer, (2) a photopolymerization initiator and (3) a polymer binder on a support. In the photosensitive lithographic printing plate material having a photopolymerizable photosensitive layer as a layer, the polymer binder (3) is a vinyl-based copolymer having a monomer unit represented by the following general formula (I) as a constituent element. A photosensitive lithographic printing plate material characterized by containing. [Chemical 1] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group or a hetero atom-containing aromatic group;
₃ represents a hydrogen atom, a methyl group or a cyano group. n is 2
Represents an integer of 6; ] 2. The photosensitive lithographic printing plate material according to claim 1, wherein the vinyl-based copolymer contains 3 to 40 mol% of the monomer unit represented by the general formula (I). 3. The vinyl-based copolymer contains 3 to 40 mol% of the monomer unit represented by the general formula (I), and a carboxyl group of the monomer unit is reacted with an epoxy group-containing unsaturated compound. The photosensitive lithographic printing plate material according to claim 1, which is a reaction product bonded at a rate of 20 to 60 mol%. 4. The photosensitive lithographic printing plate material as claimed in claim 1, wherein the developing treatment is carried out with a developing solution containing an alkali silicate and having a pH of less than 12.5. 5. The photosensitive lithographic printing plate material according to claim 1, further comprising an oxygen barrier layer on the photopolymerizable photosensitive layer. 6. The photosensitive lithographic printing plate material according to claim 1, wherein the support is an aluminum support at least roughened and anodized. 7. The support according to claim 6, which is an aluminum support which has been subjected to surface roughening and anodic oxidation treatment, and further subjected to hydrophilic treatment or subbing treatment.
The light-sensitive lithographic printing plate material described.