JP2007313674A - Surface hydrophilic member, its manufacturing method and lithographic printing plate original plate employing surface hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface hydrophilic member, the hydrophilic nature of which is high and also durability of the hydrophilic layer of which is favorable, a simple manufacturing method thereof and a lithographic printing plate original plate, by which printing scumming properties are improved and, even under severe printing conditions, no smudging develops in a printing material. <P>SOLUTION: This surface hydrophilic member has an amino propyl silane condensed layer, a polymerization initiating layer, which is formed by bonding a compound having a polymerization initiating site enabling to initiate radical polymerization and a support bonding part with the base material of a support through the support bonding part, and a hydrophilic layer, which is formed of a hydrophilic group and an unsaturated compound having a radical polymerizable part and turning into a graft polymer directly bonded with the polymerization initiating layer, in the order named on the base material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel surface hydrophilic member having a hydrophilic layer, a method for producing the same, and a lithographic printing plate precursor using the surface hydrophilic member, and in particular, a surface useful as a support for a lithographic printing plate having excellent sensitivity and stain resistance. The present invention relates to a hydrophilic member, a method for producing the same, and a lithographic printing plate precursor using a surface hydrophilic member.

Conventionally, as a hydrophilic substrate or a hydrophilic layer used in a lithographic printing plate, an anodized aluminum substrate, or an anodized aluminum substrate for further improving hydrophilicity, silicate, polyvinylphosphonic acid (for example, Patent Document 1), substrates or hydrophilic layers treated with a primer such as polyvinylbenzoic acid have been used.
Research on hydrophilic substrates or hydrophilic layers using these aluminum supports has been actively conducted. In addition, a technique using a polymer having a sulfonic acid group as an undercoat layer of a photosensitive layer is known (for example, see Patent Document 2).

On the other hand, with respect to the hydrophilic layer when a flexible support such as PET (polyethylene phthalate) or cellulose acetate is used without using a metal support such as aluminum, a swollen hydrophilic layer composed of a hydrophilic polymer and a hydrophobic polymer. (See, for example, Patent Document 3), PET support having a microporous hydrophilic cross-linked silicate surface (see, for example, Patent Document 4), hydrophilic material containing a hydrophilic polymer and cured with a hydrolyzed tetraalkylorthosilicate Techniques such as an adhesive layer (see, for example, Patent Document 5 and Patent Document 6) are known.
In addition, surface treatment such as corona treatment, glow treatment, and plasma treatment to improve the hydrophilicity by generating hydroxyl groups, carboxyl groups, etc. on the base material requires expensive equipment, so simpler lithographic printing A method for producing a plate support has also been desired.

Thus, for example, a surface member having excellent hydrophilicity is essential on the surface of a lithographic printing plate support. Further, there has been a demand for a lithographic printing plate precursor capable of obtaining a printed matter that does not cause stains even under more severe printing conditions.
JP-A-7-1853 JP 59-101651 A JP-A-8-292558 European Patent Application No. 0709228 JP-A-8-272087 JP-A-8-507727

The object of the present invention in consideration of the above problems is to provide a surface hydrophilic member having high hydrophilicity and good durability of the hydrophilic layer, and a production method capable of producing the member by a simple method. There is.
Another object of the present invention is to provide a lithographic printing plate precursor which has improved printing smearing properties and can provide a printed matter that does not cause smudging even under severe printing conditions.

Means for solving the above-mentioned problems are as follows.
<1> Consists of a compound having an aminopropylsilane condensation layer, a polymerization initiation site capable of initiating radical polymerization, and a support binding site bonded to the support base material via the support binding site on the base material And a hydrophilic layer made of a graft polymer formed by an unsaturated compound having a hydrophilic group and a radically polymerizable site and directly bonded to the polymerization initiation layer. Surface hydrophilic member.
<2> The surface hydrophilic member according to <1>, wherein the base material is polyethylene terephthalate or polyethylene naphthalate.
<3> Supporting a compound having a step of forming an aminopropylsilane condensed layer by surface-treating the substrate with aminopropylsilane on the substrate, a polymerization initiation site capable of initiating radical polymerization, and a support binding site A step of forming a polymerization initiating layer by bonding a body binding site to a support substrate, and an unsaturated compound having a hydrophilic group and a radical polymerizable site is polymerized starting from the radical generated from the polymerization initiating layer. And a step of forming a hydrophilic layer made of a graft polymer.
<4> A lithographic printing plate precursor comprising an image forming layer on the surface hydrophilic member according to <1> or <2>.

According to the present invention, it is possible to provide a surface hydrophilic member having high hydrophilicity and good durability of the hydrophilic layer, and a production method capable of producing the member by a simple method.
As another object, it is possible to provide a lithographic printing plate precursor that has improved printing stain resistance and that can obtain a printed matter that does not cause stain even under severe printing conditions.

The present invention is described in detail below.
<Surface hydrophilic member, production method thereof>
The surface hydrophilic member of the present invention comprises an aminopropylsilane condensation layer on a substrate, a compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site, via a support binding site. A polymerization initiating layer formed by bonding with a material, and a hydrophilic layer formed of an unsaturated compound having a hydrophilic group and a radical polymerizable site, and made of a graft polymer directly bonded to the polymerization initiating layer, It is characterized by having.
Further, the method for producing a surface hydrophilic member of the present invention comprises a step of forming an aminopropylsilane condensation layer obtained by surface-treating the base material with aminopropylsilane on the base material, and a polymerization initiation site capable of initiating radical polymerization. A step of bonding a support binding site of a compound having a support binding site to a support substrate to form a polymerization initiating layer; and an unsaturated compound having a hydrophilic group and a radical polymerizable site to form the polymerization initiating layer. And a step of polymerizing the radical generated from the starting point to form a hydrophilic layer made of a graft polymer.
Below, the hydrophilic layer which consists of a base material, an aminopropylsilane condensation layer, a polymerization start layer, and a graft polymer which comprises the surface hydrophilic member of this invention, and these manufacturing methods are demonstrated concretely.
In the present specification, the base material constituting the surface hydrophilic member is a “base material” before the surface treatment with aminopropylsilane, and the “base material” after the surface treatment. Those having a polymerization initiating layer are referred to as “supports”.

[Aminopropylsilane condensation layer, base material]
The surface hydrophilic member of the present invention has an aminopropylsilane condensation layer on the substrate in order to generate hydroxyl groups on the substrate surface.
Below, aminopropylsilane, its solvent, a base material, and the surface treatment method of a base material are demonstrated concretely.

(Aminopropylsilane)
In the present invention, aminopropylsilane used for surface treatment includes 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltributyloxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane is exemplified, among which 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferred, and 3-aminopropyltrimethoxysilane is particularly preferred.

  From the viewpoint of condensation reactivity, the content of aminopropylsilane is preferably 0.01 to 30% by volume, and preferably 0.1 to 10% by volume with respect to the volume of the solution obtained by dissolving the aminopropylsilane with the following solvent. More preferred.

(solvent)
As a solvent for dissolving and dispersing the aminopropylsilane, aminopropylsilane is dispersed, and from the viewpoint of uniformly forming the aminopropylsilane condensation layer on the base material, acetone, methyl ethyl ketone, ethanol, methanol, Examples include toluene, 2-methoxyethanol, 1-methoxy-2-propanol, and acetone is a preferable solvent.

(Base material)
The substrate used in the present invention (hereinafter referred to as “film” as appropriate) has a strong bond with aminopropylsilyl by surface treatment with the aminopropylsilane, and has a high concentration of hydroxyl groups, amino groups, etc. on the surface. Any of organic materials or hybrid materials of organic and inorganic materials can be used. Among these, an organic material is preferable as a base material that exhibits the effect.
As an organic material constituting the substrate used in the present invention, acrylic resin such as polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane- Polyester resins such as 4,4′-dicarboxylate and polybutylene terephthalate, epoxy resins represented by commercial products such as Epicoat (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), polycarbonate resins, polyimide resins, A novolac resin, a phenol resin, etc. can be used suitably.
Other organic materials include cellulose esters (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide, polystyrene (eg, syndiotactic polystyrene), polyolefin ( Examples include polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, and polyetherketone.
Among these, from the viewpoint of practicality, a flexible substrate is preferable, and polyethylene terephthalate and polyethylene naphthalate are preferable.
In general, a flat base material is used, but the base material is not necessarily limited to a flat base material, and a base material having an arbitrary shape such as a cylindrical shape can be used similarly.

(Process of forming an aminopropylsilane condensation layer on the substrate with the surface treated with aminopropylsilane)
In the present invention, the substrate is surface-treated with aminopropylsilane. One example is shown below, but is not limited thereto.
The aminopropylsilane is added to the solvent to make a 0.1-10.0% by volume solution. This is left at room temperature for 0.5 to 20 days from the viewpoint of allowing the condensation reaction to proceed. Since the reaction is accelerated by heating, the standing time can be shortened from 0.5 hours to 3 days under heating conditions of 30 ° C. to 60 ° C. Next, the substrate is dried after being ultrasonically cleaned with distilled water, ethanol and acetone. This substrate is immersed in the solution for 1 to 60 minutes and then taken out and baked at room temperature to 160 ° C. for 0.5 to 30 minutes to generate a hydroxyl group on the substrate. More preferably, the organic matter remaining on the surface is decomposed by UV ozone treatment to increase surface hydrophilicity.
In this way, by generating hydroxyl groups at a high density on the substrate, a polymerization initiating layer for performing graft polymerization can be bonded onto the support substrate.

<Polymerization initiating layer constituted by a compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site bonded to a support substrate via the support binding site>
The surface hydrophilic member of the present invention is composed of a compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site bonded to a support substrate via the support substrate binding site. It has a polymerization initiating layer.
Below, it describes concretely about the process of forming a specific compound and a polymerization start layer.

[Compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site]
The polymerization initiating layer in the present invention includes a compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site (hereinafter, referred to as “specific compound” as appropriate).
The support binding site and polymerization initiation site of the specific compound are specifically described below.

(Support binding site)
The support binding site is composed of a reactive group capable of reacting and binding with a functional group present on the surface of the support (mainly a hydroxyl group in the aminopropylsilane condensation layer in the present invention). As the reactive group, Specific examples include the following groups.

  The polymerization initiation site and support binding site described in detail below may be directly bonded or may be bonded via a linking group. Examples of this linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specifically, a saturated carbon group, aromatic group, ester group, amide group, ureido Group, ether group, amino group, sulfonamide group, and the like. The linking group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkoxy group, and a halogen atom.

(Polymerization start site)
The polymerization initiation site in the present invention is not particularly limited as long as it has a polymerization initiation site that can be polymerized with a polymerizable compound. For example, hydrogen abstraction type radical polymerization initiation site, photocleavage type radical polymerization Examples include a start site.
-Hydrogen abstraction-type radical polymerization initiation site-
The compound having a hydrogen abstraction-type radical polymerization initiation site may be a low-molecular radical polymerization initiator or a high-molecular radical polymerization initiator as long as it has the support-binding site in the molecule, and is generally known. Is used.
Examples of the low-molecular radical polymerization initiator include known radicals such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, and thioxanthone. Generators can be used. In addition, since sulfonium salts and iodonium salts used as photoacid generators usually act as radical generators upon irradiation with light, they may be used in the present invention.
As the radical polymerization initiator for the polymer, the active carbonyl group described in paragraphs [0012] to [0030] of JP-A-9-77891 and paragraphs [0020] to [0073] of JP-A-10-45927 can be used. A polymer compound having a chain can be used.

  The content of the radical polymerization initiator can be appropriately selected in consideration of the type of base material, the amount of desired graft polymer produced, and the like, but generally 0.1 to 40% by weight in the case of a low molecule. In the case of a polymer, the range is preferably 1.0 to 50% by weight.

Further, for the purpose of increasing sensitivity, a sensitizer can be contained in addition to the radical generator. Examples of such sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.
The sensitizer is preferably contained in an amount of about 50 to 200% by weight with respect to the radical polymerization initiator.

-Photocleavage type radical polymerization initiation site-
The photocleavable radical polymerization initiation site is a structure containing a single bond that is cleaved by light.
Single bonds that can be cleaved by light include carbonyl α-cleavage, β-cleavage reaction, light-free transfer reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—O bond, a S—N bond, a C—N bond, a N—O bond, and a C—Cl bond.

  In addition, since the polymerization initiation site containing a single bond that can be cleaved by light is the starting point of graft polymerization in the graft polymer production process, when the single bond that can be cleaved by light is cleaved, a radical is generated by the cleavage reaction. It has a function to make it. As described above, examples of the structure of the polymerization initiation site having a single bond that can be cleaved by light and capable of generating radicals include structures containing the following groups.

  Examples include aromatic ketone groups, phenacyl ester groups, sulfonimide groups, sulfonyl ester groups, N-hydroxysulfonyl ester groups, benzylimide groups, trichloromethyl groups, benzyl chloride groups, and the like.

  When such a polymerization initiation site is cleaved by exposure and a radical is generated, if there is a polymerizable compound around the radical, this radical functions as a starting point for the graft polymerization reaction, and the desired graft polymer. Can be generated.

  Specific examples [1 to 16] of a photo-opening type polymerization initiator which is an example of a compound having a polymerization initiation site capable of initiating radical polymerization and a support binding site are shown below together with the cleavage portion. However, it is not limited to these.

(solvent)
As a solvent for dissolving the specific compound, toluene, hexane, acetone or the like can be used.
At this time, the concentration of the compound in the solution or the dispersion is preferably 0.01% by mass to 30% by mass, and particularly preferably 0.1% by mass to 15% by mass. As a liquid temperature in making it contact, 0 to 100 degreeC is preferable. The contact time is preferably 1 second to 50 hours, and more preferably 10 seconds to 10 hours.

[Step of forming polymerization initiation layer]
In the present invention, the step of forming the polymerization initiating layer is preferably, but not limited to, forming the polymerization initiating layer on the support substrate by the method described below.
The said specific compound is dissolved with the said solvent, the density | concentration of this specific compound produces 0.01-10 mass%, and it apply | coats uniformly on the said support body base material. After the coating, the substrate is heated at room temperature to 130 ° C. for 5 to 120 seconds, and the support substrate after spin coating is washed with toluene and acetone.
The uniform coating method is not particularly limited, and examples thereof include spin coating and dip coating.
By having this polymerization initiating layer, an unsaturated compound having a hydrophilic group and a radical polymerizable site, which will be described below, is polymerized from the radical generated from the polymerization initiating layer as a starting point, and grafted onto the polymerization initiating layer. A hydrophilic layer made of a polymer can be formed.

<Hydrophilic layer formed of an unsaturated compound having a hydrophilic group and a radical polymerizable site, and comprising a graft polymer directly bonded to the polymerization initiation layer>
The surface hydrophilic member of the present invention is a graft polymer formed of an unsaturated compound having a hydrophilic group and a radical polymerizable moiety (hereinafter, referred to as “specific unsaturated compound” as appropriate) and directly bonded to the polymerization initiating layer. The hydrophilic layer which consists of.
Below, it describes about the formation process of a specific unsaturated compound and a hydrophilic layer.

[Unsaturated compound having hydrophilic group and radical polymerizable moiety]
In the present invention, as the specific unsaturated compound, any compound having a radical polymerizable moiety can be used. For example, a hydrophilic monomer, a hydrophobic monomer, a macromer, an oligomer, a polymerizable unsaturated group can be used. The polymer etc. which have are mentioned. In the present invention, from the viewpoint of the hydrophilicity of the conductive material, a hydrophilic polymer, a hydrophilic macromonomer, a hydrophilic monomer or the like having a hydrophilic group that is a polar group is particularly preferable.
Specific examples of the unsaturated polymerizable compound preferably used in the present invention are shown below.

(Hydrophilic polymer)
The hydrophilic polymer in the present invention is a radically polymerizable group-containing hydrophilic polymer having a radically polymerizable moiety into which an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group, or a (meth) acryl group is introduced in the molecule. Refers to a functional polymer. This radical polymerizable group-containing hydrophilic polymer needs to have a polymerizable group at the main chain end and / or side chain, and preferably has a polymerizable group at both of them. Hereinafter, a hydrophilic polymer having a polymerizable group (at the main chain end and / or side chain) is referred to as a radical polymerizable group-containing hydrophilic polymer.

Such a radically polymerizable group-containing hydrophilic polymer can be synthesized as follows.
As a synthesis method, (a) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, Next, a method of introducing a double bond by treatment with a base or the like, and (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.

In the methods (a) and (b), the hydrophilic monomer used for the synthesis of the radical polymerizable group-containing hydrophilic polymer includes (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali. Metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropion Acid or alkali metal salt and amine salt thereof, vinyl sulfonic acid or alkali metal salt and amine salt thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfone Monomers having hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or salts thereof, hydroxyl groups, amide groups and ether groups, such as acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Can be mentioned.
As the hydrophilic polymer used in the method (c), a hydrophilic homopolymer or copolymer obtained using at least one selected from these hydrophilic monomers is used.

  When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.

  Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate.

  Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. It is preferable to introduce an unsaturated group using it. Examples of the monomer having an addition polymerizable unsaturated group used for this purpose include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

(Hydrophilic macromonomer)
The method for producing a macromonomer that can be used in the present invention is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999 by the IP Publishing Bureau. Various production methods have been proposed in “Synthesis”.
Particularly useful hydrophilic macromonomers that can be used in the present invention include macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsterene sulfone. Sulfonic acid macromonomer derived from monomer of acid and its salt, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, amide macromonomer derived from N-vinylcarboxylic amide monomer, hydroxyethyl Macromonomers derived from hydroxyl group-containing monomers such as methacrylic acid, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol Macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such Lumpur acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer of the present invention.
Among these hydrophilic macromonomers, useful ones have a molecular weight in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.

(Hydrophilic monomer)
The hydrophilic monomer may be a monomer having a positive charge such as ammonium or phosphonium, or an acid having a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group or capable of dissociating into a negative charge. Examples thereof include monomers having a group, but other hydrophilic monomers having a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group can also be used.

Specific examples of the hydrophilic monomer that can be used in the present invention include the following monomers.
For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt, Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salts and amine salts thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or salts thereof, 2-dimethylaminoethyl (meta Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.

(solvent)
The solvent for dissolving and dispersing the above-mentioned specific unsaturated compound is not particularly limited as long as the specific unsaturated compound and additives added as necessary can be dissolved.
For example, when a hydrophilic compound such as a hydrophilic monomer is applied, an aqueous solvent such as water or a water-soluble solvent is preferable, and a mixture thereof or a solvent in which a surfactant is further added is preferable. . The water-soluble solvent refers to a solvent miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.
When hydrophobic compounds such as hydrophobic monomers are applied, alcohol solvents such as methanol, ethanol, 1-methoxy-2-propanol, ketone solvents such as methyl ethyl ketone, and aromatics such as toluene. A group hydrocarbon solvent is preferred.

[Film thickness of hydrophilic layer]
The thickness of the hydrophilic layer is preferably 0.05 to 5 μm, more preferably 0.1 to 1 μm. When it is less than 0.05 μm, the hydrophilic effect is not exhibited. On the other hand, when the thickness is more than 5 μm, the adhesion with the image forming layer is deteriorated and the printing durability is lowered.

[Step of forming hydrophilic layer]
Specifically, the step of forming the hydrophilic layer composed of the graft polymer in the present invention is preferably performed by the following method, but is not limited thereto.
The support having the polymerization initiation layer is immersed in an aqueous solution in which the hydrophilic monomer or the like is diluted to 1 to 100% by mass, and exposed to light for 1 second to 60 minutes using an exposure apparatus, and the support is taken out. Thereafter, the surface hydrophilic member having a hydrophilic layer can be obtained by sufficiently washing with distilled water.
The exposure apparatus is not particularly limited, and a high pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a tungsten lamp, or the like can be used.

  As described above, the surface hydrophilic member of the present invention has surface hydrophilicity and durability by sequentially having an aminopropylsilane condensation layer, a polymerization initiating layer, and a hydrophilic layer on a substrate. Since it is excellent, it is particularly useful as a support for a lithographic printing plate from which a printed matter free from smudges can be obtained.

<Lithographic printing plate precursor>
The lithographic printing plate precursor according to the invention has an image forming layer (photosensitive layer or heat-sensitive layer) on the surface hydrophilic member obtained above.
The image forming layer will be described below.

(Image forming layer)
The image forming layer (photosensitive layer or heat-sensitive layer) of the lithographic printing plate precursor according to the invention contains a positive action sensitive composition or a negative action sensitive composition.
(Positive action sensitive composition)
In the present invention, it is preferable to use the following conventionally known positive action sensitive compositions [(a) to (b)] as the positive action sensitive composition.

(A) Conventionally used positive working photosensitive composition comprising naphthoquinone diazide and a novolac resin.
(B) A chemically amplified positive working photosensitive composition comprising a combination of an alkali-soluble compound protected with an acid-decomposable group and an acid generator.

  Both (a) and (b) are well known in the art, but are further used in combination with the positive action sensitive compositions ((c) to (f)) shown below. Is preferred.

(C) A laser-sensitive positive composition comprising a sulfonic acid ester polymer and an infrared absorber, which can produce a lithographic printing plate that does not require development processing described in JP-A-10-282672.
(D) a carboxylic acid ester polymer capable of producing a lithographic printing plate which does not require development processing described in European Patent Application No. 652483 and JP-A-6-502260, an acid generator or an infrared absorber; A laser-sensitive positive composition comprising:
(E) a laser-sensitive positive composition comprising an alkali-soluble compound described in JP-A No. 11-095421 and a substance that is thermally decomposable and substantially reduces the solubility of the alkali-soluble compound when not decomposed. object.
(F) An alkali development elution positive composition comprising an infrared absorber, a novolak resin, and a dissolution inhibitor, which can produce an alkali development elution type positive lithographic printing plate.

The compounds used in the positive action sensitive compositions shown in the above (a) to (f) will be described below.
-Acid generator-
The acid generator used in the positive action sensitive composition is a compound that generates an acid by heat or light, and is generally a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, or dyes. The compound which generate | occur | produces an acid by the well-known light currently used for the photo-decoloring agent of this, a photochromic agent, a microresist, etc., those mixtures, etc. can be mentioned, These can be selected suitably and can be used.

  In the present invention, the addition amount of the acid generator is usually about 0.001 to 40% by weight, preferably 0.01 to 20% by weight, based on the total solid content of the photosensitive layer or heat-sensitive layer. 1 to 5% by weight is more preferable.

-Alkali-soluble compounds-
When the alkali-soluble compound used in the positive action sensitive composition is applied to the positive type, the alkali solubility is reduced by coexistence with the dissolution inhibitor, and the alkali solubility is restored by the decomposition of the dissolution inhibitor. It is an alkali-soluble compound.

  Examples of the alkali-soluble compound used in the positive action sensitive composition include novolac resin, polyhydroxystyrene, and acrylic resin. The novolak resin used in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolak resins include, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, novolak resins obtained from o-cresol and formaldehyde, Novolak resin obtained from octylphenol and formaldehyde, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (o-, m-, p- or m- / p-, m- / o-, o And any novolak resin obtained from formaldehyde. These novolak resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.

  Examples of alkali-soluble compounds other than the novolak resin used in the positive action sensitive composition include polyhydroxystyrenes, hydroxystyrene-N-substituted maleimide copolymers, hydroxystyrene-maleic anhydride copolymers, and alkali-soluble groups. And an acrylic polymer having an alkali-soluble group. Here, examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphonic acid group, and an imide group.

  In addition, when a hydroxystyrene polymer such as poly-p-hydroxystyrene, poly-m-hydroxystyrene, p-hydroxystyrene-N-substituted maleimide copolymer, p-hydroxystyrene-maleic anhydride copolymer is used. Preferably have a weight average molecular weight of 2,000 to 500,000, more preferably 4,000 to 300,000.

  Examples of acrylic polymers having alkali-soluble groups include methacrylic acid-benzyl methacrylate copolymer, poly (hydroxyphenylmethacrylamide), poly (hydroxyphenylcarbonyloxyethyl acrylate), poly (2,4-dihydroxyphenylcarbonyloxy). Ethyl acrylate), polymers described in Japanese Patent Application No. 8-211731, and the like. These acrylic polymers have a weight average molecular weight of 2,000 to 500,000, preferably 4,000 to 300,000.

  Examples of urethane type polymers having alkali-soluble groups include resins obtained by reacting diphenylmethane diisocyanate with hexamethylene diisocyanate, tetraethylene glycol, and 2, 21 bis (hydroxymethyl) propionic acid. Of these alkali-soluble polymers, hydroxystyrene-based polymers and acrylic copolymers having alkali-soluble groups are preferred in terms of developability.

  In the present invention, the alkali-soluble compound may be protected with an acid-decomposable group, and examples of the acid-decomposable group include an ester group and a carbamate group.

  In the present invention, the content of these alkali-soluble compounds is about 10 to 90% by weight, preferably 20 to 85% by weight, and 30 to 80% by weight in the total solid content of the photosensitive layer or the heat-sensitive layer. Further preferred. When the content of the alkali-soluble compound is less than 10% by weight, the durability of the photosensitive layer or the heat-sensitive layer is deteriorated, and when it exceeds 90% by weight, it is not preferable in terms of both sensitivity and durability. Moreover, these alkali-soluble compounds may be used alone or in combination of two or more.

-Dissolution inhibitor-
The dissolution inhibitor used in the positive action sensitive composition is a compound that decomposes and becomes alkali-soluble by the action of an acid. Examples of the dissolution inhibitor include a carboxylic acid protected with an acid-decomposable group of a chemical amplification system used in the resist field such as t-butyl ester, t-butyl carbamate, and alkoxyethyl ester, a phenol compound, and the like. Can be mentioned.

  In the present invention, the content of the dissolution inhibitor is about 5 to 90% by weight, preferably 10 to 80% by weight, based on the total solid content of the photosensitive layer or heat-sensitive layer.

  Suitable quinonediazide compounds include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the sensitive material system by both the effects of losing the ability to suppress dissolution of the alkali-soluble compound by thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in pages 339 to 352 of “Light-Sensitive Systems” (John Wiley & Sons. Inc.) by Korser can be used, and in particular, o reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. -Sulfonic acid esters or sulfonic acid amides of quinonediazides are preferred. Further, benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403. Benzoquinone- (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1 described in US Pat. Nos. 3,046,120 and 3,188,210, etc. , 2) -Diazide-5-sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further esters of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride with phenol-formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used. Other useful o-quinonediazide compounds have been reported in many patent-related literatures. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-49-38701 No. 48-13354, Japanese Examined Patent Publication No. 41-11222, Japanese Examined Patent Publication No. 45-9610, Japanese Examined Patent Publication No. 49-17478, US Pat. No. 2,797,213, No. 3,454,400. No. 3,544,323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. No. 1,227,602, No. 1,251,345, No. 1,267,005, No. 1,329,888, No. 1,330,932 Description, German Patent Invention No. 854,890 It may be mentioned those described in the specification or the like.

  In the present invention, the content of the o-quinonediazide compound is about 1 to 50% by weight, preferably 5 to 30% by weight, and more preferably 10 to 30% by weight in the total solid content of the photosensitive layer or the heat-sensitive layer. . These compounds can be used alone, but may be used as a mixture of several kinds. When the content of the o-quinonediazide compound is less than 1% by weight, the image recording property is deteriorated. On the other hand, when it exceeds 50% by weight, the durability of the image portion is deteriorated or the sensitivity is lowered.

  In the present invention, the content of the above-mentioned compound other than the o-quinonediazide compound is about 1 to 50% by weight, preferably 5 to 30% by weight, and preferably 10 to 30% in the total solid content of the photosensitive layer or the heat-sensitive layer. % By weight is preferred.

(Negative action sensitive composition)
In the present invention, conventionally known negative action sensitive compositions ((g) to (h)) shown below can be used as the negative action sensitive composition.

(G) A negative action sensitive composition comprising a polymer having a photocrosslinkable group and an azide compound.
(H) A negative action sensitive composition comprising the diazo compound described in JP-A-59-101651.
(I) A photopolymerizable negative action sensitive composition comprising a photopolymerization initiator and an addition polymerizable unsaturated compound described in US Pat. No. 262276 and JP-A-2-63054.
(H) A negative action sensitive composition comprising an alkali-soluble compound, an acid generator and an acid crosslinkable compound described in JP-A-11-095421.

  The compounds used in the negative action sensitive compositions shown in the above (g) to (h) will be described below.

-Polymer having photocrosslinkable group-
The polymer having a photocrosslinkable group used in the negative action sensitive composition is preferably a polymer having a photocrosslinkable group having an affinity for an aqueous alkaline developer, for example, in US Pat. No. 5,064,747. A polymer having a photocrosslinkable group such as —CH═CH—CO— in the main chain or side chain of the molecule; a copolymer having a cinnamic acid group and a carboxyl group described in JP-B-54-15711; Polyester resin having phenylene diacrylic acid residue and carboxyl group described in JP-A-60-165646; Polyester resin having phenylene diacrylic acid residue and phenolic hydroxyl group described in JP-A-60-203630 A polymer having a phenylene diacrylic acid residue and a sodium iminodisulfonyl group described in JP-B-57-42858. Ether resins; polymers like in a side chain described in JP 59-208552 Laid having an azide group and a carboxyl group can be used. In the present invention, the content of the polymer having a photocrosslinkable group is about 5 to 100% by weight, preferably 10 to 95% by weight, and preferably 20 to 90% by weight in the total solid content of the photosensitive layer or heat-sensitive layer. % Is preferred.

-Azide compound-
Examples of the azide compound used in the negative action sensitive composition include 2,6-bis (4-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenyl sulfide, and the like. In this invention, content of an azide compound is about 5-95 weight% in the total solid of a photosensitive layer or a heat-sensitive layer, 10-90 weight% is preferable and 20-80 weight% is further more preferable.

-Alkali-soluble compounds-
The alkali-soluble compound used in the negative action sensitive composition is the same as the alkali-soluble compound used in the positive action sensitive composition.

-Diazo compounds-
Examples of the diazo resin used in the negative action sensitive composition include a diazo resin typified by a salt of a condensate of diazodiarylamine and an active carbonyl compound, which is photosensitive, water-insoluble and organic solvent-soluble. preferable. Particularly suitable diazo resins include, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4'-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4'- Condensation products of methoxydiphenylamine 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like with formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether, etc. Organic acid salt or inorganic acid salt. Examples of organic acids at this time include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, and 1-naphthol-5-sulfone. Acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc., and inorganic acids include hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid, etc. Is mentioned.

  Further, a diazo resin whose main chain is a polyester group described in JP-A No. 54-30121; a polymer having a carboxylic anhydride residue described in JP-A No. 61-273538; and a diazo resin having a hydroxyl group A diazo resin obtained by reacting a compound; a diazo resin obtained by reacting a polyisocyanate compound and a diazo compound having a hydroxyl group can also be used.

  In the present invention, the content of the diazo resin is preferably about 0 to 40% by weight with respect to the total solid content of the photosensitive layer or heat-sensitive layer. Moreover, you may use together 2 or more types of diazo resins as needed.

-Photopolymerization initiator and addition polymerizable unsaturated compound-
As the addition polymerizable unsaturated compound and photopolymerization initiator used in the negative action sensitive composition, US Pat. No. 2,760,863, US Pat. No. 3,060,023, JP Examples thereof include addition-polymerizable unsaturated compounds having two or more terminal ethylene groups and a photopolymerization initiator described in JP-A No. 62-121448.

  In the present invention, the content of the addition polymerizable unsaturated compound is about 5 to 95% by weight, preferably 5 to 80% by weight, based on the total solid content of the photosensitive layer or heat-sensitive layer. Moreover, content of a photoinitiator is about 1 to 80 weight% with respect to a photosensitive layer or a heat sensitive layer total solid, and 5 to 50 weight% is preferable.

-Acid generator-
The acid generator used in the negative action sensitive composition is the same as the acid generator used in the positive action sensitive composition.

-Acid crosslinkable compound-
The acid crosslinkable compound used in the negative action sensitive composition refers to a compound that crosslinks in the presence of an acid, for example, an aromatic poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Among them, a compound and a heterocyclic compound are preferable, and a preferable example is a compound obtained by condensing phenols and aldehydes under basic conditions. Among the above compounds, preferred are, for example, compounds obtained by condensing phenol and formaldehyde under basic conditions as described above, similarly, compounds obtained from m-cresol and formaldehyde, and compounds obtained from bisphenol A and formaldehyde. Compounds obtained from 4,4′-bisphenol and formaldehyde, and other compounds disclosed as a resole resin in British Patent Application No. 2,082,339. These acid crosslinkable compounds preferably have a weight average molecular weight of 500 to 100,000 and a number average molecular weight of 200 to 50,000.

  Other preferred examples include aromatic compounds substituted with an alkoxymethyl or oxiranylmethyl group disclosed in EP-A-0,212,482, EP-A-0,133, Monomer and oligomer melamine-formaldehyde condensates and urea-formaldehyde disclosed in No. 216, West German Patent Application No. 3,634,671, West German Patent No. 3,711,264 Condensates, alkoxy-substituted compounds disclosed in EP 0,212,482, and the like. Yet another preferred example is a melamine-formaldehyde derivative having, for example, at least two free N-hydroxymethyl, N-alkoxymethyl or N-acyloxymethyl groups. Of these, N-alkoxymethyl derivatives are particularly preferred. Low molecular weight or oligomeric silanols can also be used as silicon-containing crosslinking agents. Examples of these are dimethyl- and diphenyl-silanediols and oligomers that have already been precondensed and contain these units, for example those disclosed in EP 0,377,155. Can be used.

[Other ingredients]
In order to obtain various lithographic printing plate characteristics, various compounds other than those described above may be added to the photosensitive layer or heat-sensitive layer of the lithographic printing plate precursor according to the present invention.

  In the photosensitive layer or heat-sensitive layer of the lithographic printing plate precursor according to the invention, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (oriental chemical industry) Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015), etc., or JP-A 62-293247 And dyes described in Japanese Patent Publication No. These dyes are preferably added after image formation because they can be easily distinguished from image portions and non-image portions. The amount added is 0.01 to 10% by weight with respect to the total solid content of the photosensitive layer or heat-sensitive layer.

  Further, the photosensitive layer or heat-sensitive layer of the lithographic printing original plate according to the present invention is described in JP-A Nos. 62-251740 and 3-208514 in order to increase the processing stability against development conditions. Nonionic surfactants such as those described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of the double-sided activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Examples thereof include trade names (for example, trade name Amorgen K, manufactured by Daiichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive layer or heat-sensitive layer of the lithographic printing original plate is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight. .

  Furthermore, a plasticizer is added to the photosensitive layer or heat-sensitive layer of the lithographic printing original plate according to the present invention, if necessary, in order to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or An oligomer or polymer of methacrylic acid is used.

  In addition to these, the onium salts and haloalkyl-substituted s-triazines, epoxy compounds, vinyl ethers, phenol compounds having hydroxymethyl groups described in Japanese Patent Application No. 7-18120, and alkoxymethyl groups. A phenol compound or the like may be added.

In the present invention, the photosensitive layer or the heat-sensitive layer is usually formed by dissolving the above components in a solvent and coating the solution on the hydrophilic layer. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyllactone, toluene, water, and the like. However, it is not limited to this. These solvents are used alone or in combination. The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by weight. In addition, the coating amount (solid content) on the hydrophilic layer obtained after coating and drying varies depending on the use, but generally speaking, it is preferably 0.5 to 5.0 g / m ² for a lithographic printing original plate. Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

(Photothermal conversion material)
In the case of recording an image of the lithographic printing plate precursor according to the present invention with an IR laser or the like, a photothermal conversion substance for converting the light energy into heat energy should be included somewhere in the lithographic printing plate precursor. Is preferred. Examples of the part to contain the photothermal conversion substance include a hydrophilic layer, a polymerization initiation layer, or between the substrate and the polymerization initiation layer, and between the polymerization initiation layer and the hydrophilic layer. May be.

  In the lithographic printing plate precursor according to the present invention, the photothermal conversion material that may be contained can be any material that can be converted into heat by absorbing light such as ultraviolet rays, visible rays, infrared rays, white rays, etc., for example, Examples thereof include carbon black, carbon graphite, pigment, phthalocyanine pigment, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred are dyes, pigments or metals that effectively absorb infrared rays having a wavelength of 760 nm to 1200 nm.

  As the dye, commercially available dyes and known dyes described in literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and metal thiolate complexes. Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) pyrylium described in US Pat. No. 3,881,924 is also preferred. Salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-2220143, JP-A-59- No. 41363, No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, and Pyryllium compounds described in JP-A-59-216146. Cyanine dyes, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, etc., and Japanese Patent Publication No. 5-13514, 5-19 Pyrylium compounds Nos disclosed in Japanese 02 is also preferably used. Examples of other preferable dyes include near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used. Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These dyes or pigments are 0.01 to 50% by weight, preferably 0.1 to 10% by weight of the total solid content of the photothermal conversion substance-containing layer, particularly preferably 0.5 to 10% by weight in the case of dyes. In this case, it can be particularly preferably used in a proportion of 3.1 to 10% by weight. When the added amount of the pigment or dye is less than 0.01% by weight, the sensitivity is low, and when it exceeds 50% by weight, the film strength of the photothermal conversion substance-containing layer is weakened.

  For the photosensitive layer or heat-sensitive layer of the lithographic printing original plate in the present invention, a surfactant for improving the coating property, for example, a fluorosurfactant as described in JP-A-62-170950 Can be added. A preferable addition amount is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight in the total solid content of the photosensitive layer or the heat-sensitive layer.

(Exposure of planographic printing plate precursor)
The lithographic printing plate precursor of the present invention produced as described above is usually subjected to image exposure and development treatment to obtain a lithographic printing plate.
Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include X-rays, ion beams, and far infrared rays. Further, i-line and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, and a KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable.

The laser output is preferably 100 mW or more, and a multi-beam laser device is preferably used in order to shorten the exposure time. The exposure time per pixel is preferably within 20 μsec. The energy applied to the negative image forming layer is preferably 10 to 300 mJ / cm ² .

(Development of planographic printing plate precursor)
After the image exposure, the lithographic printing plate precursor according to the invention is preferably developed with water or an alkaline aqueous solution.
As the developer and replenisher used for development, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, tribasic sodium phosphate, tertiary potassium phosphate, tertiary ammonium phosphate, secondary sodium phosphate, secondary potassium phosphate, secondary ammonium phosphate, sodium carbonate, carbonic acid Examples include inorganic alkali salts such as potassium, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide. In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used.
These alkali agents are used alone or in combination of two or more.

  Further, when developing using an automatic developing machine, the developer in the developing tank for a long time is added to the developer by adding an aqueous solution (replenisher) that is the same as the developer or higher in alkali strength than the developer. It is known that a large amount of a lithographic printing plate precursor can be processed without replacing the plate. This replenishment method is also preferably applied in the present invention.

Various surfactants, organic solvents, and the like can be added to the developer and the replenisher as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving the ink affinity of the printing plate image area.
The surfactant is preferably added in an amount of 1 to 20% by weight, more preferably in the range of 3 to 10% by weight. If the addition amount of the surfactant is less than 1% by weight, the effect of improving the developability cannot be sufficiently obtained, and if it is added in excess of 20% by weight, it tends to cause problems such as a reduction in strength such as image abrasion resistance. .

  In this way, the lithographic printing plate obtained by image exposure, development, washing with water and / or rinsing, if necessary, erasing treatment of unnecessary image areas, application of desensitized gum, burning treatment, etc. The post-processing conventionally performed is performed, it applies to an offset printing machine etc., and it is used for printing of many sheets.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[Example 1]
<Production of surface hydrophilic member>
(Step of surface treatment of substrate with aminopropylsilane)
3-Aminopropyltrimethoxysilane was added to acetone to make a 1% by volume solution. The solution was left at room temperature for 10 days. Next, the PET film (A4100, manufactured by Toyobo Co., Ltd.) was ultrasonically washed with distilled water, ethanol and acetone for 5 minutes and dried at 120 ° C. for 5 minutes. This PET substrate was immersed in the solution left for 10 days, and then taken out of the solution and baked in an oven at 150 ° C. for 10 minutes to treat the surface of the support with aminopropylsilane.

(Step of forming a polymerization initiation layer)
Specific example 6 of the specific compound shown below was dissolved in dehydrated toluene to make a 1.0 mass% solution, and spin-coated on the support. The spin coat was first rotated at 30 rpm for 5 seconds and then at 300 rpm for 20 seconds. After spin coating, heating was performed at 100 ° C. for 60 seconds, and the surface was washed with toluene and acetone to form a polymerization initiation layer.

(Step of forming a hydrophilic layer)
A PET film combined with the above initiator is immersed in a nitrogen bubbled acrylic acid aqueous solution (10% by mass), and exposed to a high-pressure mercury lamp (UVX0251S1LP01, manufactured by Ushio Corporation) for 10 minutes. And washed sufficiently with distilled water to obtain a hydrophilic surface member grafted with acrylic acid.
The evaluation results of the water resistant contact angle are shown in Table 1 below.

[Example 2]
In Example 1, a surface hydrophilic member was obtained by the same method except that the support was changed to PEN. The evaluation results of the water resistant contact angle are shown in Table 1 below.

[Comparative Example 1]
A surface hydrophilic member was obtained by the same process as in Example 1 except that aminopropylsilane treatment was not performed. The evaluation results of the water resistant contact angle are shown in Table 1 below.

[Comparative Example 2]
A PET film (A4100, manufactured by Toyobo Co., Ltd.) was ultrasonically washed with distilled water, ethanol and acetone for 5 minutes and dried at 120 ° C. for 5 minutes. This PET substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.). After forming a polymerization initiation layer on this film in the same manner as in Example 1, a step of forming a hydrophilic layer was performed to obtain a surface hydrophilic member. The evaluation results of the water resistant contact angle are shown in Table 1 below.

[Comparative Example 3]
The support was changed to PET, and a surface hydrophilic member was obtained in the same process as in Example 1 except that the process of forming a polymerization initiation layer and the process of forming a hydrophilic layer were not performed. The evaluation results of the water resistant contact angle are shown in Table 1 below.

(Evaluation)
-Water resistant contact angle of hydrophilic layer-
The contact angle with respect to water of the surface hydrophilic member obtained as described above was measured by CA-Z manufactured by Kyowa Interface Science Co., Ltd.

  From the results in Table 1, it can be seen that the surface hydrophilic members of Examples 1 and 2 of the present invention have excellent surface hydrophilicity. On the other hand, the support of Comparative Example 1 in which the surface of the base material was not subjected to aminopropylsilane treatment and a hydrophilic layer was formed did not have sufficient surface hydrophilicity. In addition, the support of Comparative Example 2 in which a hydrophilic layer was formed after the conventionally known UV ozone treatment on the substrate surface, and the support of Comparative Example 3 having no polymerization initiation layer and hydrophilic layer were It can be seen that a surface hydrophilic layer substantially the same as the example is developed.

[Example 3, Comparative Example 4 to Comparative Example 6]
<Preparation of original plate for lithographic printing>
The following image forming layer was applied as a positive photosensitive layer to the surface hydrophilic member obtained in Example 1 and Comparative Examples 1 to 3, to produce a positive photosensitive lithographic printing plate precursor, and exposure, development and Printability evaluation was performed.

(Image forming layer prescription)
(Alkali-soluble polymer / naphthoquinone-1,2-diazide type (conventional positive type)) 0.9 g of an ester compound of naphthoquinone-1,2-diazide-4-sulfonyl chloride and pyrogallol-acetone resin, Victoria Pure Blue BOH, 0. 05 g, a novolak resin (meta.para ratio 6: 4, weight average molecular weight 1800) 2.0 g obtained from cresol and formaldehyde, 20 g of methyl ethyl ketone, and 7 g of methyl alcohol applied to the above hydrophilic property in a positive type A lithographic printing plate precursor was used.

(Exposure, development)
The obtained positive type lithographic printing plate precursor was exposed with PS light through a step guide manufactured by Fuji Film, and then processed through an automatic processor charged with developer DP-4 (1: 8) manufactured by Fuji Film. Subsequently, it printed with the Heidel KOR-D printing machine.
The printing was continued, and the number of prints with good prints without smudges in the image area was measured. The printed material was visually checked for contamination. It is evaluated that the greater the number of good prints without stains, the better the hydrophilic durability of the lithographic printing plate precursor.

表２より、アミノプロピルシランで表面処理した支持体で画像形成層を塗布した実施例３では、非画像部に汚れのない良好な印刷物が８，０００枚以上得られ、満足すべき結果を得た。
これに対し、表面親水性に劣る比較例１の支持体を用いた比較例４の平版印刷版では、非画像部に汚れが発生し、良好な印刷物が得られなかった。また、ＵＶオゾン処理を施した後、親水性層を形成した比較例２の支持体を用いた比較例５の平版印刷版は、２０００枚を印刷した後、非画像部に汚れが発生し、親水性層の耐久性に劣ることがわかる。さらに、重合開始層及び親水性層を有さない比較例３の支持体用いた比較例５の平版印刷版は、１０００枚を印刷した後、非画像部に汚れが発生し、親水性層の耐久性に劣ることがわかる。
比較例が実施例より親水性、耐刷性に劣る原因は明確ではないが、以下の点が推測される。
比較例１、４では、アミノプロピルシラン処理をしていないため、十分な量の開始剤が表面に結合せず、グラフトが形成できないことから、親水性が劣り、汚れがない印刷物を得ることができない。
比較例２、５では、ＰＥＴ表面をＵＶオゾン処理して表面にある程度の水酸基、カルボキシル基を発生させ開始剤を結合させたが、それでも結合量は十分でなく、したがってグラフトが十分でなく親水性が劣り、耐刷性も劣るものと思われる。
比較例３、６では、アミノプロピルシラン処理だけであり、グラフトポリマーからなる親水性層を形成していなく、印刷に必要な表面親水性が十分形成できないため、親水性、耐刷性に劣るものと考えられる。
以上の結果は、本発明で用いられるグラフト処理が有効であることを示すものである。

From Table 2, in Example 3 in which the image forming layer was coated with a support surface-treated with aminopropylsilane, 8,000 or more good prints having no stain on the non-image area were obtained, and satisfactory results were obtained. It was.
On the other hand, in the planographic printing plate of Comparative Example 4 using the support of Comparative Example 1 having poor surface hydrophilicity, stains were generated in the non-image area, and a good printed matter could not be obtained. In addition, after the UV ozone treatment, the planographic printing plate of Comparative Example 5 using the support of Comparative Example 2 in which the hydrophilic layer was formed, after 2000 sheets were printed, the non-image area was stained, It can be seen that the hydrophilic layer is inferior in durability. Furthermore, in the planographic printing plate of Comparative Example 5 using the support of Comparative Example 3 having no polymerization initiation layer and hydrophilic layer, after printing 1000 sheets, the non-image area was stained, and the hydrophilic layer It turns out that it is inferior to durability.
The reason why the comparative example is inferior in hydrophilicity and printing durability to the example is not clear, but the following points are presumed.
In Comparative Examples 1 and 4, since aminopropylsilane treatment was not performed, a sufficient amount of initiator did not bind to the surface, and a graft could not be formed. Thus, a printed matter having poor hydrophilicity and no stain could be obtained. Can not.
In Comparative Examples 2 and 5, the surface of PET was treated with UV ozone to generate a certain amount of hydroxyl group and carboxyl group on the surface to bind the initiator. However, the amount of bonding was still insufficient, and therefore the graft was not sufficient and hydrophilic. Is inferior in printing durability.
In Comparative Examples 3 and 6, only the aminopropylsilane treatment is performed, the hydrophilic layer made of the graft polymer is not formed, and the surface hydrophilicity necessary for printing cannot be sufficiently formed, so that the hydrophilicity and the printing durability are inferior. it is conceivable that.
The above results show that the grafting treatment used in the present invention is effective.

Claims (4)

  A polymerization in which an aminopropylsilane condensation layer, a compound having a polymerization initiation site capable of initiating radical polymerization, and a support binding site are bonded to the support base material via the support binding site on the base material. Surface hydrophilicity characterized by sequentially comprising an initiator layer, and a hydrophilic layer formed of an unsaturated compound having a hydrophilic group and a radically polymerizable site, and comprising a graft polymer directly bonded to the initiator layer Element.   The surface hydrophilic member according to claim 1, wherein the base material is polyethylene terephthalate or polyethylene naphthalate.   A substrate-binding site of a compound having a step of forming an aminopropylsilane condensation layer by surface-treating the substrate with aminopropylsilane on the substrate, a polymerization initiation site capable of initiating radical polymerization, and a substrate-binding site To form a polymerization initiating layer by bonding to a support substrate, and to polymerize an unsaturated compound having a hydrophilic group and a radical polymerizable site from the radical generated from the polymerization initiating layer as a starting point, Forming a hydrophilic layer comprising: a method for producing a surface hydrophilic member.   A lithographic printing plate precursor comprising an image forming layer on the surface hydrophilic member according to claim 1.