JP2003262961A - Lithographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic original plate which has high adhesiveness between a hydrophilic layer and an image forming layer after an image is formed and which is excellent in printing durability so that a great number of prints with high picture quality having no dirt in a non-image part can be obtained even under severe printing conditions. <P>SOLUTION: The original plate is characterized in that it has a surface layer having hydrophilic graft chains directly bonded to the surface of a supporting body and an image forming layer successively layered on the supporting body, and reactive groups which can be bonded to each other by heat or irradiation of radiation are incorporated into the surface layer and the image forming layer. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to negative lithographic printing.
There are many prints with high sensitivity, high printing durability, and no stain on the plate precursor.
It relates to a lithographic printing plate precursor that can be given several sheets. [0002] 2. Description of the Related Art Lithographic printing is an oleophilic area that accepts ink.
Area and ink repellent area that does not accept ink but accepts dampening water
A printing method using a plate material having (hydrophilic region)
Currently, there is a widely photosensitive planographic printing plate precursor (PS plate)
It is used. PS plate supports aluminum plate
What has a photosensitive layer on the body has been put into practical use and widely used.
It is. Such PS plates are suitable for image exposure and development.
The photosensitive layer in the non-image area is removed more and the hydrophilicity and image of the substrate surface are removed.
Printing is performed using the lipophilicity of the photosensitive layer in the image area.
In such a plate material, in order to prevent contamination of the non-image area, the substrate
The surface is required to have high hydrophilicity. Conventionally, hydrophilic substrates used in lithographic printing plates or
The hydrophilic layer can be an anodized aluminum substrate, a young one.
Or anodized to increase hydrophilicity.
It is generally silicate treatment of aluminum substrate
It is done. In addition, these aluminum supports
Active research on the hydrophilic substrate or hydrophilic layer used
For example, in JP-A-7-1853
Substrate treated with primer with polyvinylphosphonic acid
However, JP-A-59-101651 discloses a photosensitivity.
A polymer having sulfonic acid groups is used as an undercoat layer.
Each technology used is described.
We also propose a technology that uses, for example, livinylbenzoic acid as a primer.
It has been proposed. On the other hand, a metal support such as aluminum is used.
Izu PET (polyethylene phthalate), cellulose
Parent when using a flexible support such as cetate
Regarding the water layer, it is described in JP-A-8-292558.
Swelled hydrophilic consisting of a hydrophilic polymer and a hydrophobic polymer
Layer, microporous as described in EP 0709228
PET support having hydrophilic cross-linked silicate surface
Japanese Laid-Open Patent Publications Nos. 8-2702087 and 8-507727
Hydrolyzed tetra containing a hydrophilic polymer as described in
Seeds such as hydrophilic layers cured with alkyl orthosilicates
Various technologies have been proposed. These hydrophilic layers are more hydrophilic than conventional ones.
And prints that do not get smudged at the start of printing are obtained.
Gave a lithographic printing plate, but peeled off after repeated printing
And there is a problem that the hydrophilicity decreases with time,
Even under more severe printing conditions, the hydrophilic layer peels off from the support.
Without separating or reducing the hydrophilicity of the surface.
Desirable is a lithographic printing plate precursor that provides a print with no stains.
It was. Here, the affinity between the hydrophilic layer and the image forming layer
Low adhesion affects printing durability, so strong adhesion between the two
Sex is required. With the recent development of laser, near infrared
Solid lasers and semiconductors that have a light emitting region from the line to the infrared region
With lasers (hereinafter referred to as infrared lasers)
Miniaturization is progressing. Such infrared lasers are
Make a printing plate directly according to digital data such as
It is very useful as an exposure light source when Infrared laser
Negative-type lithographic printing plates that can be exposed by infrared absorption
And an initiator that generates radicals and acids by light or heat
And a negative type containing a polymerizable or crosslinkable compound
An image recording material is used as the recording layer. Usually said negative
Type image recording materials are radicals generated by light or heat,
Polymerization reaction or crosslinkability of polymerizable compounds with acid as initiator
Causes the formation of a cross-linked structure in the compound, exposing the exposed area
Uses a recording method that forms the image area by curing the recording layer
doing. Such a negative type image forming material is an infrared ray.
The recording layer is solubilized by the energy of laser irradiation.
Compared with the positive type
When a metal plate such as aluminum is used for the body, image formation
The heat to be used for the diffusion to the support, the support and the image shape
The image-forming layer is sufficiently cured at the interface with the layer.
The problem is that the strength of the image area is insufficient and the printing durability is poor.
there were. Therefore, for example, image formation by polymerization is performed.
In negative-type image forming materials, it accelerates the curing reaction.
Development process for the purpose of forming a strong and robust image area
It is common to perform the heat treatment before. Recording layer using such an image forming mechanism
JP-A-8-108621 discloses a printing plate using
No. and JP-A-9-34110
A photopolymerizable or thermopolymerizable composition with a recording layer (photosensitive layer)
The technique used is known. These recording layers are highly sensitive
Although it has excellent image formability, it is hydrophilized as a support
When a processed substrate is used, the interface between the recording layer and the substrate
There is a problem of low adhesion and poor printing durability.
It was. [0009] Disadvantages of the above prior art
The object of the present invention, which was made in consideration of the
High adhesion between the image forming layer and the image forming layer
However, there are many high-quality prints that do not cause dirt due to non-image areas.
Providing lithographic printing plate precursors with excellent printing durability that can be obtained in several sheets
There is. [0010] [Means for Solving the Problems] The present inventors have intensively studied.
As a result, a surface layer (hereinafter, referred to as a hydrophilic graft chain) exists.
(Referred to as hydrophilic layer as appropriate) and the image forming layer.
By containing a bridging compound or a polymerizable compound,
Find out that the purpose is achieved and complete the present invention
It came to. That is, the lithographic printing plate precursor according to the present invention is formed on a support.
Have hydrophilic graft chains directly attached to the support surface
A surface layer and an image forming layer in order.
And the image forming layer are exposed to heat or radiation.
It contains a compound having a reactive group that can be bonded.
It is a sign. The hydrophilic layer and the image forming layer in the present invention are
As a particularly useful means of joining each other
(A) An acid crosslinkable compound is added to the hydrophilic layer and the image forming layer.
Contained for irradiation of heat or radiation during image formation
Therefore, an acid crosslinking reaction occurs, and the hydrophilic layer and the image forming layer
And (B) a hydrophilic layer and an image forming layer
When a compound having a polymerizable group is contained and an image is formed
Causes polymerization reaction by the heat or radiation of
And a method of bonding the hydrophilic layer and the image forming layer.
It is. The lithographic printing plate precursor according to the present invention comprises a hydrophilic graph.
A surface layer with a chain is present between the support and the imaging layer.
To function as a heat insulation layer,
The energy generated by irradiation must not diffuse to the support.
In order to use it efficiently in the image formation reaction,
Curing of the steel proceeds sufficiently to the deep part and the hydrophilic layer
Both of the image forming layers are heated or irradiated with radiation.
Contains a compound having a reactive group to which
In areas where energy has been applied by heat or radiation
The reactive groups bind to each other at the interface of the two layers
By this, the adhesion between the hydrophilic layer and the image forming layer is remarkably
Improved, sufficient strength in the image area is ensured, and high
Printing durability can be realized. Further, the hydrophilic layer according to the present invention includes a support.
There is a hydrophilic graft chain directly bonded to the support surface.
Therefore, it is firmly bonded to the support substrate and has excellent durability, and
High parent consisting of a layer of hydrophilic polymer with high mobility
It will have a surface that expresses water,
By providing an image forming layer, under severe printing conditions
Many non-image areas with excellent print quality with no smudges
It is thought that the obtained lithographic printing plate can be obtained. The present invention will be described in detail below. Of the present invention
The planographic printing plate precursor is directly bonded to the support surface on the support.
Surface layer having a hydrophilic graft chain formed thereon and an image forming layer
Are sequentially stacked. First
The structure of the hydrophilic layer that is suitably used will be described. [Surface layer having hydrophilic graft chain] In the present invention
Surface layer with hydrophilic graft chain is hydrophilic graph
The chain may be directly bonded to the surface of the support,
In addition, it is easy to bind hydrophilic graft chains to the support surface.
An intermediate layer is provided and a hydrophilic compound is grafted thereon.
May be used. Furthermore, the hydrophilic surface in the present invention
Is a polymer in which a hydrophilic graft chain is bonded to a trunk polymer compound.
Or a hydrophilic graft chain as a trunk polymer
Polymer in which functional group capable of bonding and crosslinking is introduced
Is used on the support surface by coating or coating crosslinking.
And hydrophilic graphs with crosslinkable groups at the ends
Coating or coating using a composition containing a chain and a crosslinking agent
Also included are those placed on the support surface by crosslinking.
The The characteristics of the hydrophilic compound in the present invention are as follows.
The terminal or side chain of the aqueous graft chain is the surface of the support or
A glass that is chemically bonded directly to the support surface layer and exhibits hydrophilicity.
Have a structure in which the foot portion is not substantially cross-linked
It is in. Graft part that expresses hydrophilicity by this structure
Is limited in mobility or buried in a strong cross-linked structure
And has a feature that can maintain high mobility.
For this reason, compared with a hydrophilic polymer having a normal cross-linked structure.
In comparison, it is considered that excellent hydrophilicity is expressed.
The molecular weight of such a hydrophilic graft chain is Mw500 ~
The preferred molecular weight is Mw1000.
˜1 million, more preferably Mw200
It is in the range of 0 to 500,000. In the present invention, (a) a hydrophilic graft
Intermediate chain provided directly on or on the support surface
What is bonded on the layer is called "surface graft"
(B) The hydrophilic graft chain is introduced into the polymer cross-linked membrane structure
When using the one contained in the
This is referred to as an “in-crosslinked hydrophilic layer”. Further, in the present invention, the support is not suitable.
Or a material with an intermediate layer on a support is called a `` base material ''.
The (A: Method for producing surface graft) On substrate
How to make surfaces with hydrophilic groups consisting of grafted chains
As a method, the substrate and the graft chain are attached by chemical bonding.
And a double bond that can be polymerized from the base material.
There are two methods to polymerize the compound
The First, the base material and the graft chain are chemically bonded.
The method of making it adhere is demonstrated. In this way
Is a functional group that reacts with the substrate at the end or side chain of the graft chain
A compound having a group, this functional group and the surface of the substrate
Can be grafted by chemically reacting with a functional group
it can. As the functional group that reacts with the base material,
There is no particular limitation as long as it can react with a functional group.
For example, a silane coupling group such as alkoxysilane,
Isocyanate group, amino group, hydroxyl group, carboxyl
Group, sulfonic acid group, phosphoric acid group, epoxy group, allyl group,
Methacryloyl group, acryloyl group, etc.
Yes. Has a reactive functional group at the end or side chain of the graft chain
Compounds that are particularly useful as conducting polymers are
Hydrophilic with a silyl group at the end or side chain of the graft chain
Compound, having an amino group at the end or side chain of the graft chain
Hydrophilic compound, carboxyl group at the end of graft chain or
Hydrophilic compound with side chain, epoxy group of graft chain
Hydrophilic compound at the terminal or side chain, isocyanate group
Is a hydrophilic compound having at the end or side chain of the graft chain
The Moreover, as a hydrophilic compound used at this time,
There is no particular limitation as long as it is hydrophilic.
Kuryl acid, polymethacrylic acid, polystyrene sulfone
Acid, poly-2-acrylamido-2-methylpropanes
Sulfonic acid and their salts, polyacrylamide, polyvinyl chloride
Nylacetamide and the like can be mentioned. Other,
Of hydrophilic monomers used in the following surface graft polymerization
Polymers or copolymers containing hydrophilic monomers are preferred
Can be used for It has a double bond that can be polymerized from the base material.
Of polymerizing a compound to form a graft chain
Is generally referred to as surface graft polymerization. Surface gra
Polymerization method means plasma irradiation, light irradiation, heating, etc.
To give active species on the substrate surface and
By polymerization of a compound having a polymerizable double bond.
Refers to a method of bonding to a substrate. Surface graft polymerization for practicing the present invention
As a method, any known method described in the literature is used.
be able to. For example, New Polymer Experiments 10, Polymer Science
Edited by Kyoritsu Publishing Co., Ltd., 1994, P135
As surface graft polymerization, photo-graft polymerization, plastic
A zuma irradiation graft polymerization process is described. Also adsorption
Technical Handbook, NTS Corporation, supervised by Takeuchi, 1999.2
Lines, p203, p695 include radiation such as gamma rays and electron beams
An irradiation graft polymerization method is described. Photograft polymerization
As a specific method of the method, JP-A-63-92658
, JP-A-10-296895 and JP-A-11-
119413 can be used.
The Plasma irradiation graft polymerization method, radiation irradiation grafting
In the polymerization method, the above-mentioned documents and Y.C. Ikad
a et al, Macromolecules vo
l. 19, page 1804 (1986), etc.
The method can be applied. Specifically, PET
Which polymer surface is treated with plasma or electron beam
To generate radicals on the surface, and then the activity table
Reacting a surface with a monomer having a hydrophilic functional group
Graft surface layer, that is, a surface layer having a hydrophilic group
Can be obtained. Photograft polymerization is the above statement.
In addition to offerings, JP-A-53-17407 (Kansai Pay)
And JP 2000-212313 (Dainippon)
Light) on the surface of the film substrate, as described in
Apply polymerizable composition, then aqueous radical polymerization compound
It is also carried out by bringing light into contact with an object
be able to. Useful for forming hydrophilic graft surface layer
Such a compound has a polymerizable double bond, and
It is necessary to have a hydrophilic property. this
These compounds have double bonds in the molecule.
For example, hydrophilic polymers, hydrophilic oligomers,
Any of these compounds can be used as a reactive monomer
Can do. Particularly useful compounds are hydrophilic monomers.
Hydrophilic monomers useful in the present invention include ammonium,
A positively charged monomer, such as suphonium, young
Are sulfonic acid group, carboxyl group, phosphoric acid group, phospho group
Have negative charges such as acid groups or can dissociate into negative charges
Examples include monomers having acidic groups,
For example, hydroxyl group, amide group, sulfonamide group, alcohol
Hydrophilic having non-ionic groups such as xy group and cyano group
A functional monomer can also be used. Particularly useful hydrophilic monomers in the present invention
As specific examples, the following monomers can be mentioned.
The For example, (meth) acrylic acid or its alkali
Metal salts and amine salts, itaconic acid or its alkali
Metal salts and amine salts, allylamine or its halo
Hydrogenate, 3-vinylpropionic acid or its
Alkali metal salts and amine salts, vinyl sulfonic acid
Are alkali metal salts and amine salts thereof, styrene sulfone
Acids or alkali metal salts and amine salts thereof, 2-sulfur
Photoethylene (meth) acrylate, 3-sulfopropylene
(Meth) acrylate or alkali metal salts thereof
Amine salt, 2-acrylamido-2-methylpropane
Sulfonic acids or alkali metal salts and amine salts thereof,
Acid phosphooxypolyoxyethylene glycol
(Meth) acrylate or a salt thereof, 2-dimethyl
Tylaminoethyl (meth) acrylate or its
Hydrogenated salt, 3-trimethylammonium propiate
Ru (meth) acrylate, 3-trimethylammonium
Propyl (meth) acrylamide, N, N, N-trime
Tyl-N- (2-hydroxy-3-methacryloyloxy
Cypropyl) ammonium chloride, etc.
be able to. In addition, 2-hydroxyethyl (meth) a
Chlorate, (meth) acrylamide, N-monomethylo
(Meth) acrylamide, N-dimethylol (me
) Acrylamide, N-vinylpyrrolidone, N-vinyl
Ruacetamide, polyoxyethylene glycol mono
(Meth) acrylate and the like are also useful. (B: hydrophilic graft chain-introduced crosslinked hydrophilic layer
Production method) The hydrophilic graft chain in the present invention was introduced.
Crosslinked hydrophilic layers are generally used as a method for synthesizing graft polymers.
Create a graft chain using a known method and cross-link it
It can produce by doing. Specifically, the graph
The synthesis of polymer is "graft polymerization and its application" Fumio Ide
Author, published in 1977, Polymer publication society,
Experiential 2, Polymer Synthesis and Reactions, edited by the Society of Polymer Science, Kyoritsu Shuppan
Co., Ltd. (1995). The synthesis of the graft polymer is basically as follows:
1. Polymerize the branch monomer from the trunk polymer. To trunk polymer
2. To bind the branched polymer. Co-branching branch polymer to trunk polymer
It is divided into three methods (macromer method)
The Whichever of these three methods is used, the book
The hydrophilic surface in the invention can be produced.
In addition, from the viewpoint of manufacturability and control of the membrane structure, “3.
The “chromar method” is excellent. Grammar using macromer
The synthesis of the ft chain is described in “New Polymer Experimental 2”
"Reaction and Reaction" edited by Polymer Society, Kyoritsu Publishing Co., Ltd. 1995
It is listed. Also, Yamashita Yu et al. “Chemistry of Macromonomer
And industry "IP, 1989, also described in detail
Yes. Specifically, acrylic acid, acrylamide, 2-
Acrylamide-2-methylpropanesulfonic acid, N-
As an organic cross-linked hydrophilic layer such as vinyl acetamide
Using the specifically described hydrophilic monomers,
A hydrophilic macromer can be synthesized according to the method. Hydrophilic macromer capsule used in the present invention
Especially useful are acrylic acid, methacrylic acid,
Macromers derived from monomers containing ruboxyl groups
-2-acrylamido-2-methylpropanesulfone
Derived from monomers of acids, styrene sulfonic acids, and their salts
Sulfonic acid macromers, acrylamide,
Amide-based macromers such as tacrylamide, N-vinyl alcohol
N-vinyl carbonates such as cetamide and N-vinylformamide
Amide macros derived from rubonamide monomers
Mer, hydroxyethyl methacrylate, hydroxy ester
Til acrylate, glycerol monomethacrylate, etc.
, A macromer derived from a hydroxyl group-containing monomer
Xylethyl acrylate, methoxy polyethylene glycol
Acrylate, polyethylene glycol acrylate
Alkoxy group or ethylene oxide group-containing mode
A macromer derived from a nomer. Polye
Tylene glycol chain or polypropylene glycol
A monomer having a chain is also useful as a macromer of the present invention.
Can be used. Useful of these macromers
The molecular weight is in the range of 400 to 100,000, preferably 1
000 to 50,000, particularly preferred range is 1500 to 20,000
It is a circle. If the molecular weight is 400 or less, the effect cannot be exhibited.
In addition, if it is 100,000 or more, with the copolymerization monomer that forms the main chain
Polymerizability deteriorates. After synthesizing these hydrophilic macromers,
One of the cross-linked hydrophilic layers into which graftable graft chains are introduced
The method has a reactive functional group with the hydrophilic macromer described above
Graft copolymer with other monomers
And then copolymerize with the synthesized graft copolymer
A cross-linking agent that reacts with the reactive functional groups of the body is coated on the support
Then, it is a method of making it crosslink by reacting with heat.
Other methods include hydrophilic macromers and photocrosslinkability.
A graft polymer having a group or a polymerizable group
And apply it on the support and react by light irradiation.
The method of making it crosslink is mentioned. In this way, a hydrophilic graft is formed on the substrate.
A hydrophilic surface can be provided where the chains are present. Hydrophilic
The thickness of the layer that forms the surface can be selected according to the purpose.
In general, a range of 0.001 μm to 10 μm is preferable,
The range of 0.01 μm to 5 μm is more preferable, 0.1
The range of μm to 2 μm is most preferable. If the film thickness is too thin
Scratch resistance tends to decrease.
The payability tends to deteriorate. High hydrophilicity of substrate surface
The graft chain must completely cover the substrate surface.
There is no need. Introduce graft chains on the surface of known hydrophilic substrates
The graft chain is 0.1% of the total surface area of the substrate.
If it introduce | transduces above, the effective hydrophilic improvement effect will express.
More preferably, the graft chain is based on the total surface area of the substrate.
1% or more, more preferably 10% or more
Yes. [Surface graft polymerization by applying energy]
Method] Next, it is used when forming the hydrophilic layer in the present invention.
Surface graft polymerization by applying energy
The law is described in detail. In addition, by energy grant
The surface graft polymerization method is (a) of the hydrophilic layer forming method.
It is a suitable example of the “surface graft” according to the above. Energy
-The surface graft polymerization method by application constitutes the base material
The surface of a support such as PET is directly
Polymerization is started by generating radicals on the surface by processing with a strand.
The active surface and then the hydrophilic functional group
By reacting with a monomer having
Surface layer with grafted chains, i.e. having hydrophilic groups
A surface layer can be obtained. By applying energy
In a preferred embodiment of the surface graft polymerization method, the support is previously provided.
By adding a compound having a polymerization initiating ability,
Active sites can be easily formed with low energy.
Since there are many active points to be generated, a simple method is used.
Can form a surface with higher hydrophilicity.
The The graft polymerization is caused by light irradiation or the like.
As the method itself, a known method can be applied. light
As a specific method of the graft polymerization method, JP-A-63-92
No. 658, JP-A-10-296895, and
Use the method described in JP-A-11-119413
Can. Specifically, a polymerization initiator and
Pre-coating a polymerizable composition comprising a polymerizable compound in advance
In addition, a hydrophilic compound having a polymerizable group is contacted thereon.
It is a method of touching and irradiating light. Create a surface graft
Among the methods, light is applied by applying light.
It is preferable to take a graft polymerization method. (Hydrophilic compound having a polymerizable group) Enel
Polymerizability used in surface graft polymerization by applying ghee
The hydrophilic compound having a group is a hydrophilic monomer described later,
Or at least one selected from the hydrophilic monomers
Polymerization into hydrophilic homopolymers and copolymers obtained
Vinyl groups, allyl groups, (meth) acrylic groups
Radicals introduced with ethylene addition polymerizable unsaturated groups such as
This refers to a hydrophilic compound containing a polymerizable group.
It has a polymerizable group at least at the terminal or side chain, and
Are preferably those having a polymerizable group at the terminal.
Those having polymerizable groups at the ends and side chains are preferred. Such ethylene addition polymerizable unsaturated groups
The introduced radical polymerizable group-containing hydrophilic compound is as follows.
Can be synthesized. Synthesis methods include hydrophilic monomers and
Copolymerization of monomers with ethylenically polymerizable unsaturated groups
A method having a hydrophilic monomer and a double bond precursor
The monomer is copolymerized and then double-bonded by treatment with a base or the like.
A method of introducing a compound, with a functional group of a hydrophilic compound and ethylene
Method for reacting a monomer having a polymerizable unsaturated group
Is mentioned. From the viewpoint of synthesis suitability, it is particularly preferable
And functional groups of hydrophilic compounds and ethylene addition polymerizable unsaturated
In this method, a monomer having a group is reacted. The above radical-polymerizable group may be a main chain terminal and / or
Is the hydrophilicity used for the synthesis of hydrophilic compounds in the side chain
Monomers include (meth) acrylic acid or its acrylate.
Lucari metal salt and amine salt, itaconic acid or its
Alkali metal salts and amine salts, 2-hydroxyethyl
(Meth) acrylate, (meth) acrylamide, N-
Monomethylol (meth) acrylamide, N-dimethylo
(Meth) acrylamide, allylamine or
Hydrohalic acid salt of 3-vinylpropionic acid or
Is its alkali metal salt and amine salt, vinyl sulfone
Acids or alkali metal salts and amine salts thereof, 2-sul
Rufoethyl (meth) acrylate, polyoxyethylene
Glycol mono (meth) acrylate, 2-acryla
Mid-2-methylpropanesulfonic acid, acid phospho
Oxypolyoxyethylene glycol mono (meth) ac
Carboxyl group such as relate, sulfonic acid group, phosphoric acid
Group, amino group or salt thereof, hydroxyl group, amide group
And monomers having hydrophilic groups such as ether groups
It is done. Contains allyl groups that copolymerize with hydrophilic monomers
As monomers, allyl (meth) acrylate, 2-
Examples include allyloxyethyl methacrylate. Ma
As a monomer having a double bond precursor, 2- (3
-Chloro-1-oxopropoxy) ethyl methacrylate
There is a spider. Carboxyl groups in hydrophilic monomers,
Amino groups or their salts, hydroxyl groups and epoxy groups
To introduce unsaturated groups using reactions with functional groups such as
A monomer having an addition-polymerizable unsaturated group used for
(Meth) acrylic acid, glycidyl (meth) acrylic acid
Relate, allyl glycidyl ether, 2-isocyana
Examples include toethyl (meth) acrylate. Hydrophilic having a polymerizable group at the terminal and / or side chain
As a preferred example of the hydrophilic compound, a hydrophilic macromonomer is
Can be mentioned. Surface graft polymerization by energy application
The macromonomer production method used in
“Macromo” published by IPC Publishing on September 20, 1st
Chapter 2 of "Nomer's Chemistry and Industry" (Editor: Yuya Yamashita)
Various production methods have been proposed for "Synthesis of Macromonomer"
The Especially hydrophilic macromonomer used in this method
Useful things such as acrylic acid and methacrylic acid
Macromolecules derived from monomers containing carboxyl groups
Nomer, 2-acrylamido-2-methylpropanesulfur
The phosphonic acid, vinyl styrene sulfonic acid, and salts thereof
A sulfonic acid-based macromonomer derived from a monomer,
(Meth) acrylamide, N-vinylacetamide, N
-Vinylformamide, N-vinylcarboxylic acid amide
Hydroamide, an amide macromonomer derived from a monomer
Xylethyl methacrylate ク, hydroxyethyl acrylate
Containing hydroxyl groups such as
Macromonomer derived from monomer, methoxy ester
Tyl acrylate, methoxy polyethylene glycol
Acrylate, polyethylene glycol acrylate, etc.
Monomers containing alkoxy groups or ethylene oxide groups
It is a macromonomer derived from Also polyethylene
Len glycol chain or polypropylene glycol chain
A monomer having a macromonomer used in the present method
Can be used as useful. These macro models
The useful molecular weight of the nomer ranges from 250 to 100,000.
A particularly preferable range is 400 to 30,000. (Useful in combination with the above hydrophilic macromonomer.
Hydrophilic monomer) and hydrophilic having the above-mentioned polymerizable group
In addition to hydrophilic macromonomer, add hydrophilic monomer
May be. Polymerization rate by adding hydrophilic monomer
Can be raised. The amount of hydrophilic monomer added is
Among hydrophilic compounds having all polymerizable groups, 0 to 6 in solid content
0% by mass is preferred. If it is 60% by mass or more, the coatability is poor
It is not suitable because it cannot be applied uniformly. Terminal and / or side
Useful in combination with hydrophilic compounds having a polymerizable group in the chain
Examples of hydrophilic monomers include ammonium and phosphonic acid.
Positively charged monomers such as um
Phonoic acid group, carboxyl group, phosphoric acid group, phosphonic acid group
Which negative charge has an acidic group that can dissociate into a negative charge
In addition, for example,
Hydroxyl group, amide group, sulfonamido group, alkoxy group,
Hydrophilic monomer having nonionic group such as cyano group
Can also be used. Surface graph by applying energy
In combination with hydrophilic macromonomer
In addition, as specific examples of particularly useful hydrophilic monomers,
Suitable for forming hydrophilic graft surface layer
The listed monomers can be cited as well. A composition containing such a hydrophilic compound
The solvent used for the hydrophilic macromonomers is the main component.
If the polymer or hydrophilic monomer is soluble, there are no restrictions.
However, an aqueous solvent such as water or a water-soluble solvent is preferable.
Surfactant added to these mixtures and solvents
Are preferred. Water-soluble solvent is mixed with water at an arbitrary ratio.
It refers to a compatible solvent, and as such a water-soluble solvent,
For example, methanol, ethanol, propanol, ethyl
Alcohol solvents such as lenglycol and glycerin,
Acids such as acetic acid, ketone solvents such as acetone, formaldehyde
And amide solvents such as imide. If necessary, it can be added to the solvent
The surfactant only needs to be soluble in the solvent.
Examples of such surfactants include n-dodecylben.
Anionic surfactants such as sodium zensulfonate
Or n-dodecyltrimethylammonium chloride
Cationic surfactant such as polyoxyethylene nonyl
Phenol ether (commercially available products such as emal
Gen 910, manufactured by Kao Corporation, etc.), polyoxyethylene
Sorbitan monolaurate (for example,
Trade name "Tween 20"), polyoxyethylene
Nonionic surfactants such as uryl ether
It is. When contacting the composition in a liquid state,
The hydrophilic compound composition can be applied by a coating method.
The coating amount when forming the coating layer is 0.1 to 0.1 in terms of solid content.
10 g / m²Is preferred, in particular 1 to 5 g / m²Is preferred
Yes. 0.1 g / m²If it is less than 1, sufficient surface hydrophilicity can be obtained.
10g / m²Uniform coating film exceeding
Is not preferred because it is difficult to obtain. [Support] Surface graph by applying energy
The support used in the ft polymerization method is the polymerization described above
The end or side chain of the hydrophilic compound having a functional group is directly or
Support that can be chemically bonded via trunk polymer compound
It has a body surface. The support itself is such a special feature.
Intermediate layer having such characteristics
May be provided on a support (substrate). (Support substrate) Surface by applying energy
The support substrate used in the graft polymerization method is a plastic substrate.
Stick film (eg cellulose diacetate, triacetic acid
Cellulose, cellulose propionate, cellulose butyrate
, Cellulose acetate butyrate, cellulose nitrate, polyethylene
Terephthalate, polyethylene, polystyrene, poly
Propylene, polycarbonate, polyvinyl acetal
Etc.), an intermediate layer described later also serves as a support.
But can also be used to form an intermediate layer on other supports
You can also Support (substrate) applicable to the present invention
Is preferably a dimensionally stable plate.
E.g. paper, plastic (e.g. polyethylene
(Polypropylene, polystyrene, etc.)
Paper, metal plate (eg, aluminum, zinc, copper)
Etc.) The above metal was laminated or vapor-deposited
Paper or plastic film is included. The present invention
As the support used for the polyester film, the polyester film or
Is preferably an aluminum plate, among which the hydrophobicity
Polyester film that can also serve as a polymer-containing layer
Rum and aluminum plates with good dimensional stability are suitable for use
I can. The support of the present invention includes the above-mentioned energy
Supports used in surface graft polymerization by gheeing
What was mentioned as a substrate, also in other aspects of the hydrophilic layer
It can be used as well. (Layer that exhibits polymerization initiating ability)
In the surface graft polymerization method by applying ghee,
Polymerization starts by applying energy to the surface of the carrier
Polymerizable compounds and polymerization initiators as compounds that exhibit high performance
Is preferably added. Layer that exhibits polymerization initiating ability
(Hereinafter referred to as the intermediate layer as appropriate)
Dissolve them in a solvent that can be dissolved, and support them by methods such as coating
Formed on the body surface and hardened by heating or light irradiation
can do. (I) Polymerizable compound The polymerizable compound used for the intermediate layer is adhesive to the support.
With good energy and energy such as actinic ray irradiation
Polymerizable at the terminal and / or side chain contained in the upper layer
Especially if a hydrophilic compound having a group can be added
There is no limitation, but in particular, sparse having a polymerizable group in the molecule.
Aqueous polymers are preferred. Such a hydrophobic polymer and
Specifically, polybutadiene, polyisoprene
Diene homopolymers such as ethylene and polypentadiene,
Le (meth) acrelane 卜, 2-allyloxyethyl meta
Homopolymers of allyl group-containing monomers such as Kuririn 卜;
Furthermore, the polybutadiene, polyisoprene, poly
Diene monomer such as lipentadiene or allyl group
Styrene containing a monomer-containing monomer as a structural unit (meth)
With acrylic ester, (meth) acrylonitrile, etc.
Binary or multi-component copolymers; unsaturated polyesters, unsaturated
Japanese polyepoxide, unsaturated polyamide, unsaturated polyac
Carbon-carbon bismuth in molecules such as
Linear polymer or three-dimensional polymer having a double bond; etc.
Is mentioned. In this specification, “acrylic,
When referring to either or both of “krill”, “(meta)
Sometimes referred to as “acrylic”. Polymerizable compound content
The amount is preferably in the range of 0 to 100% by mass in the middle layer.
A range of 10 to 80% by mass is particularly preferable. (Ii) Polymerization initiator Intermediate in surface graft polymerization by energy application
In order to express the polymerization initiating ability by applying energy to the layer
It is preferable to contain a polymerization initiator. Used here
The polymerization initiator to be obtained has a predetermined energy, for example, active
Polymerization started by light irradiation, heating, electron beam irradiation, etc.
Known thermal polymerization initiator, photopolymerization initiator, etc.
Can be appropriately selected and used according to the purpose. Na
However, photoreaction with higher reaction rate (polymerization rate) than thermal polymerization
Is preferable from the viewpoint of manufacturing suitability.
Therefore, it is preferable to use a photopolymerization initiator. Enel
Photopolymerization that can be used in surface graft polymerization by applying ghee.
The initiator is active against the irradiated actinic radiation and is intermediate
A polymerizable compound contained in the layer, and a terminal contained in the upper layer or
Polymerization with a hydrophilic compound having a polymerizable group in the side chain
If it is possible, there is no particular limitation.
Dical polymerization initiator, anionic polymerization initiator, cationic polymerization
An initiator or the like can be used. Specific examples of such a photopolymerization initiator include
For example, p-tert-butyltrichloroacetate
Phenone, 2,2'-diethoxyacetophenone, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
Acetophenones such as ON; benzophenone (4,
4'-bisdimethylaminobenzophenone, 2-chloro
Thioxanthone, 2-methylthioxanthone, 2-ethyl
Luthioxanthone, 2-isopropylthioxanthone,
Ketones such as: benzoin, benzoin methyl ether
, Benzoin isopropyl ether, benzoin iso
Benzoin ethers such as butyl ether; benzyl
Dimethyl ketal, hydroxycyclohexylphenyl
And benzyl ketals such as ketones.
The content of the polymerization initiator is 0.01 to solid content in the intermediate layer.
A range of 20% by weight is preferred and a range of 0.1-10% by weight.
An enclosure is particularly preferred. Applying the polymerizable compound and the polymerization initiator
The solvent used in the process is one in which those components dissolve.
If there is no particular limitation. From the viewpoint of ease of drying and workability
Are preferably solvents whose boiling point is not too high, specifically,
What has a boiling point of about 40 ° C. to 150 ° C. may be selected. Ingredients
Physically, acetone, methyl ethyl ketone, cyclohexane
Sun, ethyl acetate, tetrahydrofuran, toluene, ethanol
Tylene glycol monomethyl ether, ethylene glycol
Monoethyl ether, ethylene glycol dimethyl
Ether, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, acetyl amine
Seton, cyclohexanone, methanol, ethanol,
1-methoxy-2-propanol, 3-methoxypropa
Nord, diethylene glycol monomethyl ether, di
Ethylene glycol monoethyl ether, diethylene glycol
Recall dimethyl ether, diethylene glycol die
Till ether, propylene glycol monomethyl ether
Ruacetate, propylene glycol monoethyl ether
Ruacetate, 3-methoxypropyl acetate, etc.
Can be mentioned. These solvents can be used alone or in combination.
Can be used. And the concentration of solids in the coating solution
Is suitably from 2 to 50% by weight. Coating amount when the intermediate layer is formed on the support
Is the mass after drying, 0.1-20 g / m²Is preferred
1-15 g / m²Is preferred. Application amount 0.
1g / m²Less than that, sufficient polymerization initiating ability cannot be expressed.
Insufficient grafting of aqueous compound, desired hydrophilicity
There is a concern that the coating amount is 20 g / m.²Beyond
Then, the film property tends to decrease, and film peeling is likely to occur.
Therefore, neither is preferable. As described above, the above intermediate
Arrange the composition for layer formation by coating and remove the solvent.
By doing so, an intermediate layer is formed.
It is preferable that the film be hardened by heating and / or light irradiation.
That's right. In particular, after drying by heating, light irradiation is performed in advance.
If the film is hardened, a certain degree of curing of the polymerizable compound is expected.
To achieve grafting of hydrophilic compounds.
Effectively prevents the middle layer from falling off
This is preferable. Here, light irradiation is used for pre-curing
The reason is the same as described in the section of the photopolymerization initiator.
It depends. The heating temperature and time will allow the coating solvent to dry sufficiently.
However, from the point of manufacturing suitability, the temperature
Is preferably 100 ° C. or less and the drying time is preferably within 30 minutes.
Heating within a drying temperature of 40 to 80 ° C. and a drying time within 10 minutes
More preferably, the conditions are selected. Light irradiation performed as desired after heat drying
Can use the light source used for image formation as described above
Is implemented by forming a hydrophilic layer and applying energy
Do not inhibit the formation of bonds between the active sites of the intermediate layer and the graft chains.
From the viewpoint that the polymerizable compound present in the intermediate layer
Even if it is partially radically polymerized, it is completely radically polymerized.
It is preferable to irradiate light to the extent that
Generally, it depends on the intensity of the light source.
It is preferable to be within. A guide to such pre-curing and
Therefore, the film remaining rate after solvent cleaning is 10% or more, and
In addition, the initiator remaining rate after pre-curing is 1% or more
Is mentioned. (Energy application) By energy application
In the surface graft polymerization method, a hydrophilic surface is formed.
There are no particular restrictions on the energy application method, and the substrate surface
A hydrophilic polymer having an active site on the surface and having a polymerizable group
Any method that can give energy that can be combined with
Any of these can be used, but cost and equipment simplicity
From the point of view, a method of irradiating actinic rays is preferable. In this method
Energy application method used to form a hydrophilic surface in
For whole surface heating or radiation irradiation such as whole surface exposure
The method according to this is mentioned. Good for giving energy to the entire surface
The preferred exposure and heating conditions are the polymerization contained in the aforementioned intermediate layer.
A compound capable of expressing an initiating ability is developed to exhibit the ability to initiate polymerization.
Select appropriately based on the point that the initiator can be activated.
You can. Examples of specific exposure and heating means include
By infrared laser, ultraviolet lamp, visible light, etc.
Light irradiation, electron beam irradiation such as γ-ray, thermal head, heat
Heating zone using trawl, non-contact heater or hot air
Applying thermal energy by using
It is. These light sources include, for example, mercury lamps, meta
Luhalide lamp, xenon lamp, chemical lamp,
There are carbon arc lamps. As radiation, electron beam,
There are X-rays, ion beams, far-infrared rays, and the like. G line,
i-line, Deep-UV light, high-density energy beam
(User beam) is also used. The laser used for laser exposure
The carbon dioxide laser, nitrogen laser, Ar laser
The, He / Ne laser, He / Cd laser, Kr laser
Gas laser, liquid (pigment) laser, ruby laser, etc.
Solid state laser such as Nd / YAG laser, GaAs / GaA
Semiconductor lasers such as lAs and InGaAs lasers, KrF
Laser, XeCl laser, XeF laser, Ar₂Et
Xima laser etc. are mentioned. Especially, wavelength 700 ~
YAG, a semiconductor laser that emits infrared light of 1200 nm
Exposure by solid high power infrared laser such as laser is suitable.
is there. As a specific embodiment generally used, heating
Direct or indirect full surface heating by equipment etc., infrared laser
High-illuminance flash such as scanning exposure by the Xenon discharge lamp
Suitable for whole surface exposure such as X-ray exposure or infrared lamp exposure
It is mentioned in. When actinic light exposure is performed, purple
Outside line, visible light is preferred, and the polymerization rate is excellent
UV exposure is particularly preferred. The main wavelength of actinic rays is
It is preferable that it is 250 nm or more and 800 nm or less.
As a light source used for ultraviolet exposure, for example, low-pressure mercury
Lamp, high pressure mercury lamp, fluorescent lamp, xenon lamp, carbon
Ner clamp, tungsten incandescent lamp, sunlight, etc.
Is given. The time required for light irradiation is the desired degree of hydrophilicity
Depending on the light source used, usually a few seconds to 24:00
Between. In this way, energy is applied to the entire surface of the substrate.
It has an active site generated on the surface of the substrate and a polymerizable group
A hydrophilic compound with high mobility.
Lithographic printing plate support on which a hydrophilic surface having a ft chain is formed
A body is obtained. In a preferred embodiment, the side chain
By adding a hydrophilic compound having a compatible group,
In addition to the polymerizable group on the side chain of the graft chain bonded to the surface,
A water-based graft chain is bonded to form a branched structure.
Formation of a hydrophilic graft with a high degree of mobility
Further increase in both density and mobility
It exhibits high hydrophilicity. Next, the addition to the hydrophilic layer and the image forming layer is performed.
Reactive groups that can bond to each other when exposed to heat or radiation
Representative of negative-working image-forming layers
Examples of acid-crosslinking image-forming layers and polymerization-curing image-forming layers
An example will be described. In the lithographic printing plate precursor according to the present invention,
Aim to increase adhesion between hydrophilic layer and image forming layer after image formation
In the surface layer where the hydrophilic graft chain is present (hydrophilic
Layer) and the image-forming layer.
It is characterized by containing a group. Where (A) image
Describes the case of using an acid-crosslinked layer as a forming layer
The In the case of an acid-crosslinking type image forming layer, (A) a hydrophilic layer and
And an acid-crosslinking compound in both the image forming layer
Due to heat or radiation irradiation during image formation,
A cross-linking reaction is caused to bond the hydrophilic layer and the image forming layer.
Can be made. [A: Acid crosslinkable compound to be introduced into hydrophilic layer]
(A) When applied to the embodiment of the acid-crosslinking type image forming layer
As a method of introducing an acid crosslinkable compound into the hydrophilic layer,
A hydrophilic monomer having an acid crosslinking reactive group in the compound and
Mixed with the hydrophilic compound used to form the hydrophilic layer described above.
By providing it on the base material, hydrophilicity having an acid crosslinking reactive group
A graft surface can be obtained. Making these acid crosslinkable
As an example of a compound, N-alkoxymethyl (meth) acryl
Luamide, glycidyl methacrylate, 3,4-epoxy
Examples include cicyclohexylmethyl methacrylate. This
Among them, N-alkoxymethyl having higher hydrophilicity
(Meth) acrylamide is most preferred. Acid in the hydrophilic layer
The content of the crosslinking reactive group is 5 to 70% by mass with respect to all functional groups.
Is preferable, and 10 to 50 mass% is more preferable. [(A) Acid cross-linked image forming layer] This embodiment
Image forming layer used in (A) (hereinafter referred to as acid cross-linked layer as appropriate)
Includes an acid crosslinking compound and an acid generator.
A negative action sensitive composition is preferred. (A) Acid
In the cross-linked layer, heat or radiation during image formation
The acid generator is decomposed to generate acid, and the action of the acid crosslinkable compound
Acid crosslinkable groups in the image forming layer, and the parent
Strong cross-linking structure between acid crosslinkable reactive groups contained in the water layer
A structure is formed. As a result, the alkali solubility of the image area is reduced.
Not only become insoluble in the developer, but also with the hydrophilic layer
Increased adhesion, high printing durability, and many prints with no stains
It is thought that (Acid-crosslinking compound) (A) The acid crosslinking compound used in the acid crosslinking layer is a polymer.
In the main chain or side chain of the compound, carboxylic acid group, hydroxyl group,
Those having acid-crosslinkable functional groups such as a gnolic hydroxyl group are preferred.
Good. Of polymer compounds having carboxylic acid groups or hydroxyl groups
Examples include polyhydroxystyrene, hydroxystyrene
Copolymer of len and methyl methacrylate, 2-hydroxy
Cymethacrylate and cyclohexyl methacrylate,
Copolymer of til methacrylate, poly (styrene / buty
Methacrylate / methyl methacrylate / methacryl
Acid), poly (butyl methacrylate / methacrylic acid),
Poly (vinylphenol / 2-hydroxyethyl methacrylate)
Relate), poly (styrene / butyl methacrylate /
2-hydroxyethyl methacrylate / methacrylic
Acid), poly (styrene / ethyl methacrylate / 2-
Droxyethyl methacrylate / methacrylic acid), poly
(N-methoxymethylmethacrylamide / 2-phenyl
Methyl methacrylate / methacrylic acid)
The Polymer compounds having phenolic hydroxyl groups
For example, phenol and formaldehyde
Condensation polymer (hereinafter referred to as “phenol formaldehyde resin”)
That's it. ), M-cresol and formaldehyde
Polymer (hereinafter referred to as “m-cresol formaldehyde tree
It is called “fat”. ), P-cresol and formaldehyde
A polycondensate of m- / p-mixed cresol and formaldehyde
Condensation polymer with hydride, phenol and cresol (m-, p
-Or m- / p-mixed) and form
A novolak resin such as a condensation polymer with an aldehyde, and
The polycondensation of pyrogallol and acetone
Yes. Alternatively, a monomer having a phenol group in the side chain
Copolymers obtained by copolymerizing can also be used. Use
As a monomer having a phenol group, a phenol group
Acrylamide, methacrylamide, acrylic
Acid ester, methacrylate ester, or hydroxy
Examples include styrene. Specifically, N- (2-hydride
Loxyphenyl) acrylamide, N- (3-hydroxy
Cyphenyl) acrylamide, N- (4-hydroxyph
Enyl) acrylamide, N- (2-hydroxypheny)
) Methacrylamide, N- (3-hydroxypheny
) Methacrylamide, N- (4-hydroxypheny)
E) Methacrylamide, o-hydroxyphenyl acrylate
Rate, m-hydroxyphenyl acrylate, p-hy
Droxyphenyl acrylate, o-hydroxypheny
Methacrylate, m-hydroxyphenyl methacrylate
, P-hydroxyphenyl methacrylate, o-hy
Droxystyrene, m-hydroxystyrene, p-hydride
Loxystyrene, 2- (2-hydroxyphenyl) ethyl
Acrylate, 2- (3-hydroxyphenyl) ethyl
Acrylate, 2- (4-hydroxyphenyl) ethyl
Acrylate, 2- (2-hydroxyphenyl) ethyl
Methacrylate, 2- (3-hydroxyphenyl) ester
Tyl methacrylate, 2- (4-hydroxyphenyl)
Ethyl methacrylate, 2- (N '-(4-hydroxy
Phenyl) ureido) ethyl acrylate, 2- (N ')
-(4-Hydroxyphenyl) ureido) ethyl methacrylate
A relation or the like can be preferably used. The mass average molecular weight of the polymer is 5.0 × 10²
~ 2.0 × 10^FiveAnd the number average molecular weight is 2.0 × 10²~
1.0 × 10^FiveAre preferable from the viewpoint of image formability.
If these acid crosslinkable compounds are used alone,
Alternatively, two or more types may be used in combination. Combination
In that case, please refer to US Pat. No. 4,123,279.
T-Butylphenol and form as described
Condensation polymers with aldehydes and octylphenol
3 to 8 carbon atoms such as condensation polymers with maldehyde
Phenol and formal having an alkyl group as a substituent
A condensation polymer with aldehyde may be used in combination. In this embodiment (A), these acid crosslinks
The content of the compound is 10 to 9 in the total solid content of the image forming layer.
It is about 0% by mass, preferably 20-85% by mass.
0-80 mass% is more preferable. Containing acid crosslinkable compounds
When the content is less than 10% by mass, the image forming layer or heat sensitive
The durability of the protective layer deteriorates, and when it exceeds 90% by mass,
It is not preferable in terms of both degree and durability. Also these acid racks
Only one type of bridging compound may be used, or
May be used in combination of two or more. (Acid generator) (A) The acid generator used for the acid crosslinking layer is 200 to 50.
Irradiate light in the wavelength region of 0 nm, or 100 ° C. or higher
It refers to a compound that generates an acid when heated to. Previous
Examples of the acid generator include a photoinitiator for photocationic polymerization and a photopolymerization agent.
Photoinitiator for dical polymerization, photodecolorant for pigments, photochromic agent,
Alternatively, known acids used in microresists etc.
Known compounds that can generate acid upon thermal decomposition, such as generators
And mixtures thereof, etc.
You can select and use. For example, diazonium
Diazonium salt, ammonium salt, phosphonium salt,
Iodonium salt, sulfonium salt, selenonium salt, a
Onium salts such as ruthenium salts, JP-A 63-29833
No. 9 organic halogen compounds and JP-A-2-161
Organometallic / organic halides described in Japanese Patent No. 445
Represented by halides, iminosulfonates, etc.
Disulfo, a compound that generates sulfonic acid by photolysis
Compounds, or groups or compounds that generate these acids
Is introduced into the main chain or side chain of the polymer, or
Or, Japanese Patent Application Laid-Open No. 2001-142 previously proposed by the present applicant.
No. 230, described in paragraph numbers [0197] to [0222]
Examples include acid generators. In this embodiment (A)
The amount of the acid generator added is the total solid content of the acid-crosslinking image forming layer.
It is usually about 0.001 to 40% by mass with respect to the shape,
0.01-20 mass% is preferable, 0.1-5 mass% is
Further preferred. (Photothermal conversion agent) (A) A lithographic printing plate precursor using an acid-crosslinking image forming layer,
When forming an image by scanning exposure with laser light,
Convert light energy into thermal energy for lithographic printing plate precursors
Therefore, it is preferable to contain a photothermal conversion agent for this purpose.
Here, the photothermal conversion agent that may be contained is an ultraviolet ray.
Absorbs rays, visible rays, infrared rays, white rays, etc. into heat
Any substance that can be converted can be used, for example carbon
Black, carbon graphite, pigment, phthalocyanine
Pigments, metal powders, metal compound powders and the like. Special
In addition, a wavelength of 760 nm to 1200 nm is preferable.
Dyes, pigments or metal powders that effectively absorb infrared rays, gold
It is a genus compound powder. In the present invention, it is used as a photothermal conversion agent.
Commercially available pigments and color indexes
(CI) Handbook, “Latest Pigment Handbook” (Japan Pigment Technical Association)
Edition, 1977), "Latest Pigment Application Technology" (CMC
Published in 1986), "Printing ink technology" issued by CMC
Edition, published in 1984)
The The types of pigments are black pigment, yellow pigment, oren
Di-color pigment, brown pigment, red pigment, purple pigment, blue pigment,
Green pigments, fluorescent pigments, metal powder pigments, other polymers
Compound dyes may be mentioned. Specifically, insoluble azo pigments, a
Zorlake pigment, condensed azo pigment, chelate azo pigment, lid
Russianine pigments, anthraquinone pigments, perylene and
Perinone pigment, thioindigo pigment, quinacridone
Pigment, dioxazine pigment, isoindolinone face
Material, quinophthalone pigment, dyed lake pigment, azine face
Materials, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments,
Inorganic pigments, carbon black and the like can be used. The pigment may be used without surface treatment,
A surface treatment may be applied. As a surface treatment method
For example, surface coating with hydrophilic resin or lipophilic resin
Methods, methods of attaching surfactants, reactive substances (eg
Silica sol, alumina sol, silane coupling agent
And epoxy compounds, isocyanate compounds) on the pigment surface
The method of making it couple | bond with. The surface treatment method is
"Characteristics and application of metal soap" (Shoshobo), "Printing ink technique
”(CMC Publishing, 1984) and“ Latest pigment application ”
Technology "(CMC Publishing, 1986)
The Among these pigments, those that absorb infrared rays are infrared rays.
It is preferable in that it is suitable for use in a laser emitting light. Heels
Carbon black is the preferred pigment that absorbs infrared rays.
Good. The particle size of the pigment is in the range of 0.01-1 μm.
Preferably in the range of 0.01 to 0.5 μm
More preferable. As the dye, commercially available dyes and literature
(For example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, Showa
45), “Chemical Industry”, May, 1986 issue, p. 45-
51 “Near-infrared absorbing dyes”, “Development of functional dyes in the 90s
Development and Market Trends ”, Chapter 2, Section 2.3 (1990) CMC
-) Or known dyes described in patents can be used
The Specifically, azo dyes, metal complex azo dyes, pyrazo
Lonazo dye, anthraquinone dye, phthalocyanine dye
Material, carbonium dye, quinoneimine dye, polymethine
Infrared absorbing dyes such as dyes and cyanine dyes are preferred. Further, for example, Japanese Patent Laid-Open No. 58-125246.
Publication No. 59-84356 Publication No. 60-7878
Cyanine dyes described in No. 7 etc., JP-A-58-1
No. 73696, No. 58-181690, No. 5
Methine dyes described in 8-194595 etc.
Japanese Utility Model Publication Nos. 58-112793 and 58-224793.
Publication No. 59-48187 Publication No. 59-7399
No. 6, No. 60-52940, No. 60-637
Naphthoquinone dyes described in No. 44, etc., JP-A-5
Squarylium described in 8-112792 etc.
Dyes described in British Patent 434,875
Cyanine dye, US Pat. No. 4,756,993
Dyes described in US Pat. No. 4,973,5
Cyanine dyes described in Japanese Patent No. 72, JP-A-1
Dyes described in Japanese Patent No. 0-268512, 11
Phthalocyanine described in Japanese Patent No. 235883
Compounds. Also, as a dye, US Pat. No. 5,156,
The near infrared absorption sensitizer described in No. 938 is also preferable.
Appropriately used and US Pat. No. 3,881,924
The substituted aryl benzo (thio
E) pyrylium salt, described in JP-A-57-142645
Trimethine thiapyrylium salt, JP-A 58-
No. 181051, No. 58-220143, No.
59-41363, 59-84248,
No. 59-84249, No. 59-146063
No. 59-146061
Lium compound, described in JP 59-216146 A
Cyanine dyes described, US Pat. No. 4,283,4
Pentamethine thiopyril described in No. 75
Um salt, etc., and Japanese Patent Publication No. 5-13514, 5-197
Pyrylium compounds described in Japanese Patent No. 02, commercial products
As Epolite III-178 made by Eporin,
Epolite III-130, Epolite III-125
Etc. are also preferably used. Examples of preferred other dyes and
In U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described as (I) and (II)
Can be mentioned. Some specific examples are shown below. [0061] [Chemical 1][0062] [Chemical 2]Of these dyes, particularly preferred
Cyanine dye, squarylium dye, pyrylium
Examples thereof include salts and nickel thiolate complexes. The image forming layer according to the present invention has a photothermal conversion agent.
Metal fine particles can also be used. Of fine metal particles
Many are light-to-heat convertible and self-heating. Good
Preferred metal fine particles include, for example, Si, Al, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,
Zr, Mo, Ag, Au, Pt, Pd, Rh, In, S
n, W, Te, Pb, Ge, Re, Sb alone or
Alloy or oxide or sulfide fine particles
Is mentioned. More preferably, Ag, Au, Cu, P
t, Pd single metal or alloy fine particles
The The average diameter of the fine metal particles that can be used in the present invention is:
Preferably 1 to 500 nm, more preferably 1 to 100
nm, particularly preferably 1 to 50 nm. Its degree of dispersion
May be polydisperse, but monodisperse with a coefficient of variation of 30% or less
Is preferred. The amount of the photothermal conversion agent added to the image forming layer is
In the case of a dye or a dye, 30% by mass of the total solid content of the image forming layer
Can be added. Preferably 1 to 25% by mass
And particularly preferably 7 to 20% by mass. Metal fine
In the case of a particulate photothermal conversion agent, 5% of the total solids of the image forming material
˜50 mass%, preferably 10-30 mass
%, Particularly preferably 15 to 20% by mass. This
Within the range, a good sensitivity improvement effect can be obtained. The photothermal conversion agent is not necessarily contained in the image forming layer.
Even if not, for example, the photothermal conversion layer is adjacent to the image forming layer.
May be added there, or it may be added to the intermediate layer or later
The water-soluble overcoat layer described above may be contained. Image form
Of each layer such as stratification, intermediate layer and overcoat layer
Because at least one layer contains a photothermal conversion agent
Infrared absorption efficiency increases and sensitivity can be improved.
it can. Next, it is applied to (B) a polymerization curing type image forming layer.
The case will be described. [B: Polymerizable compound introduced into hydrophilic layer] This embodiment (B) Heavy
In the case of introducing a polymerizable compound into the hydrophilic layer in the co-cured layer
As a method, (1) having a polymerizable group precursor in the compound
Used to form the hydrophilic monomer and the aforementioned hydrophilic layer
Create a graft layer on a substrate by mixing with a hydrophilic compound
Thereafter, a method of introducing a polymerizable group by treatment with a base or the like,
(2) of hydrophilic graft chains directly bonded to the substrate surface
Method for reacting a monomer having a functional group and a polymerizable group
There is. The polymerizable group precursor in the method (1)
As monomers having 2- (3-chloro-1-oxy)
And sopropoxy) ethyl methacrylate. Up
The hydrophilic group capable of reacting with the polymerizable group in the method (2)
The functional group of the raft chain includes a carboxyl group and an amino group
Or their salts, hydroxyl groups and epoxy groups are listed.
As a monomer having a polymerizable group, (meth)
Acrylic acid, glycidyl (meth) acrylate, allyl
Glycidyl ether, 2-isocyanatoethyl (meth)
An acrylate etc. are mentioned. Method (1) above and
In (2), the radical weight contained in the hydrophilic layer
The content of the compatible group is 5 to 70 with respect to all the functional groups of the hydrophilic layer.
It is preferable to contain 10% by mass.
More preferable. [(B) Polymerization-Curing Image Forming Layer] This Embodiment
Polymerization-curable image forming layer used in (B) (hereinafter, suitable
As the polymerization hardened layer), it has a polymerizable group.
Negative production comprising a compound and a radical polymerization initiator
Sensitive compositions are preferred. (B) In the polymerization hardened layer
Is a radical caused by heat or radiation during image formation.
In the image forming layer, radicals generated from the polymerization initiator
The polymerizable groups contained in the hydrophilic layer are
A polymerization reaction occurs in a chain, and the image portion is cured. this
This reduces the alkali solubility of the image area and makes it unusable in the developer.
Not only does it dissolve, but also improves adhesion to the hydrophilic layer, resulting in high resistance.
It is thought that a large number of prints without stains can be obtained by printing.
The (Polymerizable compound) (B) Used for polymerized cured layer
The compound having a polymerizable group (polymerizable compound)
At least one terminal ethylenically unsaturated bond, preferably
It is possible to arbitrarily select from two or more compounds
Yes. These include, for example, monomers, prepolymers,
That is, dimer, trimer and oligomer, or them
Chemical forms such as mixtures of these and their copolymers
It has. Examples of monomers and their copolymers
Unsaturated carboxylic acids (e.g. acrylic acid,
Rilic acid, itaconic acid, crotonic acid, isocrotonic acid,
Selenic acid etc.) and aliphatic polyhydric alcohol compounds
Tellurium, unsaturated carboxylic acid and aliphatic polyamine compound
Examples include amides. Aliphatic polyhydric alcohol compound and unsaturated cal
Specific examples of monomers of esters with boric acid include
Ethyl glycol diacrylate
, Triethylene glycol diacrylate, 1,3
-Butanediol diacrylate, tetramethylene glycol
Cold diacrylate, propylene glycol diacryl
Rate, neopentyl glycol diacrylate, tri
Methylolpropane triacrylate, trimethylol
Propanetri (acryloyloxypropyl) ate
, Trimethylolethane triacrylate, hexane
Diol diacrylate, 1,4-cyclohexanedio
Diacrylate, tetraethylene glycol diac
Relate, pentaerythritol diacrylate, pen
Taerythritol triacrylate, pentaerythritol
Tetraacrylate, dipentaerythritol dia
Chryrate, dipentaerythritol pentaacrean
Dipentaerythritol hexaacrylate, sol
Bitol triacrylate, sorbitol tetraacrylate
Rate, sorbitol pentaacrylate, sorbitol
Lehexaacrylate, tri (acryloyloxyethyl)
L) Isocyanurate, polyester acrylate
There are gomers. Methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythrito
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, dipentaerythritol pentamethacrylate
Sorbitol trimethacrylate, sorbitol
Tetramethacrylate, bis [p- (3-methacrylo
Xyl-2-hydroxypropoxy) phenyl] dimethyl
Methane, bis- [p- (methacryloxyethoxy) phenyl
Nenyl] dimethylmethane and the like. Itaconic acid esters include ethylene glycol
Recall Diitaconate, Propylene Glycol Diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The As crotonic acid ester, ethylene glycol
Dicrotonate, tetramethylene glycol dicrotone
, Pentaerythritol dicrotonate, sorbite
And tetratetracrotonate. Isocrotonic acid
As stealth, ethylene glycol diisocrotonate
, Pentaerythritol diisocrotonate, sorbi
Examples include tall tetraisocrotonate. Maleic acid
Steal includes ethylene glycol dimaleate, tri
Ethylene glycol dimaleate, pentaerythritol
Examples include dimalate and sorbitol tetramaleate. The
In addition, a mixture of the aforementioned ester monomers can also be mentioned.
it can. In addition, an aliphatic polyamine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
There are As another example, Japanese Patent Publication No. 48-417
As described in Japanese Patent No. 08, two or more per molecule
Polyisocyanate compound having an isocyanate group
In addition, a polymer containing a hydroxyl group represented by the following general formula (I):
Polymerization of 2 or more molecules in a molecule to which nyl monomer is added
Vinyl urethane compounds containing a functional vinyl group
It is. [0075] CH₂= C (R¹) COOCH₂CH (R²) OH General Formula (I) (However, R¹And R²Is H or CH_ThreeIndicates. ) Japanese Patent Laid-Open No. 51-37193, Japanese Patent
Urethane action as described in No. 2-32293
Relates, JP-A-48-64183, JP-B-49-
No. 43191 and Japanese Patent Publication No. 52-30490
Polyester acrylates, such as epoxies
Epoxy actives made by reacting a resin with (meth) acrylic acid
Polyfunctional acrylates and methacrylates such as relates
Can be mentioned. Furthermore, Journal of Japan Adhesion Association vol.
20, no. 7, 300-308 pages (1984)
Introduced as photocurable monomers and oligomers
You can also use what you have. These polymerizations
In the total solid content of the (B) polymerization hardened layer,
It is 5-70 mass%, Preferably it is 10-50 mass%. (Polymerization initiator) Heavy used for the polymerized cured layer
Depending on the wavelength of the light source used, the initiator, patent, literature, etc.
Various photoinitiators, thermal initiators, or two known
Select and use the above initiator combination system (initiating system) as appropriate.
Can be. Visible light of 400 nm or more, Ar laser
-Second harmonic of semiconductor laser, SHG-YAG
Various light initiation systems have also been proposed when using a laser as the light source.
For example, as described in US Pat. No. 2,850,445
The photoreducible dye listed above, or a combination of dye and initiator
Systems such as organic peroxides and dyes
Sho 59-1504, JP 59-140203,
No. 59-189340, Japanese Unexamined Patent Publication No. 62-174203
No., JP-B 62-1641, US Pat. No. 476605
No. 5), a system of a dye and an active halogen compound (JP-A 63-
258903, JP-A-2-63054, etc.), dyes
And borate compound systems (JP-A-62-143044,
JP-A-62-1050242, JP-A-64-13140
, JP 64-13141, JP 64-1314
No. 2, JP-A 64-13143, JP-A 64-131
44, JP-A 64-17048, JP-A 1-229
003, JP-A-1-298348, JP-A-1-13
8204 etc.). In particular, an infrared laser is used as an exposure source.
Photothermal conversion agent and radical generation as initiator when used
Combinations with agents are used. Radical generation at this time
Preferred compounds as agents include onium salts, and specific examples
Iodonium salt, diazonium salt, sulfonium
Salt. For such initiators, the applicant of the present application
Japanese Patent Application No. 2000-132478 previously proposed
Are described in detail in the drop numbers [0034] to [0040],
These can also be applied to the present invention. Polymerization initiator content
Is about 1 to 80% by mass relative to the total solid content of the polymerized cured layer
It is a degree, and 5-50 mass% is preferable. (Photothermal conversion agent) Using the method of this embodiment (B)
The lithographic printing plate precursor can also be scanned with laser light
When forming an image, using the above method (A)
As with lithographic printing plate precursor, light energy is heat energy
It is preferable to contain a photothermal conversion agent for conversion into
Good. In the lithographic printing plate precursor by the method of this embodiment (B)
As the photothermal conversion agent that may be included, the above
Using the same photothermal conversion agent as used in (A)
it can. [Other Components] The image according to the present invention is described below.
Formation layer [common to (A) acid cross-linking layer and (B) polymerization hardened layer]
In order to obtain various lithographic printing plate properties,
In addition to the above, various compounds may be added. For example, the image forming layer is large in the visible light region.
Dyes with good absorption can be used as image colorants
it can. These dyes are used for image areas and non-images after image formation.
Since it is easy to distinguish the parts, it is preferable to add them.
The addition amount is 0.01% with respect to the total solid content of the image forming layer.
It is a ratio of -10 mass%. Further, the image forming layer according to the present invention has a development.
In order to broaden the stability of the treatment to the conditions,
In 251740 and JP-A-3-208514
Nonionic surfactants as described, JP 59
No.-121044 and JP-A-4-13149
Adding amphoteric surfactants as described
it can. Non-ionic and amphoteric surfactant lithographic plates
The ratio of the printing original plate to the image forming layer is 0.05 to 15
% By mass is preferred, more preferably 0.1 to 5% by mass.
is there. Furthermore, the image forming layer according to the present invention can be used as necessary.
Plasticizers are added to provide flexibility, etc.
The For example, butyl phthalyl, polyethylene glycol
, Tributyl citrate, diethyl phthalate, phthalic acid
Dibutyl, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trio phosphate
Cutyl, tetrahydrofurfuryl oleate, acrylic
Used for acid and methacrylic acid oligomers and polymers
I can. In the present invention, the image forming layer is usually the above-mentioned layer.
Dissolve each component in a solvent and apply on the hydrophilic layer
It is formed by. The solvent used here is Ethi
Range chloride, cyclohexanone, methyl ethyl ketone
T, methanol, ethanol, propanol, ethyl
Glycol monomethyl ether, 1-methoxy-2-
Propanol, 2-methoxyethyl acetate, 1-methyl
Toxi-2-propyl acetate, dimethoxyethane,
Methyl lactate, ethyl lactate, N, N-dimethylacetami
N, N-dimethylformamide, tetramethylurea
A, N-methylpyrrolidone, dimethyl sulfoxide,
Examples include ruphoran, γ-butyrolactone, toluene, water, etc.
However, the present invention is not limited to this. this
These solvents are used alone or in combination. In solvent
The concentration of the above components (total solid content including additives) is preferably
Is 1-50 mass%. Also obtained after coating and drying
The coating amount (solid content) on the hydrophilic layer varies depending on the application.
However, generally speaking, the lithographic printing plate precursor is 0.5 to 5.
0g / m²Is preferred. As the coating amount decreases,
Although the apparent sensitivity is increased, the film characteristics of the image recording film are low.
I will give you. Various methods can be used for coating.
For example, bar coater coating, spin coating,
Spray coating, curtain coating, dip coating, air na
If coating, blade coating, roll coating, etc.
it can. Image forming layer of planographic printing original plate in the present invention
Include surfactants for improving coating properties, such as
As described in Japanese Patent Publication Sho 62-170950.
A nitrogen-based surfactant can be added. Preferred supplement
The added amount is 0.01 to 1% by mass in the total solid content of the image forming layer.
More preferably, it is 0.05-0.5 mass%. [Other components] (Overcoat layer) In the lithographic printing plate precursor according to the invention
Prevents contamination of the image forming layer surface with lipophilic substances.
Therefore, a water-soluble overcoat layer is provided on the image forming layer.
be able to. Water-soluble overcoat used in the present invention
It is preferable to use a water-soluble layer that can be easily removed during printing.
A resin selected from the organic polymer compounds. here
The water-soluble organic polymer compound used in
The film formed by has a film-forming ability,
Specifically, polyvinyl acetate (however, hydrolysis rate 65%
Above), polyacrylic acid and its alkali metals
Salt or amine salt, polyacrylic acid copolymer and
Alkali metal salt or amine salt of polymethacrylic acid
And alkali metal salts or amine salts thereof, polymethacrylate
Luric acid copolymer and alkali metal salt or amine thereof
Salt, polyacrylamide and its copolymer, polyhydride
Roxyethyl acrylate, polyvinylpyrrolidone and
Copolymers thereof, polyvinyl methyl ether, polyvinyl chloride
Rumethyl ether / maleic anhydride copolymer, poly-2
-Acrylamide-2-methyl-1-propanesulfone
Acids and alkali metal salts or amine salts thereof, poly-2-
Acrylamide-2-methyl-1-propanesulfonic acid
A copolymer and its alkali metal salt or amine salt,
Gum arabic, fibrin derivatives (eg carboxymethyl)
Rucellose, carboxyethyl cellulose, methyl cell
Lurose, etc.) and modified products thereof, white dextri
, Pullulan, enzymatically degraded etherified dextrin, etc.
I can make it. Depending on the purpose, these resins
A mixture of two or more of these can also be used. In addition, the photothermal deformation is applied to the overcoat layer.
You may add a water-soluble thing among exchange agents. In addition,
-The bar coat layer has a water
For solution coating, polyoxyethylene nonyl pheny
Luether, polyoxyethylene dodecyl ether, etc.
Nonionic surfactants can be added. Oh
The dry coating amount of the bar coat layer is 0.1 to 2.0 g / m.²
Is preferred. Within this range, on-machine developability is not impaired,
Good surface of image-forming layer due to lipophilic substances such as clogging stains
Good pollution prevention. The lithographic printing of the present invention thus obtained
The plate precursor is imagewise exposed, developed, and lithographically printed by conventional methods.
It becomes a version. This lithographic printing plate precursor is recorded with an infrared laser.
it can. In addition, heat from UV lamps and thermal heads
Recording is also possible. In the present invention, wavelength 760
a solid-state laser that emits infrared light having a wavelength of 1 nm to 1200 nm
And image exposure with a semiconductor laser is preferred.
The laser output is preferably 100 mW or more, and the exposure time is
Use multi-beam laser devices to shorten
Are preferred. The exposure time per pixel is 20μ.
Preferably it is within seconds. The recording material is irradiated
Energy is 10-300mJ / cm²Prefer to be
That's right. After exposure with an infrared laser, the
The image recording material is preferably water or an alkaline aqueous solution
Developed with Use alkaline aqueous solution as developer
The developer and replenisher of the image recording material of the present invention,
In this case, a conventionally known alkaline aqueous solution can be used. example
For example, sodium silicate, potassium, tribasic sodium phosphate
Um, potassium, ammonium, dibasic sodium phosphate
Um, potassium, ammonium, sodium carbonate,
Same potassium, same ammonium, sodium bicarbonate, same
Potassium, ammonium, sodium borate, potassium
Um, ammonium, sodium hydroxide, ammonium
Inorganic alkali salts such as um, potassium and lithium
Can be mentioned. Monomethylamine, dimethylamino
, Trimethylamine, monoethylamine, diethylamine
Min, triethylamine, monoisopropylamine, di
Isopropylamine, triisopropylamine, n-butyl
Tylamine, monoethanolamine, diethanolamine
, Triethanolamine, monoisopropanolamine
, Diisopropanolamine, ethyleneimine, ethyl
Organic alkali agents such as range amine and pyridine are also used.
The These alkaline agents are used alone or in combination of two or more.
Used. Further, when developing using an automatic processor
Is the same as the developer or more alkaline than the developer.
By adding a strong aqueous solution (replenisher) to the developer
Do not change the developer in the developer tank for a long time.
Known to be able to process large amounts of lithographic printing plate precursors
Yes. This replenishment method is preferably applied also in the present invention.
It is. The planographic printing plate obtained as described above is
If desired, after applying desensitized gum, it is used in the printing process.
can do. Planographic printing plates can be used for offset printing machines, etc.
It is used for printing a large number of sheets. Planographic seal of the present invention
The printing plate precursor has a hydrophilic layer excellent in durability and hydrophilicity, and
In addition, both the hydrophilic layer and the image forming layer are bonded to each other.
In the image area.
Both layers have high adhesion, and high printing durability is achieved. [0093] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. [Example 1] (Preparation of base material) PET film with a film thickness of 0.188 mm
(Toyobo Co., Ltd. M4100)
The polymerizable composition was applied using a rod bar No. 17 at 80 ° C.
And dried for 2 minutes. Next, this coated film is transferred to 4
00W high-pressure mercury lamp (UVL-400P, R & D industry)
And manufactured for 10 minutes. As an intermediate layer
The composition used is as follows.   ・ Allyl methacrylate / methacrylic acid polymer               (Molar ratio 80/20, molecular weight 100,000) 4g   ・ Ethylene oxide modified bisphenol A diacrylate                         (Toa Gosei Co., Ltd. M210) 4g   ・ 1.6g of 1-hydroxycyclohexyl phenyl ketone   ・ 16 g of 1-methoxy-2-propanol (Formation of hydrophilic layer)
Mido, N-methoxymethylmethacrylamide (mass ratio 6
0: 40,10 wt%) and sodium hypochlorite
(NaClO_Four, 0.01 wt%)
Using a 400w high-pressure mercury lamp in an argon atmosphere, 30
Light irradiation for a minute. Ion exchange of film obtained after light irradiation
Wash well with water and then acrylamide, N-methoxymethyl
A hydrophilic layer 1 grafted with methacrylamide was obtained. (Image forming layer) On the obtained hydrophilic layer 1,
The image forming layer coating liquid composition 1 is applied, and the planographic printing plate precursor 1
Got. [Image forming layer coating solution composition 1 (acid-crosslinking type)]   ・ IRG22 (IR dye, Nippon Kayaku) 0.1g   ・ Crosslinking agent A 0.21g   ・ Phenol-formaldehyde novolak                       (Mass average molecular weight 12000) 2.1 g   ・ Diphenyliodonium-9,10-             Dimethoxyanthracene sulfonate 0.02g ・ Megafuck F-176       (Dainippon Ink & Chemicals, Inc. fluorine-based surfactant) 0.06 g   ・ Methyl ethyl ketone 15g   ・ 12g 2-methoxy-1-propanol The crosslinking agent A is 1- [α-methyl-
α- (4-hydroxyphenyl) ethyl] -4- [α,
α-bis (4-hydroxyphenyl) ethyl] benzene
The hexamethoxymethyl form of was used. [Example 2] (Synthesis of hydrophilic compound having a polymerizable group at the terminal) N-me
Toximethyl methacrylamide 5.0g, acrylic
15g, 3-mercaptopropionic acid 0.88g,
After dissolving in 49 g of DMAc (dimethylacetamide), nitrogen
The temperature was raised to 60 degrees under an atmosphere, and AIBN (azobisbutyro
Nitrile) 200 mg was added and reacted for 6 hours. After reaction
Reprecipitated with methanol, dried and terminal carboxylic acid pre-treated
16.9 g of polymer was obtained (acid value 0.183 meq / g
Molecular weight 5.46 × 10^Three). 15 g of prepolymer
Dissolved in 64.7 g of til sulfoxide, glycidyl meta
1.17 g acrylate, N, N-dimethyldodecylami
(Catalyst) 88 mg, hydroquinone (polymerization inhibitor) 1
Add 1mg and react for 7 hours at 140 ° C under nitrogen atmosphere.
It was. Add the reaction solution to acetone to precipitate the polymer,
After washing thoroughly, the terminal methacrylate macromonomer (P-
1) 12.5 g (molecular weight 5.6 × 10^Three)Obtained. (Formation of hydrophilic layer) Used in Example 1 above.
On a support similar to that of the rod bar 1
Apply with No. 2 and dry at room temperature, under argon atmosphere
400W high pressure mercury lamp (UVL-400P, R & D industry)
For 30 minutes. After light irradiation
The obtained film is thoroughly washed with ion-exchanged water, and the hydrophilic layer 2
Got.   ・ Hydrophilic compound (P-1) having a polymerizable group at the terminal 1 g   ・ Acrylamide 1g   ・ Water 18g (Image forming layer) On the obtained hydrophilic layer 2,
The same image used when forming the image forming layer of Example 1
The image forming layer coating solution composition 1 is applied, and the planographic printing plate precursor 2 is prepared.
Obtained. [Evaluation] The obtained lithographic printing plate precursors 1 and 2
A semiconductor laser (wavelength 8) as a heat mode laser
25 nm, beam diameter: 1 / e²= 6 μm), linear speed
Adjust the plate output to 110mW at a degree of 8m / sec and expose
It was. After exposure to heat treatment at 110 ° C for 1 minute, Fuji Photo
Film Co., Ltd. developer, DP-4 (1: 8), rinse
Processing through an automatic processor charged with liquid FR-3 (1: 7)
I managed. Next, Fuji Photo Film Co., Ltd. gum GU-7
Process the plate with (1: 1) and mark with Heidel KOR-D machine
Printed. Reproduces the image faithfully, and the non-image area is clean.
20000 good prints are obtained and printing durability is excellent.
I understood it. Comparative Example 1 The support used in Example 1 was
Acrylamide, N-methoxymethyl methacrylamide
(Mass ratio 60:40, 10 wt%)
Acrylic acid (10 wt%) that does not contain
Sodium chlorite (NaClO_Four0.01wt%)
The same conditions as the hydrophilic layer of Example 1
Irradiate with light, wash with a parent grafted with acrylic acid
Aqueous layer 3 was obtained. On the obtained hydrophilic layer 3, the above Example 1 was used.
Application of the same image forming layer as that used when forming the image forming layer
The liquid composition 1 was applied to obtain a planographic printing plate precursor 3. this
When evaluated under the same conditions as in Example 1 and Example 2,
After the number of printed sheets reaches 5,000, a slight jump appears in the image area.
Occurred. When the printing was stopped and observed, the image forming layer
A partial omission is observed in the printing plate, and the printing durability is longer than that in each of the previous examples.
It turned out to be inferior. (Example 3) (Formation of hydrophilic layer) In Example 1,
The support used was acrylic acid (10 wt%), hypochlorous acid
Sodium salt (NaClO_Four, 0.01 wt%)
Immerse in an aqueous solution and illuminate under the same conditions as the hydrophilic layer of Example 1
Spray and wash the hydrophilic layer grafted with acrylic acid
create. Then, this hydrophilic layer is glycidyl methacrylate.
(10 wt%), hyodoquinone (0.01 wt%)
%) In a methanol solution containing 1% at 40 ° C.,
About 10% of the acrylic acid part reacts with methacrylate
A tacryloylated hydrophilic layer 4 was obtained. (Image forming layer) On the obtained hydrophilic layer 4,
Apply the image forming layer coating liquid composition 2 with a wire bar,
Image forming layer dried at 115 ° C. for 45 seconds in a warm air dryer
Formed. The coating amount of the image forming layer after drying is 1.2 to 1.
3g / m²It was in the range. [0104] [Image forming layer coating solution composition 2 (polymerization curing type)]   ・ Infrared absorber (IR-12) 0.08g   ・ Onium salt (SB-1) 0.30g   ・ Dipentaerythritol hexaacrylate 1.00g   ・ Allyl methacrylate and methacrylic acid     Copolymer with a molar ratio of 80:20     (Weight average molecular weight 120,000) 1.00g   ・ Victoria Pure Blue Naphthalenesulfonate 0.04g   ・ Silicon surfactant 0.03g   (TEGO GLIDE100 (product name)       Tego Chemie Service GmbH)   ・ Methyl ethyl ketone 9.0g   ・ Methanol 10.0g   1-methoxy-2-propanol 8.0g It should be noted that the image forming layer coating solution 2 was used.
Infrared absorber (IR-12) and onium salt (SB-
The structure of 1) is as shown below. [0106] [Chemical Formula 3] [Overcoat layer] Next, polyvinyl alcohol
Lecol (degree of saponification 98.5 mol%, degree of polymerization 500) 2
Coating for overcoat layer in which 0 g is dissolved in 480 g of distilled water
Aluminum prepared by adjusting the cloth liquid and forming the above image forming layer
Apply to the hot plate using a wire bar,
Dry at 100 ° C for 3 minutes to form an overcoat layer
Thus, a negative type planographic printing plate precursor 4 was obtained. The coating amount after drying is
2.2 / m²Met. [Evaluation] The obtained lithographic printing plate precursor 4 was washed with water.
Made by Creo with a cold 40W infrared semiconductor laser
Laser output with Trendsetter 3244VFS
Power 9W, outer drum rotation speed 210rpm, plate energy
-100mJ / cm², With a resolution of 2400 dpi
Exposed. Automatic development by Fuji Photo Film Co., Ltd. after exposure
Development was performed using a machine Stablon 900N. Developer is
Both the feed and replenishers are manufactured by Fuji Film Co., Ltd., DN-
3C 1: 1 water dilution was used. The temperature of the developing bath is 30 ° C
It was. The finisher is Fuji Photo Film
A 1: 1 water dilution of FN-6 manufactured by KK was used. Develop line
Made lithographic printing plate 4 manufactured by Komori Corporation
Printing was performed using a printing press Lislon. Fuji photo as dampening water
Shin Film EU-3: 1% and isopropanol
GE manufactured by DIS as an ink containing 10% aqueous solution
OSN ink was used. As a result, the image is reproduced faithfully,
20,000 sheets of good printed matter with no stain on the non-image area
It was found that the printing durability was excellent. Comparative Example 2 On the support used in Example 1
In the same manner as in Comparative Example 1, a hydrophilic layer 3 was formed. Obtained
On the hydrophilic layer 3, the polymerization-curable image forming layer of Example 3 is
The same image forming layer coating liquid composition 2 as used at the time of forming
The lithographic printing plate precursor 5 was obtained by coating. This is the same as Example 3.
When evaluated under the same conditions, the number of printed sheets reached 5000.
After that, a slight jump occurred in the image area. Stop printing
When observed, a partial omission is seen in the image forming layer,
It was found that the printing durability was inferior to that of Example 3. the above
As is clear from each example, the planographic printing plate precursor of the present invention
Regardless of the type of image forming layer, the hydrophilic layer and the image forming layer
The adhesiveness of the two is good, and even if printing continues, the two peel off.
It was possible to achieve high printing durability. [0110] According to the present invention, the hydrophilic layer after image formation and
High adhesion of image forming layer, under severe printing conditions
However, a flat plate with excellent printing durability that can produce many high-quality printed materials.
It has been found that a printing plate precursor is provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA12 AB03 AC08 AD01                       CB41 CB43 CB45 CB47 CC11                       CC17 CC20 DA36                 2H096 AA06 BA01 CA05 EA04                 2H114 AA04 AA22 AA23 AA27 BA02                       BA05 BA10 DA41 EA01 EA03                       EA04 EA08 GA01

Claims (1)

What is claimed is: 1. A surface layer having a hydrophilic graft chain directly bonded to the surface of the support and an image forming layer on the support, and an image forming layer. And a lithographic printing plate precursor comprising a compound having a reactive group capable of bonding to each other by heating or irradiation with radiation.