JP2003233176A - Photopolymerizable resin composition and photosensitive planographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable resin composition and a photosensitive planographic printing plate material capable of ensuring both sensitivity and preservability and capable of obtaining a planographic printing plate having good printing resistance, high resolution and good linearity. <P>SOLUTION: The photopolymerizable resin composition comprises at least one alkali-soluble polymer, a compound having an ethylenic addition- polymerizable group, a photopolymerization initiator, a colorant and a compound represented by formula (1) or (2) shown in a claim. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable resin composition and a photosensitive lithographic printing plate material, and more specifically, to a photosensitive material excellent in sludge, printing durability, stain recovery and linearity. Regarding lithographic printing plate material.

[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 is performed based on image information using a laser, and this is developed to obtain a lithographic printing plate. The manufacturing method is generalized.

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 lithographic printing plate material. Therefore, a system for forming a lithographic printing plate is known.

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

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

As a light source for exposing / making a photopolymerizable photosensitive lithographic printing material, an Ar laser (488 nm) or F
A long-wavelength visible light source such as a D-YAG laser (532 nm) is used. More recently, for example, InG
aN-based or ZnSe-based material, 350 nm to 45 nm
A semiconductor laser that can continuously oscillate in the 0 nm range is in a 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 at a low cost due to its structure. Furthermore, conventional FD-YA
There is a possibility that a photosensitive lithographic printing plate material having a shorter photosensitive area capable of working under a brighter safe light can be used as compared with a system using a G or Ar laser.

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.

A photosensitive lithographic printing plate material using such a photopolymerizable composition may undergo polymerization during storage and is called a dark reaction. In order to suppress the polymerization due to this dark reaction, it is generally performed to add a polymerization inhibitor, but when the photosensitive lithographic printing plate material is often accompanied by a decrease in sensitivity, therefore, A new technique for suppressing the dark reaction is desired.

Further, the photopolymerization type lithographic printing plate generally has a poor printing durability, and various improvements of the photopolymerizable composition have been studied in order to improve this, but there is still room for improvement. It is the current situation. Further, this improvement in printing durability is generally in a trade-off relationship with performance such as linearity, and improvement in these performances is also demanded at the same time.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems. That is, in the present invention, it is possible to achieve both sensitivity and storability, and further,
An object of the present invention is to provide a photopolymerizable composition and a photosensitive lithographic printing plate material which have good printing durability, high resolution, and good linearity.

[0011]

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

1. Light containing at least one alkali-soluble polymer, a compound having an ethylenic addition-polymerizable group, a photopolymerization initiator, a colorant and a compound represented by the general formula (1) or (2). Polymerizable resin composition.

2. In a photosensitive lithographic printing plate material having at least a photopolymerizable layer and an overcoat layer on a support, the photopolymerizable layer has at least one alkali-soluble polymer, a compound having an ethylenic addition polymerizable group, and photopolymerization. Initiator, colorant and the above general formula (1) or (2)
A photosensitive lithographic printing plate material containing a compound represented by:

The present invention will be described in more detail below. (Photopolymerizable resin composition) The photopolymerizable resin composition according to the present invention comprises at least one alkali-soluble polymer, a compound having an ethylenic addition-polymerizable group, a photopolymerization initiator, a colorant and the above-mentioned, which will be described later. The compound represented by the general formula (1) or (2) is contained as described below, but in addition to this, various additives described below may be contained.

The photopolymerizable resin composition according to the present invention is preferably used as a photosensitive lithographic printing plate material as will be described later, but it can be applied to a photoresist or the like in addition to this. When applied to a photosensitive lithographic printing plate material, it is preferably used for a photopolymerizable layer.

(Metal Support) The support used in the photosensitive lithographic printing plate material of the present invention (hereinafter also simply referred to as a support) is
For example, a metal plate made of aluminum, stainless steel, chromium, nickel, or the like, or a plastic film such as a polyester film, a polyethylene film, or a polypropylene film laminated or vapor-deposited with the above metal thin film can be used. A film, a nylon film, or the like whose surface is hydrophilized can be used, but an aluminum support is preferably used, and in this case, pure aluminum or aluminum alloy may be used.

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. Etc. are used.

The support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface before roughening (graining treatment). As degreasing treatment, trichlene,
A degreasing treatment using a solvent such as thinner and an emulsion degreasing treatment using an emulsion such as kesilon or triethanol are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which 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 generated on the surface of the support.In this case, dip in desmutting with an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to apply a treatment.

Examples of the above-mentioned roughening method include a mechanical method and an electrochemical method, but it is preferable to electrochemically roughen the surface in an acidic medium. The methods of roughening the surface may be combined.

The method of electrochemically roughening the surface is not particularly limited, but a method of electrochemically roughening in an acidic medium, that is, an acidic electrolytic solution is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical graining method can be used, but it is preferable to use a hydrochloric acid-based or nitric acid-based electrolytic solution. Regarding the electrochemical graining method, for example, Japanese Patent Publication No. 48-28123, British Patent No. 896,563, and Japanese Patent Laid-Open No. 53-67507.
The method described in the publication can be used.

This surface roughening method can be generally performed by applying a voltage in the range of 1 to 50 V, but it is preferable to set the voltage in the range of 10 to 30 V.

The 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. The amount of electricity is 100-500
A range of 0 c / dm ² can be used, but 100 to
It is preferable to select from the range of 2000 c / dm ² .

The temperature for carrying out this roughening method is 10 to 50 ° C.
However, it is preferable to select from the range of 15 to 45 ° C.

Electrification using nitric acid-based electrolyte as 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 10-200A /
A range of dm ² can be used, but 50 to 150 A
It is preferable to select from the range of / dm ² . Electricity is 10
A range of 0 to 5000 c / dm ² can be used, but 100 to 2000 c / dm ² , and further 200 to 100
It is preferable to select from the range of 0 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. The electrolyte may contain nitrates, chlorides,
Amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like 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 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 is carried out with an alkaline aqueous 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 method of mechanically roughening the surface is not particularly limited, but a brush polishing method and a honing polishing method are preferable. Roughening by the brush polishing method, for example,
A rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm is rotated and, for example, a particle diameter of 10 to 100 is applied to the surface of the support.
It can be carried out by pressing a brush while supplying a slurry in which particles of volcanic ash having a diameter of μm are uniformly dispersed in water.
Roughening by honing polishing is performed, for example, with a particle size of 10 to 1
Particles of volcanic ash having a size of 00 μm can be uniformly dispersed in water, pressure is applied from a nozzle to eject the particles, and the particles can be obliquely collided with the surface of the support for roughening. Moreover, for example, 100 to 100 μm of abrasive particles having a particle size of 10 to 100 μm are provided on the surface of the support.
2.5 × 10 ³ to 10 × 10 ³ pieces at intervals of 200 μm /
Roughening can also be carried out by laminating sheets applied so as to have a density of cm ² and applying pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the above-mentioned method, it is preferable to immerse it in an acid or alkali aqueous solution in order to remove the abrasive, the aluminum scraps and the like that have invaded 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 . It is preferable that after the dipping treatment with an alkaline aqueous 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 method and the electrochemical surface roughening method as described above may be used individually for surface roughening,
Further, the surface may be roughened by combining, but a method of roughening by combining is preferable.

Next, the support can be subjected to an anodic oxidation treatment. 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. 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 amount of anodized coating is
For example, an aluminum plate is treated with a chromic acid phosphoric acid solution (phosphoric acid 85%
Liquid: 35 ml, chromium (IV) oxide: 20 g is dissolved in 1 liter of water) to dissolve the oxide film, and the mass change of the plate before and after the dissolution of the coating 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, in the present invention, after the above treatments, the surface of the support is preferably treated with an aqueous solvent containing polyvinyl phosphonic acid, and the aqueous solvent is preferably an aqueous solution. .

The aqueous solution containing polyvinylphosphonic acid means that the concentration of polyvinylphosphonic acid is 0.01%.
An aqueous solution containing -30% is preferable, and particularly preferably,
It is preferable to use an aqueous solution of 0.05 to 10%. If the content concentration is lower than the above range, the effect of the present invention is small, and if the content concentration is higher than the above range, the liquid viscosity may be high and handling may be difficult.

It is also preferable that the above-mentioned aqueous solution further contains a compound other than polyvinyl phosphonic acid, and as the compound to be contained, conventionally known water-soluble resin, water-dispersible inorganic fine particles, acids, bases and the like can be used. Can be mentioned.

Specifically, as the water-soluble resin, as the hydrophilic resin, for example, polyvinyl alcohol,
Polysaccharide, polyvinylpyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, sucrose octaacetate, ammonium alginate, sodium alginate, polyvinylamine, polyallylamine, polystyrene sulfonic acid, polyacrylic Examples thereof include acids, water-soluble polyamides and maleic anhydride copolymers.

Examples of the water-dispersible inorganic fine particles include colloidal silica and necklace-shaped colloidal silica described in JP-A-2001-232746.

As the acids, phosphoric acid, sulfuric acid, nitric acid,
Hydrochloric acid, other strong acids or salts thereof may be mentioned.

Examples of the bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

In the present invention, the compound that can be used together with these polyvinyl phosphonic acids is preferably contained in a concentration of 0 to 40%, more preferably 0 to 20%.

The treatment time with the aqueous solution containing polyvinyl phosphonic acid according to the present invention is 0.5 seconds to 3 seconds.
It is preferably within minutes, more preferably within 1 second to within 1 minute, and particularly preferably 2 seconds to 30 seconds. If less than this, the effect of the present invention may be reduced, and
If it is more than this range, the productivity is inferior, so the above range is preferable.

The treatment temperature during the treatment with the above-mentioned aqueous solution is 40 to 100 depending on the temperature of the aqueous solution and the substrate to be treated.
It is preferably in the range of ℃, more preferably 50 ~
90 ° C, particularly 60 to 80 ° C is preferable. At lower temperatures, the effect of the present invention may be small, and at higher temperatures, the above range is preferable from the viewpoint of production stability.

(Compounds represented by the general formulas (1) and (2)) The compounds represented by the general formulas (1) and (2) according to the present invention will be described below.

In the general formula (1), n represents 1 or 2, and when n = 1, R ₁ represents a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl group, a substituted alkyl group or an alkenyl group. Or a substituted alkenyl group, R ₂
Is a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group (eg methyl, ethyl and propyl group), a substituted alkyl group, an alkenyl group (eg allyl group), a substituted alkenyl group, an alkoxy group (eg methoxy and ethoxy group), an alkylthio group (Eg ethylthio group), substituted alkylthio group, arylthio group (eg phenylthio group), substituted arylthio group, aryl group (eg phenyl group), substituted aryl group (eg p-tolyl group), acyl group (eg acetyl and propionyl group) An acyloxy group (eg acetoxy and propionyloxy group),
Alkoxycarbonyl group (eg methoxycarbonyl and ethoxycarbonyl group), alkylsulfonyl group (eg methylsulfonyl group), carbamoyl group, substituted carbamoyl group, amide group, substituted amide group, sulfamoyl group, substituted sulfamoyl group, sulfonamide group, substituted sulfone It represents an amide group, a carboxy group or a cyano group.
When n = 2, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents a linear or branched alkylene group having 1 to 20 carbon atoms.

As described above, R ₁ is preferably a hydrogen atom or an alkyl group, but is preferably a hydrogen atom or a methyl group. R ₂ is a carbon number 2 such as ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and eicosamethylene. To an alkylene group having 20 to 20 carbon atoms are preferred, an alkylene group having 2 to 10 carbon atoms is more preferred, and an octamethylene group is particularly preferred.

In the general formula (2), n is 1 or
Or 2 and when n = 1, R₃Is a hydrogen atom, carbon
Alkyl group having 1 to 18 carbon atoms, alke having 3 to 18 carbon atoms
Nyl group, C3-C8 cycloalkyl group, C7
18 arylalkyl groups (wherein the aryl moiety is
Rogen, nitro, alkyl having 1 to 4 carbons or carbon
It may be substituted with the alkoxy of the formulas 1 to 4)
Is an aryl group having 6 to 12 carbon atoms (the aryl moiety is
Halogen, nitro, alkyl having 1 to 4 carbons or charcoal
(May be substituted with alkoxy having a prime number of 1 to 4)
Represent, R_FourIs a hydrogen atom, hydroxy group, alkoxy
Group, alkyl group, substituted alkyl group, alkenyl group or
Represents a substituted alkenyl group, and when n = 2, R₃Is carbon
An alkylene group having 1 to 10 carbon atoms or 6 to 12 carbon atoms
An arylene group (wherein the aryl moiety is halogen, nitro,
Alkyl having 1 to 4 carbons or Al having 1 to 4 carbons
Coxy may be substituted). R_FourIs hydrogen
Atom, hydroxy group, halogen atom, alkyl group (eg
Methyl, ethyl and propyl groups), substituted alkyl groups,
An alkenyl group (for example, an allyl group), a substituted alkenyl group,
Alkoxy group (eg methoxy group, ethoxy group),
Kirthio group (eg ethylthio group), Substituted alkylthio group
Groups, arylthio groups (eg phenylthio groups), substituted groups
Reelthio group, aryl group (eg phenyl group), substitution
Aryl group (for example, p-tolyl group), acyl group (for example,
Acetyl and propionyl groups), acyloxy groups (eg
Acetoxy and propionyloxy groups), alkoxy groups
Rubonyl groups (eg methoxycarbonyl and ethoxyca
Rubonyl group), alkylsulfonyl group (eg methyls
Rufonyl group), carbamoyl group, substituted carbamoyl group,
Amido group, substituted amide group, sulfamoyl group, substituted sulfone group
Famoyl group, sulfonamide group, substituted sulfonamide
Represents a group, a carboxy group or a cyano group. Preferably,
R when n = 1 ₃Is -C₁₂H_{twenty five}And R_FourIs acetyl
It is a ru basis.

The compound represented by the general formula (1) or (2) according to the present invention is preferably contained in the photopolymerizable resin composition in an amount of 0.01 to 15% by mass. Even when it is contained in the photosensitive lithographic printing plate material, the above range is preferable.

(Compound having ethylenic addition-polymerizable group) The compound having an ethylenic addition-polymerizable group according to the present invention is preferably a monomer having an ethylenically unsaturated bond group, which is a photosensitive lithographic plate. When applied to a printing plate material, it may be contained in any layer, but it is preferably contained in a photopolymerizable layer (hereinafter sometimes simply referred to as a photosensitive layer).

As the compound having an ethylenic addition-polymerizable group according to the present invention, known monomers (hereinafter sometimes simply referred to as monomers) can be used. Specific examples thereof include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxy. Hexanolide acrylate, acrylate of 1,3-dioxane alcohol ε-caprolactone adduct, 1,3
-Monofunctional acrylic acid esters such as dioxolane acrylate, or methacrylic acid in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate, itaconic acid, crotonic acid, maleic acid ester, for example, ethylene glycol diacrylate,
Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate,
Tripropylene glycol diacrylate, hydroxy pivalate neopentyl glycol diacrylate,
Neopentyl glycol adipate diacrylate,
Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclo Decane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, bifunctional acrylic acid ester such as diacrylate of diglycidyl ether of 1,6-hexanediol, or methacrylate, itaconate, crotonate of these acrylates. Methacrylic acid in place of maleate, itaconic acid, crotonic acid, maleic acid ester such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane Reacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid- Polyfunctional acrylic acid such as dipentaerythritol triacrylate, propionic acid-dipentaerythritol tetraacrylate, hydroxypivalylaldehyde modified dimethylolpropane triacrylate, or methacrylic acid obtained by replacing these acrylates with methacrylate, itaconate, crotonate or maleate. Acid, itaconic acid, crotonic acid, malein Can be mentioned esters can also be used these oligomers.

Also, a prepolymer of the above-mentioned monomer can be used in the same manner as above. Examples of the prepolymer include compounds such as those described below,
A prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerization property can also be suitably used. These prepolymers may be one type or two types.
One or more kinds may be used in combination, 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- epichlorohydrin - (meth)
Epoxy acrylates such as acrylic acid, phenol novolac-epichlorohydrin- (meth) acrylic acid in which (meth) acrylic acid is introduced into an epoxy resin, for example, ethylene glycol-adipic acid-tolylene diisocyanate-2-hydroxyethyl acrylate, 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 and polysiloxane-diisocyanate-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 photosensitive layer of the present invention comprises a phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane acrylic acid benzoate. , An alkylene glycol type acrylic acid-modified, urethane-modified acrylate, and the like, and addition-polymerizable oligomers and prepolymers having a structural unit formed from the monomer.

Examples of the monomers preferably used in the present invention include phosphoric acid ester compounds containing at least one ethylenic double bond. The compound is a compound in which at least a part of the hydroxyl groups of phosphoric acid is esterified, as long as it has an ethylenic double bond in the molecule, and a compound having a (meth) acryloyl group is particularly preferable.

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. Of these, compounds having two or more acryl groups or methacryl groups in the molecule are preferred in the present invention, and further, the compounds have a molecular weight of 10,000 or less, more preferably 5,000.
Those of 0 or less are preferable.

The photosensitive layer according to the present invention contains the above-mentioned monomer in an amount of 1.0 to 8 of the photosensitive resin composition for coating 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. Further, the content ratio of the monomer in the photopolymerizable resin composition according to the present invention is preferably within the above range.

(Alkali-Soluble Polymer) The photopolymerizable resin composition according to the present invention contains an alkali-soluble polymer, which can be applied to a photosensitive lithographic printing plate material. Therefore, the photosensitive layer, the overcoat layer and the like according to the present invention preferably contain an alkali-soluble polymer (binder). The alkali-soluble polymer is preferably soluble in an alkali developing solution of a developing solution when developing a photosensitive lithographic printing plate material,
Those containing a vinyl-based copolymer comprising at least one kind of the monomers (monomers) described in (1) to (17) below are preferable.

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

(2) Monomers having an aliphatic hydroxyl group, for example, 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-cyclohexyl acrylamide, N-phenyl acrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenyl acrylamide, 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.

As the alkali-soluble polymer, polyvinyl butyral resin, polyurethane resin,
Any other alkali-soluble polymer such as polyamide resin, polyester resin, epoxy resin, novolac resin, or natural resin may be used in combination with the vinyl copolymer according to the present invention.

The content of the alkali-soluble polymer in the composition for coating the photosensitive layer according to the present invention is preferably 10 to 90% by mass with respect to the photosensitive layer, and 15 to 7 is preferable.
The range of 0 mass% is more preferable, and the range of 20 to 50 mass% is particularly preferable from the viewpoint of sensitivity. Furthermore,
The above vinyl-based copolymer is preferably 50 to 100% by mass in the alkali-soluble polymer,
It is more preferably 100% by mass. Also, the photopolymerizable resin composition according to the present invention preferably contains an alkali-soluble polymer in the above range.

The alkali-soluble polymer according to the present invention is
Those having an acid value in the range of 10 to 150 are preferable. More preferably, it is in the range of 30 to 120, and further 50 to
A range of 90 is more preferable. This has the advantage that the polarities of the entire photosensitive layer can be balanced, and the aggregation of pigment in the photosensitive layer coating liquid can be prevented.

(Photopolymerization Initiator) In the photopolymerizable resin composition according to the present invention, it is preferable to use a compound capable of generating radicals by actinic rays (hereinafter, also referred to as a photopolymerization initiator). When the composition is applied to a photosensitive lithographic printing plate material, it is preferably contained in the photopolymerizable layer (photosensitive layer).

What can be preferably used as the photopolymerization initiator is described in, for example, J. Carbonyl compounds, organosulfur compounds, persulfides, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar.
Examples thereof include redox compounds, azo compounds, diazo compounds, halogen compounds, photoreducible dyes, and the like, and the compounds disclosed in British Patent 1,459,563 are also preferable.

Specifically, the following examples can be mentioned, but the invention is not limited thereto. That is, benzoin methyl ether, benzoin-i-propyl ether,
Benzoin derivatives such as α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,
Benzophenone derivatives such as 4'-bis (dimethylamino) benzophenone; 2-chlorothioxanthone, 2-i
A thioxanthone derivative such as propylthioxanthone;
Anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N
-Acridone derivatives such as butylacridone; α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, and JP-B-59-1281
JP-A-61-19621 and JP-A-60-6.
Triazine derivatives described in JP-A-0104; JP-A-59-59
-1504 and 61-243807; organic peroxides described in JP-B-43-23684 and 4;
4-6413, 44-4413, 47.
-1604 and U.S. Pat. No. 3,567,453
Diazonium compounds described in U.S. Pat.
8,328, 2,852,379 and 2,9
No. 40,853, organic azide compounds;
-22062, 37-13109, and 3
8-18015 and 45-9610, o-quinonediazides; JP-B-55-39162
JP-A-59-14023 and "Macromolecules" 10
Vol., 1307 (1977), various onium compounds; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent No. 1
09,851, 126,712 and "Journal of Imaging Science (J. Image.
Sci. ) ”, Volume 30, p. 174 (1986), Metal Allene Complexes; Japanese Patent Application Nos. 4-56831 and 4-89.
(Oxo) sulfonium organic boron complex described in No. 535;
JP-A-59-152396, JP-A-61-151
Titanocenes described in Japanese Patent No. 197; "Coordination Chemistry Review (Coordinati
on Chemistry Review) "84 volumes,
85-277 (1988) and JP-A-2-182.
No. 701, a transition metal complex containing a transition metal such as ruthenium; 2,4,5-triarylimidazole dimer, as described in JP-A-3-209477; carbon tetrabromide, JP-A-59. Organic halogen compounds and the like described in JP-A-107344.

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 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 content of these polymerization initiators in the photosensitive layer is not particularly limited, but is 0.1 to 20 relative to 100 parts by mass of the compound having an ethylenic addition polymerizable group according to the present invention.
Parts by mass are preferred. The mixing ratio of the photopolymerization initiator and the sensitizing dye is 1: 100 to 100: 1 in terms of molar ratio.
preferable. Further, the content ratio of the photopolymerization initiator in the photopolymerizable resin composition according to the present invention is also preferably within the above range.

(Intermediate Layer) The photosensitive lithographic printing plate material according to the invention is preferably provided with an intermediate layer, and the layer may be provided at any position of the photosensitive lithographic printing plate material. It is preferably provided between the polymerizable layer and the support, and the structure of the intermediate layer may be one layer or an intermediate layer composed of two or more layers.

The thickness of the intermediate layer as the photosensitive lithographic printing plate material is preferably 0.1 to 1000 mg / m ² .
More preferably 0.5 to 500 mg / m ² ,
Particularly preferably, it is 1 to 300 mg / m ² . If the amount is less than the above range, the printing durability may be deteriorated, and if the amount is more than the above range, there may be a cause of defective development over time, and the above range is preferable.
In this case, the thickness of the intermediate layer, when it is composed of a plurality of layers, means the total thickness of all of them.

The intermediate layer preferably contains the above-mentioned polymer binder and, in addition to the above-mentioned compound having an ethylenic addition-polymerizable group, etc., it contains additives other than these. May be.

(Overcoat Layer) An overcoat layer (also referred to as a protective layer or an oxygen barrier layer) is preferably provided on the upper side of the photosensitive layer according to the present invention. The layer preferably has high solubility in a developing solution (generally an alkaline aqueous solution) described below.

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 can 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 can be applied onto the photosensitive layer and dried to form a protective layer. The thickness of the protective layer is preferably 0.1 to 5.0 μm, and particularly preferably 0.5 to 3.0 μm for the photosensitive lithographic printing plate material. The protective layer may further contain a surfactant, a matting agent, etc., if necessary.

As a method of applying the protective layer, a known method described later 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.

(Colorant) The colorant according to the present invention includes:
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 Co., Ltd.), Color Index Handbook, etc. are mentioned, and pigments are preferable.

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

Of these, it is preferable to select and use a pigment that has substantially no absorption in the absorption wavelength range of the spectral sensitizing dye corresponding to the exposure laser used. 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. Further, the amount of the pigment added is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the solid content of the coating composition of the photopolymerizable layer. The content of the pigment (colorant) in the photopolymerizable resin composition is also preferably within the above range.

As an exposure light source, an argon laser (48
8nm) or SHG-YAG laser (532nm)
In the case of using a violet pigment, a violet pigment or a blue pigment is preferably used from the viewpoint of the absorption of the pigment in the above-mentioned photosensitive wavelength region and the visibility of the image after development. Examples of such substances include cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue fast 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.

(Various Additives) In the photopolymerizable resin composition according to the present invention, in addition to the above-mentioned components, an ethylenically unsaturated double bond monomer is unnecessary as long as the effects of the present invention are not impaired. It is also possible to add a polymerization inhibitor to prevent such polymerization. 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 ceria 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 5% with respect to the mass of the total solid content of the above 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 10% of the total composition.

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.

Further, within a range not impairing the performance of the present invention,
A surfactant can be contained as a coatability improving agent. Of these, fluorine-based surfactants are preferable.

(Coating) Solvents used for preparing a coating composition for the photosensitive layer or overcoat layer of the photosensitive lithographic printing plate material according to the present invention include, for example, alcohols:
Derivatives of polyhydric alcohols include sec-butanol,
Isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, esters Classes: Ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like are preferred.

The prepared coating composition (layer coating solution) can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of the coating method of the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method and an extrusion coater method. Can be mentioned.

When the drying temperature of the photosensitive layer or the like 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.

(Image forming method) As a light source for imagewise exposing the photosensitive lithographic printing plate material of the present invention, for example, a laser,
Examples thereof include 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. Xenon lamp, halogen lamp,
A carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, an electrodeless light source and the like can be preferably used.

In the case of collective exposure, a photosensitive lithographic printing plate material may be overlaid with a mask material having a desired light exposure image pattern formed of a light shielding material, and the entire surface may be 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 controlled to be exposed 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, an argon laser, a He--Ne gas laser, a YAG laser, a semiconductor laser or 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 cylinder inner surface scanning, the recording material is fixed on the inner surface of the drum, and the laser beam is irradiated from the inside.
Main scanning is performed in the circumferential direction by rotating part or all of the optical system, and sub-scanning is performed in the axial direction by linearly moving part or all of the optical system parallel to the axis of the drum. In planar scanning, a polygon mirror or galvanometer mirror and an fθ lens are combined to perform main scanning of laser light,
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 imagewise exposed 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, potassium, ammonium; sodium diphosphate, potassium, ammonium; sodium bicarbonate, potassium bicarbonate,
Same ammonium; sodium carbonate, same potassium, same ammonium; sodium hydrogen carbonate, same potassium, same ammonium; sodium borate, same potassium, same ammonium; sodium hydroxide, same potassium, same ammonium and same inorganic lithium agent such as lithium The alkaline developer used may be mentioned.

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.

[0111]

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 (Synthesis of Binder) In a three-necked flask under a nitrogen stream,
Add 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile, and put in an oil bath at 80 ° C in a nitrogen stream. The reaction was carried out for 6 hours. Then, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. Weight average molecular weight measured by GPC is about 50,000, DSC
Glass transition temperature (T
g) was about 85 ° C.

(Preparation 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 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 performed for 1 minute under conditions of m ² and voltage of 15V. At this time, the center line average roughness (Ra) of the surface is 0.6.
It was 5 μm.

After the above-mentioned treatment, the treatment was carried out by immersing in the following solution. Solution temperature 80 ° C. Vinylphosphonic acid 0.2% Polyvinylphosphonic acid 1.5% An aluminum plate was passed through the above solution for 30 seconds and dried.

(Preparation of photosensitive lithographic printing plate material) A photopolymerizable photosensitive layer coating solution having the following composition was coated on the above support with a wire bar so as to have a dryness of 1.4 g / m ^2, and
Dry at 1.5 ° C for 1.5 minutes. After that, further on the photosensitive layer,
2.0 g of dry coating solution for overcoat layer
Apply with an applicator so that it becomes m ^2, and
Photosensitive lithographic printing plate material having an overcoat layer on the photosensitive layer after drying at 5 ° C for 1.5 minutes (Sample Nos. 1 to 9)
Was produced.

[0116]   <Photosensitive layer coating liquid>   Acrylic copolymer 1 (synthetic binder, molecular weight Mw = 50,000) 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.) 35.0 parts   Polytetramethylene glycol diacrylate     (PTMGA-250: Kyoeisha Chemical Co., Ltd.) 10.0 parts   Polyfunctional urethane acrylate     (U-15HA: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5.0 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 0.5 part   Compounds of general formula (1) or (2) or comparison                                               Compounds shown in Table 1 and addition amount   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   <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 (F1405: manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 part   900 parts of water

[0117]

[Chemical 3]

(Image formation) With respect to the photopolymerizable photosensitive lithographic printing plate material thus prepared, a CTP exposure device (Tigerca) equipped with an FD-YAG laser light source was used.
t: manufactured by ECRM) was used to perform image exposure at a resolution of 2540 dpi (dpi is the number of dots per 2.54 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) : CTP automatic developing machine (PHW32-V: Te) equipped with Mitsubishi Chemical Co., Ltd.
Preheat (100 ℃ 10 by chnigraph)
Second) and then developed to obtain a lithographic printing plate.

<Developer composition> (Aqueous solution containing the following additives) A potassium silicate 8.0% by mass Perex NBL: manufactured by Kao Corporation 3.0% by mass caustic potassium pH = 12.3 addition amount ( Evaluation of lithographic printing plate) The lithographic printing plate obtained as described above was examined or evaluated as follows. The same procedure was performed for Example 2.

<Sensitivity> No film loss in the image area was observed, and the halftone dot exposure area of 175 lines / 50% had a light amount twice that of the exposure amount that could be reproduced to 50% on the prepared lithographic printing plate surface. Laser power was used as the sensitivity.

<Printing durability> A lithographic printing plate prepared by exposing and developing an image of 175 lines with an appropriate exposure amount was coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) to produce coated paper and printing ink ( Toyo Ink Co., Ltd. Toyo King High Echo M Beni and dampening water (Tokyo Ink Co., Ltd. H liquid SG-51)
After printing 1000 sheets continuously, wipe the plate surface with an ultra plate cleaner, and use the number of prints with spot thinning in highlights and entanglement in shadows as an index of printing durability. did. One press life refers to the work of wiping with a cleaner after continuous printing of 1000 sheets. The larger the value, the better the performance.

<Storability> The above photosensitive lithographic printing plate material
It was stored in a dark place for 7 days at 0% RH and 55 ° C., and evaluated in the same manner as the above-described evaluation of sensitivity.

<< 90% Halftone Reproduction >> Halftone dots are drawn with linearity uncorrected by the above laser power (twice the amount of light), and development processing is performed. The area of the image part in the area of 2 mm × 2 mm was calculated and shown in Table 1 as a dot percentage.

The results of the above are shown in Table 1 together with the characteristics of each sample (photosensitive lithographic printing plate material).

[0125]

[Table 1]

Example 2 Spectral sensitizing dye 1 of Example 1,
2 and IRGACURE 784, the following compounds 1 to 7 were added, and the following compound 8 was added to the overcoat layer.
Samples 1 to 9 of Example 2 were prepared in the same manner as in Example 1 with the following coating liquid using.

Compound 1 0.7 parts by mass Compound 2 0.7 parts by mass Compound 3 0.7 parts by mass Compound 4 0.7 parts by mass Compound 5 0.7 parts by mass Compound 6 0.7 parts by mass Compound 7 4.0 Mass part <Overcoat layer coating liquid> Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Industry) 87 parts Water-soluble polyamide (P-70: manufactured by Toray) 10 parts Compound 8 2 parts Surfactant (F1405: large) (Manufactured by Nippon Ink Kogyo Co., Ltd.) 0.5 part Water 900 parts Also, using a self-made apparatus equipped with an InGaN semiconductor laser having an oscillation wavelength of 405 nm, exposure was performed in the same manner as in Example 1. The results are shown in Table 2.

[0128]

[Table 2]

[0129]

[Chemical 4]

[0130]

INDUSTRIAL APPLICABILITY The present invention makes it possible to achieve both sensitivity and storability, and further provides a lithographic printing plate having good printing durability, high resolution, and good linearity. A composition and a photosensitive lithographic printing plate material could be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/00 503 G03F 7/00 503 7/033 7/033 7/11 501 7/11 501 F term ( reference) 2H025 AA01 AA02 AA12 AB03 AC08 AD01 BC32 BC42 BC51 CA01 CA14 CA18 CA23 CA30 CA39 CA41 CB14 CB16 CB43 CB45 CB52 CC11 DA01 FA03 FA17 2H096 AA07 AA08 BA05 BA20 DA10 EA04 GA08 2H114 AA04 AA23 EA02 4J011 NA17 NB01 4J026 AA31 AA45 AA48 AA50 AC09 BA25 BA27 BA28 BA36 BA50 DB05 DB06 DB36 GA07 GA08

Claims (2)

[Claims] 1. At least one alkali-soluble polymer, a compound having an ethylenic addition-polymerizable group, a photopolymerization initiator, a colorant and a compound represented by the following general formula (1) or (2). A photopolymerizable resin composition comprising: [Chemical 1] In the formula, n represents 1 or 2, and when n = 1, R
₁ represents a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, R ₂ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, a substituted alkyl group, an alkenyl group,
Substituted alkenyl group, alkoxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, aryl group, substituted aryl group, acyl group, acyloxy group, alkoxycarbonyl group, alkylsulfonyl group, carbamoyl group, substituted carbamoyl group, amide Base,
It represents a substituted amide group, a sulfamoyl group, a substituted sulfamoyl group, a sulfonamide group, a substituted sulfonamide group, a carboxy group or a cyano group. When n = 2, R ₁ is
A hydrogen atom or an alkyl group is shown, and R ₂ has 1 to 1 carbon atoms.
20 linear or branched alkylene groups are shown. [Chemical 2] In the formula, n represents 1 or 2, and when n = 1, R
₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, or an alkyl group having 6 to 12 carbon atoms Represents an aryl group, R ₄ represents a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, and when n = 2, R ₃ represents a group having 1 to 10 carbon atoms. It represents an alkylene group or an arylene group having 6 to 12 carbon atoms. R ₄ is a hydrogen atom, a hydroxy group, a halogen atom,
Alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkoxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, aryl group, substituted aryl group, acyl group, acyloxy group, alkoxycarbonyl group, alkylsulfonyl Represents a group, a carbamoyl group, a substituted carbamoyl group, an amide group, a substituted amide group, a sulfamoyl group, a substituted sulfamoyl group, a sulfonamide group, a substituted sulfonamide group, a carboxy group or a cyano group. 2. A photosensitive lithographic printing plate material having at least a photopolymerizable layer and an overcoat layer on a support, wherein the photopolymerizable layer contains at least one alkali-soluble polymer and an ethylenic addition polymerizable group. A photosensitive lithographic printing plate material comprising a compound having the compound, a photopolymerization initiator, a colorant and the compound represented by the general formula (1) or (2).