JP2003262958A - Image recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative image recording material adaptable to a heat mode for forming a lithographic printing plate excellent in printing durability (the number of sheets printable) in which ablation by laser scanning during recording is suppressed, an image of high picture quality having no contamination in a non-image part can be formed, and the formed image part has high strength. <P>SOLUTION: The recording material contains (A) a polymer compound having at least one kind of structural unit expressed by general formula (1), (2) or (3) by ≥0.1 mol% and <30 mol%, soluble or swellable with water or an alkaline aqueous solution, (B) a photothermal converting agent, and (C) a compound which generates a radical by exposure to light at the wavelength the photothermal converting agent absorbs the light. The material can form an image by heat-mode exposure. In formulae, each of A<SP>1</SP>, A<SP>2</SP>and A<SP>3</SP>represents oxygen atom, sulfur atom or -N(R<SP>21</SP>)-, wherein R<SP>21</SP>represents an alkyl group, each of G<SP>1</SP>, G<SP>2</SP>and G<SP>3</SP>represents a divalent organic group, each of X and Z represents oxygen atom, sulfur atom or the like, Y represents oxygen atom, sulfur atom, phenylene group or the like, and each of R<SP>1</SP>to R<SP>20</SP>represents a monovalent organic group. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses an infrared laser.
Image formation by heat mode exposure
For details on heat-mode negative image recording materials
Is a lithographic plate with high image area strength and excellent printing durability.
The present invention relates to a negative type image recording material capable of forming a printing plate. [0002] 2. Description of the Related Art Recent developments in lasers
In particular, an individual having a light emitting region from the near infrared to the infrared region.
For body lasers and semiconductor lasers, high output and downsizing
It is. Therefore, digital data such as computers
These records are used as exposure light sources when making plates directly from
The user is very useful. In the infrared region mentioned above
Red using an infrared laser
Negative lithographic printing plate materials for external lasers are infrared absorbers
And radical initiators that generate radicals by light or heat
And a lithographic printing plate having a recording layer containing a polymerizable compound
It is a fee. Usually, such a negative image recording material is used.
The radicals generated by light or heat are used as initiators.
Causing a reaction, curing the recording layer in the exposed area,
A recording method is used to form. Such negative type
The image forming material of this type depends on the energy of infrared laser irradiation.
Compared to the positive type which causes solubilization of the recording layer
It has a low productivity and promotes a curing reaction by polymerization, thereby producing a strong image.
In order to form the image area, heat treatment is performed before the development process.
It is common. Recording of such a polymerization system by light or heat
JP-A-8-108621 discloses a printing plate having a layer.
No. and JP-A-9-34110
A photopolymerizable or thermally polymerizable composition as a recording layer
Technology is known. These recording layers form high-sensitivity images
Although it has excellent properties, it is hydrophilized as a support.
At the interface between the recording layer and the support.
There was a problem that adhesion was low and printing durability was poor. Ma
In order to improve sensitivity, a high-power infrared laser is used.
However, the recording layer during laser scanning
Ablation may occur, contaminating the optical system
There was also a problem. [0004] The present invention solves the above problems.
The purpose of the present invention is to record
Ablation in laser scanning is suppressed and non-
It is possible to form high-quality images with no stains on the image area.
A lithographic printing plate with high image area strength and excellent printing durability
To provide a negative type image recording material that can be formed.
The [0005] [Means for Solving the Problems] The present inventors have intensively studied.
As a result, a polymer compound soluble in water or an alkaline aqueous solution and
Specific structural units in the polymer composition at 0.1 mol% or less
By using a resin containing less than 30 mol%, the image
Can form a lithographic printing plate with high strength and high printing durability
The present invention has been completed. That is, the image of the present invention
The recording material is (A) the following general formulas (1), (2), (3)
At least one of the structural units represented by
Water or less, more than 30 mol%, water or
Is a polymer compound that is soluble or swellable in an alkaline aqueous solution
(B) the photothermal conversion agent and (C) (B) the photothermal conversion agent absorb
It is possible to obtain
A compound that produces dicar, and heat mode dew
An image can be formed by light. Furthermore, before
The heat mode-compatible negative image recording material is (D)
A cal-polymerizable compound may be contained. [0006] [Chemical 2] (Wherein A¹, A², A^ThreeEach independently
Oxygen atom, sulfur atom, -N (R^{twenty one})-, R^{twenty one}Is
The alkyl group which may have a substituent is represented. G¹, G², G^Three
Each independently represents a divalent organic group. X and Z are
Each independently an oxygen atom, a sulfur atom, -N (R^{twenty two})-
And R^{twenty two}Represents an alkyl group which may have a substituent. Y
Is a phenyl atom which may have an oxygen atom, a sulfur atom or a substituent.
Ren group, -N (R^{twenty three})-, R^{twenty three}Has a substituent
Represents a good alkyl group. R¹~ R²⁰Are independent
Represents a monovalent organic group. ) In the image recording material of the present invention,
As a high molecular compound that performs the function of
(1), (2), at least the structural unit represented by (3)
1 type or more, 0.1 mol% or more of the polymer composition, 3
What contains less than 0 mol% is used. The following is not clear
I will explain the effect. In particular, this binder
Lithographic printing plate compatible with heat mode
Explains the effect when used for the recording layer of the original
To do. The structure represented by the general formulas (1), (2), (3)
The position has a functional group with high radical reactivity.
Therefore, radicals are generated during infrared laser scanning exposure.
Immediately after the cross-linking reaction between polymer binders
The Containing such a structural unit in the polymer composition
In-cured film formation, ie insoluble in developer and organic solvent
It happens very quickly. Usually using radical polymerization
In the case of cured film formation, a cured film with sufficient strength is often used.
To suppress radical polymerization inhibition by external oxygen to obtain,
Oxygen blocking on the upper layer of the recording layer for the purpose of sufficient reaction
A layer (protective layer) is provided, but the binder of the present invention is used.
In the case of
Yes. Therefore, it is no longer necessary to provide an oxygen barrier layer
It has a merit. However, the content of this structural unit is 30 mol.
%, The cured film is formed, that is, a developer or an organic solvent.
Although insolubilization to
I had a problem that it was easy to live. The scratch left here
A film mechanically scratches the recording layer surface with the tip of a nail or the tip of a needle.
The part remains as a film even after development processing.
When this happens, it is a non-image area.
However, if it is transferred to printed matter as an image,
That's what it says. In this way, scratches are likely to form a scratch film.
If you use a lithographic printing plate precursor that supports auto mode,
Play with care when handling or playing as an exposure device
Hands such as a residual film appearing on the plate holder of the tossetter
The printing plate has poor ring characteristics. Therefore, the general formula (1),
(2) At least one of the structural units represented by (3)
Containing 0.1 mol or more and less than 30 mol% of seed, radical
By using an onium salt compound as an initiator, curability
To solve the above problems related to scratched film without damaging
I was able to. In addition, more laser
Crosslink reaction occurs immediately after the occurrence of dicarls
Other small molecules in the recording layer to form a hardened film with high density
Components such as photothermal conversion agents cause ablation.
However, emission from the recording layer is suppressed, and the optical system is contaminated.
It is considered that the dyeing is suppressed. Also, having such a structural unit
And other materials that make up the binder polymer and image recording material
Compatibility with components, for example, compounds that generate radicals is improved.
To prevent the phase separation of the composition over time.
Therefore, it is considered that the storage stability is excellent. In the present invention, “heat mode pair”
“Adaptive” means that recording by heat mode exposure is possible.
Means. Hereinafter, heat mode exposure in the present invention
The definition of is described in detail. Hans-Joachim
Time, IS & Ts NIP 15: 1999 I
international Conference o
n Digital Printing Technology
logs. P. 209, as described in
Light absorbers (eg, dyes) are photoexcited in photoconductor materials.
Through chemical or physical changes.
From photoexcitation to chemical or physical changes in light-absorbing materials
There are roughly two modes in this process.
Is known. One is the photo-excited light-absorbing material
Any photochemical interaction with other reactants in the photomaterial
(E.g. energy transfer, electron transfer)
As a result, the activated reactant is shown in the image above.
Causes chemical or physical changes necessary for formation
And the other is photoexcited light absorption.
The collected material generates heat and deactivates, and the heat is used to react with it.
Cause the chemical or physical changes necessary for image formation as described above.
It is a so-called heat mode that wakes up. In addition, substance is station
It explodes explosively by the energy of light gathered in places
Ablation and one molecule absorb many photons at once
There are special modes such as multiphoton absorption, but they are omitted here.
The An exposure process using each of the above modes
This is called photon mode exposure and heat mode exposure. Fo
The technical difference between ton mode exposure and heat mode exposure
A few photons to be exposed for the energy of the target reaction
It can be used by adding the amount of energy.
For example, consider using n photons to cause a reaction.
Yeah. Photon mode exposure uses photochemical interaction
Therefore, the principle of conservation of quantum energy and momentum is important.
Use one photon of energy by subcontracting
I can't. In other words, to cause some kind of reaction
Relationship of “one photon energy amount ≧ reaction energy amount”
is required. On the other hand, after heat excitation in heat mode exposure
To generate heat and convert light energy into heat
The amount of energy can be added. Therefore, "n pieces
The relationship of “photon energy amount ≧ reaction energy amount”
That will be enough. However, heat addition is necessary for this energy amount addition.
Limited by diffusion. In other words, the exposure area that we are paying attention to now
The next light from the minute (reaction point) until the heat escapes by heat diffusion
If an excitation-deactivation process occurs and heat is generated, the heat is reliably stored.
Product addition results in a temperature rise in that part. But next
If the heat generation is slow, the heat escapes and does not accumulate. One
In heat mode exposure, the same total exposure energy is used.
Even when there is a short amount of light irradiation
Result when irradiated with low energy for a long time
However, a shorter time is advantageous for heat accumulation. Of course, in photon mode exposure, subsequent reactive species
A similar phenomenon may occur due to the diffusion of
In fact, this does not happen. That is, photosensitive material
In photon mode, the exposure power
Density (W / cm²) (= Energy density per unit time
Sensitivity of the photosensitive material (reaction required for image formation)
Energy amount) is constant, but heat mode
Will increase the intrinsic sensitivity of the photosensitive material with respect to the exposure power density.
Will be. Therefore, it is practically used as an image recording material.
In addition, fix the exposure time enough to maintain the required productivity.
Then, when comparing each mode, photon mode exposure
Is usually about 0.1 mJ / cm²Achieved high sensitivity
Because the reaction occurs at any small exposure dose,
The problem of low exposure fogging in unexposed areas is likely to occur. Against this
In heat mode exposure, the exposure amount is not more than a certain level.
The reaction with the thermal stability of the photosensitive material
Usually 50mJ / cm²Degree is required, but low exposure
The problem of fog is avoided. In effect, heat mode exposure is sensitive.
Exposure power density on the plate surface of the material is 5000 W / cm²Less than
Necessary, preferably 10,000 W / cm²Necessary
It becomes important. However, although not detailed here, 5.0
× 10^FiveW / cm²Use the above high power density laser
It is favorable because of problems such as ablation and contamination of the light source.
It ’s not good. [0015] BEST MODE FOR CARRYING OUT THE INVENTION The image recording material of the present invention is described below.
And will be described in detail. The image recording material of the present invention comprises (A)
The structural unit represented by the general formula (1), (2), (3)
That is, at least one kind is 0.1 mol% or more and 30 mol%
Soluble or swell in water or aqueous alkaline solution
Polymer compound (hereinafter referred to as specific alkali-soluble polymer
), (B) a photothermal conversion agent, and (C) (B) light.
Heat mode of light of a wavelength that the heat conversion agent can absorb
Containing compounds that generate radicals upon exposure to light
It is characterized by. In addition, the heat mode compatible negative print
The image recording material contains (D) a radical polymerizable compound.
be able to. The following is used for the image recording material of the present invention.
Each possible compound will be described in turn. [(A) Specific alkali-soluble polymer]
It is bright and used as a binder component in image recording materials.
The child compound is represented by the general formula (1), (2), (3)
0.1 mol% or more of at least one of the structural units,
Soluble in water or alkaline aqueous solution containing less than 30 mol%
Alternatively, it is a polymer compound that swells. [0017] [Chemical 3] In the general formula (1), R¹~ R^ThreeHaso
Each independently represents a monovalent organic group, but a hydrogen atom, substituted
And an alkyl group which may have a group.
R ¹, R²Is preferably a hydrogen atom, R^ThreeIs a hydrogen atom,
A methyl group is preferred. R^Four~ R⁶Are independently monovalent
Represents an organic group of R^FourAs a hydrogen atom or a substitution
And an alkyl group which may have a group.
Are preferably a hydrogen atom, a methyl group or an ethyl group. Also,
R^Five, R⁶Each independently represents a hydrogen atom or a halogen atom.
Child, alkoxycarbonyl group, sulfo group, nitro group,
An ano group, an alkyl group which may have a substituent, and a substituent
Aryl group which may be substituted, alkoxy which may have a substituent
Si group, aryloxy group which may have a substituent, substituent
An alkylsulfonyl group that may have a substituent,
Good arylsulfonyl groups, etc.
Has a hydrogen atom, an alkoxycarbonyl group, and a substituent.
An alkyl group that may be substituted, and an aryl group that may have a substituent
preferable. Here, the substituent that can be introduced is methoxy.
Sicarbonyl group, ethoxycarbonyl group, isopropio
Xoxycarbonyl group, methyl group, ethyl group, phenyl group, etc.
Is mentioned. A¹, X are independently oxygenated
Child, sulfur atom, or -N (R^{twenty one}) −, Where
R^{twenty one}As a hydrogen atom, an alkyl optionally having a substituent.
And the like. G¹Represents a divalent organic group
However, the alkyl group which may have a substituent is preferable. Than
Preferably, it may have a substituent having 1 to 20 carbon atoms.
Alkyl group, cyclyl having 3 to 20 carbon atoms
It may have a cycloalkyl group and a substituent having 6 to 20 carbon atoms.
Aromatic groups, etc. are mentioned.
A linear or branched alkyl group having 1 to 10 carbon atoms,
Cycloalkyl which may have a substituent having 3 to 10 carbon atoms
Group, an aromatic group which may have a substituent of 6 to 12 carbon atoms
It is preferable in terms of performance such as strength and developability. Where G¹As a substituent in
A group in which an elementary atom is bonded to a heteroatom, such as a hydroxyl group, an
Those that do not contain mino groups, thiol groups, or carboxyl groups
preferable. Such a hydrogen atom bonded to a heteroatom
As a initiator having a group in the linking group portion and an initiator described later
When an onium salt compound is used in combination, the storage stability deteriorates. [0021] [Formula 4] In the general formula (2), R⁷~ R⁹Haso
Each independently represents a monovalent organic group, but a hydrogen atom, substituted
And an alkyl group which may have a group.
R ⁷, R⁸Is preferably a hydrogen atom, R⁹Is a hydrogen atom,
A methyl group is preferred. R^Ten~ R¹²Are each independently 1
The organic group is a valent organic group.
For example, hydrogen atom, halogen atom, dialkylamino
Group, alkoxycarbonyl group, sulfo group, nitro group,
An ano group, an alkyl group which may have a substituent, and a substituent
Aryl group which may be substituted, alkoxy which may have a substituent
Si group, aryloxy group which may have a substituent, substituent
An alkylsulfonyl group that may have a substituent,
Good arylsulfonyl groups, etc.
Has a hydrogen atom, an alkoxycarbonyl group, and a substituent.
Alkyl group which may be substituted, aryl group which may have a substituent
Is preferred. Here, as the substituent that can be introduced,
What was mentioned in Formula (1) is illustrated similarly. A²Each independently represents an oxygen atom, sulfur
Yellow atom or -N (R^{twenty one})-, Where R^{twenty one}When
For example, a hydrogen atom or an alkyl group which may have a substituent.
And so on. G²Represents a divalent organic group, but is substituted
An alkyl group which may have a group is preferred. Preferably,
Alkyl group which may have a substituent having 1 to 20 carbon atoms, carbon
Cycloalkyl optionally having a substituent of 3 to 20 primes
Group, aromatic group which may have a substituent having 6 to 20 carbon atoms
Among them, the number of carbons that may have a substituent
1 to 10 linear or branched alkyl group, 3 to 3 carbon atoms
Cycloalkyl group optionally having 10 substituents, carbon number
Aromatic groups optionally having 6 to 12 substituents are strong and developable
It is preferable in terms of performance such as property. Where G²Substituent in
As a group in which a hydrogen atom is bonded to a heteroatom, for example
Hydroxyl group, amino group, thiol group, carboxyl group
What does not contain is preferable. Such hydrogen atoms are heterogeneous.
Those having a group bonded to an atom in the linking group moiety, and those described later.
Storage stability when combined with an onium salt compound as an initiator
Deteriorates. Y is an oxygen atom, a sulfur atom, -N
(R^{twenty three})-Or a phenylene group which may have a substituent
Represent. Where R^{twenty three}As having a hydrogen atom and a substituent
And an alkyl group that may be used. [0024] [Chemical formula 5] In the general formula (3), R¹³~ R¹⁵Is
Each independently represents a monovalent organic group,
And an alkyl group that may have a substituent.
R¹³, R¹⁵Is preferably a hydrogen atom, R¹⁵Is a hydrogen field
A child or a methyl group is preferred. R¹⁶~ R²⁰Are independent
Represents a monovalent organic group, R¹⁶~ R²⁰For example, hydrogen
Atom, halogen atom, dialkylamino group, alkoxy
Carbonyl group, sulfo group, nitro group, cyano group, substituent
An alkyl group that may have a substituent and an ant that may have a substituent
Group, an alkoxy group which may have a substituent, a substituent
May have an aryloxy group and a substituent.
Alkylsulfonyl group, aryl optionally having substituent (s)
Sulfonyl group, etc., among them, hydrogen atom,
Lucoxycarbonyl group, optionally substituted alkyl
An aryl group which may have a group or a substituent is preferable. Introduction
Examples of the substituent that can be used are those shown in the general formula (1).
Is exemplified. A^Three, Z is an oxygen atom, a sulfur atom, or
Is -N (R^{twenty one})-. R^{twenty one}As general formula (1)
The same thing as in is mentioned. G^ThreeRepresents a divalent organic group,
The alkyl group which may have is preferable. Preferably carbon
Alkyl group which may have a substituent having 1 to 20 carbon atoms
Cycloalkyl group optionally having 3 to 20 substituents, charcoal
An aromatic group that may have a substituent having a prime number of 6 to 20 is listed.
In particular, the carbon number of 1 to 1 which may have a substituent
0 linear or branched alkyl group, 3 to 10 carbon atoms
Cycloalkyl group which may have a substituent, carbon number 6-1
The aromatic group which may have 2 substituents has strength, developability, etc.
It is preferable in terms of performance. Where G^ThreeAs a substituent in
Is a group in which a hydrogen atom is bonded to a heteroatom, such as hydroxy
Does not contain a group, amino group, thiol group or carboxyl group
Those are preferred. Such hydrogen atoms are bonded to heteroatoms.
Having a combined group in the linking group portion, and an initiator to be described later
Storage stability deteriorates when combined with onium salt compound
To do. Heat type negative image recording of the present invention
Used as an essential ingredient in the material (A) Specific alkali is acceptable
The soluble polymer is less of the synthesis methods 1) to 3) shown below.
Both can be manufactured by one. Synthesis Method 1) Represented by the following general formula (4)
0.1 mol% or more of at least one radical polymerizable compound
Less than 0 mol% and a structural unit represented by the following general formula (4)
One or more other radically polymerizable compounds not having
Copolymerization is carried out by the usual radical polymerization method.
After synthesizing the precursor of the child compound,
Ton is extracted, L is desorbed, and expressed by the general formula (1)
A method for obtaining a desired polymer compound having a structure. this
In the production of polymer compound precursors, generally known suspensions are used.
Suspension polymerization method or solution polymerization method can be applied
The As the constitution of the copolymer, a block copolymer,
Random copolymer, graft copolymer, etc.
May be. [0029] [Chemical 6] In the formula, L represents an anionic leaving group. Good
Preferred examples include halogen atoms and sulfonate esters.
It is done. R^Three~ R⁶, A¹And G¹, X in general
The same ones listed in formula (1) can be used.
The In addition, the base used to cause the elimination reaction
Either inorganic or organic compounds can be used.
Yes. Preferred inorganic compound bases include sodium hydroxide
, Potassium hydroxide, sodium carbonate, sodium bicarbonate
Um, potassium carbonate, potassium bicarbonate, etc.
Organic compound bases include sodium methoxide, nato
Gold such as lithium ethoxide, potassium t-butoxide
Genus alkoxide, triethylamine, pyridine, diiso
Organic amine compounds such as propylethylamine
I can get lost. Radical polymerizable compound represented by the general formula (4)
As the product, the following compounds (M-1) to (M-12)
Can be mentioned as an example,
There is no. [0031] [Chemical 7] [0032] [Chemical 8]These radically polymerizable compounds are commercially available products.
Or, the patent application 20 previously proposed by the present inventors
Easy by the synthesis method described in the specification of 00-24969
Available at: Synthesis Method 2) Specific methods as detailed below
0.1 or more of radically polymerizable compounds having a functional group
More than mol% and less than 30 mol% and have no specific functional group
One or more other radically polymerizable compounds are
Copolymerized by dical polymerization to synthesize trunk polymer compounds
After that, the functional group of the side chain and the following general formula (5) or
(6), a compound having the structure represented by (7),
And represented by the general formula (1) or (2), (3).
A method for obtaining a desired polymer compound having a structure. Trunk height
There are generally known suspension polymerization methods for the production of molecular compounds
Alternatively, a solution polymerization method or the like can be applied. That weight
The composition is composed of block copolymer, random copolymer
Any of a coalescence, a graft copolymer, etc. may be sufficient. [0035] [Chemical 9] In the general formula (5), R^Four~ R⁶Is the general formula
The same ones listed in (1) can be used.
The Of a low molecular weight compound having a group represented by the general formula (5)
Examples include 2-hydroxylethyl acrylate, 2
-Hydroxylethyl methacrylate, 4-hydroxy
Butyl acrylate, 4-hydroxybutyl methacrylate
, Acrylic acid, methacrylic acid, acrylic acid chloride
Methacrylic acid chloride, N, N-dimethyl-2-a
Minoethyl methacrylate, 2-chloroethyl methacrylate
Rate, 2-isocyanate ethyl methacrylate, 3-
Propyl isocyanate, glycidyl acrylate
Relate, glycidyl methacrylate, 3,4-epoxy
Cycyclohexylmethyl acrylate, 3,4-epoxy
Cycyclohexylmethyl methacrylate, 2-bromoe
Tyl methacrylate, 3-bromopropyl methacrylate
, 2-hydroxyethyl methacrylamide, 4-hydride
Roxybutyl methacrylamide, itaconic acid, etc.
It is. In the general formula (6), R^Ten~ R¹²The above general
The same ones listed in formula (2) can be used.
The Of a low molecular weight compound having a group represented by the general formula (6)
Examples include ethylene glycol monovinyl ether,
Propylene glycol monovinyl ether, butylene
Recall monovinyl ether, diethylene glycol
No vinyl ether, 1-chloroethyl vinyl ether,
1-aminoethyl vinyl ether, 4-chloromethyls
Examples include tylene, p-styrene carboxylic acid, etc.
The In the general formula (7), R¹⁶~ R²⁰The above general
The same ones listed in formula (3) can be used.
The As a compound having a structure represented by the general formula (7)
Are allyl alcohol, allylamine, diallylamine
, 2-allyloxyethyl alcohol, 2-chloro-1
-Butene, allyl isocyanate, etc.
The Examples of specific functional groups include hydroxy acid
Group, carboxyl group, carboxylic acid halide group, carvone
Acid anhydride group, amino group, halogenated alkyl group, isocyanate
Examples include ananate group and epoxy group. These functional groups
Examples of the radical polymerizable compound having 2-hydroxy
Silethyl acrylate, 2-hydroxylethyl meta
Acrylate, 4-hydroxybutyl acrylate, 4-
Hydroxybutyl methacrylate, acrylic acid, methacrylate
Lauric acid, acrylic acid chloride, methacrylic acid chloride,
N, N-dimethyl-2-aminoethyl methacrylate,
2-chloroethyl methacrylate, 2-isocyanate
Tyl methacrylate, propyl methacrylate 3-isocyanate
Relate, glycidyl acrylate, glycidyl methacrylate
Relate, 3,4-epoxycyclohexylmethyl acetate
Relate, 3,4-epoxycyclohexylmethyl meta
Chlorate, 2-bromoethyl methacrylate, 3-butyl
Lomopropyl methacrylate, 2-hydroxyethyl methacrylate
Tacrylamide, 4-hydroxybutyl methacrylate
And itaconic acid. Furthermore, other radicals having no specific functional group
Examples of cal-polymerizable compounds include, for example, acrylic acid ester.
Stealth, methacrylates, N, N-2 substituted amines
Kurylamides, N, N-2-substituted methacrylamides,
Styrenes, acrylonitriles, methacrylonitrile
Radically polymerizable compounds selected from the group
The Specifically, for example, alkyl accelerators
(The alkyl group preferably has 1 to 20 carbon atoms.
Acrylic esters such as
For example, methyl acrylate, ethyl acrylate, acrylic acid
Propyl, butyl acrylate, amyl acrylate, acrylic
Ethyl hexyl acrylate, octyl acrylate, acrylic
Acid-t-octyl, chloroethyl acrylate, 2,2
-Dimethylhydroxypropyl acrylate, 5-hydride
Loxypentyl acrylate, trimethylolpropane
Monoacrylate, pentaerythritol monoacrylate
Glycidyl acrylate, benzyl acrylate
, Methoxybenzyl acrylate, furfuryl acrylic
Rate, tetrahydrofurfuryl acrylate, etc.),
Aryl acrylates (eg phenyl acrylate)
Such), Alkyl methacrylate (of the alkyl group)
Methacryl such as those having 1 to 20 carbon atoms are preferred)
Acid esters (eg methyl methacrylate, ethyl
Methacrylate, propyl methacrylate, isopropyl
Methacrylate, amyl methacrylate, hexylme
Tacrylate, cyclohexyl methacrylate, benzy
Methacrylate, chlorobenzyl methacrylate,
Cutyl methacrylate, 4-hydroxybutyl methacrylate
Rate, 5-hydroxypentyl methacrylate, 2,
2-Dimethyl-3-hydroxypropyl methacrylate
, Trimethylolpropane monomethacrylate, pen
Taerythritol monomethacrylate, glycidyl meta
Chlorate, furfuryl methacrylate, tetrahydro
Furfuryl methacrylate), aryl methacrylate
(Eg phenyl methacrylate, cresyl meta
Acrylate, naphthyl methacrylate, etc.), Styrene such as styrene and alkylstyrene
(E.g., methyl styrene, dimethyl styrene,
Limethyl styrene, ethyl styrene, diethyl styrene
, Isopropyl styrene, butyl styrene, hexyl
Styrene, cyclohexylstyrene, decylstyrene,
Benzyl styrene, chloromethyl styrene, trifluoro
Rumethylstyrene, ethoxymethylstyrene, acetoxy
Dimethyl styrene), alkoxy styrene (eg
Methoxystyrene, 4-methoxy-3-methylstyrene
, Dimethoxystyrene, etc.), halogen styrene (eg
For example, chlorostyrene, dichlorostyrene, trichlors
Tylene, tetrachlorostyrene, pentachlorostyrene
, Bromostyrene, dibromostyrene, iodostyrene
, Fluorstyrene, trifluorostyrene, 2-butyl
Lom-4-trifluoromethylstyrene, 4-fluoro
-3-trifluoromethylstyrene), acryloni
Examples include tolyl and methacrylonitrile. these
One type or two or more types can be used. Synthesis method 3) The above general formula (6) or
An unsaturated group represented by (7), and further than the unsaturated group
Radius having ethylenically unsaturated groups rich in addition polymerization
Copolymerize with one or more of calpolymerizable compounds,
The desired height having the structure represented by formula (2) or (3)
To obtain a molecular compound (provided that general formula (6) or (7)
The content of the structural unit having an unsaturated group represented by
It is 0.1 mol% or more and less than 30 mol% in the compound.
Adjust the feed amount), or the above general formula
The unsaturated group represented by (6) or (7) and the unsaturated group
Furthermore, ethylenically unsaturated groups rich in addition polymerization
0.1 mol% or less of one or more radical polymerizable compounds having
On the other hand, less than 30 mol% and other groups having no such groups
One or more radical polymerizable compounds and a normal radical
Copolymerization by a polymerization method, and the general formula (2) or
A desired polymer compound having the structure represented by (3) is obtained.
Method. For the production of polymer compounds, generally known suspensions
Polymerization method or solution polymerization method can be applied
The As the constitution of the copolymer, a block copolymer,
Random copolymer, graft copolymer, etc.
May be. The unsaturated group represented by the general formula (6) and the unsaturated group
More ethylenic unsaturation than addition of hydration groups
As the radically polymerizable compound having a group,
Chlorate, vinyl methacrylate, 2-phenyl vinyl
Acrylate, 2-phenyl vinyl methacrylate,
1-propenyl acrylate, 1-propenyl methacrylate
Rate, vinyl acrylamide, vinyl methacrylate
An example is given. An unsaturated group represented by the general formula (7);
More ethylenic unsaturation than addition of saturated groups
As the radical polymerizable compound having a group, allyl
Chlorate, allyl methacrylate, 2-allyloxye
Tyl acrylate, 2-allyloxyethyl methacrylate
, Propargyl acrylate, propargyl methacrylate
Rate, N-allyl acrylate, N-allyl methacrylate
Rate, N, N-diallyl acrylate, N, N-dia
Lyl methacrylate, allyl acrylamide, allyl methacrylate
An example is tacrylamide. Any of these production methods (synthesis methods)
Do one or combine (A)
A specific alkali-soluble polymer may be obtained. General formula
Content of structural unit represented by (1), (2), (3)
Is in the range of 0.1 mol% or more and less than 30 mol%.
And a more preferable range is 10 to 25 mol%.
The Within this range, curability and printing durability, and scratch residue film
There is a tendency that the suppression of is good. Specific alkali-soluble polymerization according to the present invention
The compound has various performances such as non-image area removability.
For this purpose, a radical polymerizable compound having an acid group is copolymerized.
May be. Such an acid group having radical polymerizability
For example, carboxylic acid, sulfonic acid, phosphoric acid group, etc.
Particularly preferred are carboxylic acids. Cal
Examples of radically polymerizable compounds containing boronic acid include
Acrylic acid, methacrylic acid, itaconic acid, croton
Acid, incrotonic acid, maleic acid, p-carboxyl
There are ethylene and the like, and particularly preferred are acrylic acid,
Methacrylic acid, p-carboxylstyrene. this
One or more of these can be used,
The content preferably used for the polymerization component is 0 to 50 mol%.
Particularly preferably, image strength by alkaline water development is used.
From the viewpoint of suppressing damage, it is 0-30 mol%
The If it exceeds 30 mol%, the image strength is increased by alkaline water development.
Will be more susceptible to damage. Used for the synthesis of such polymer compounds.
Examples of the solvent that can be used include ethylene dichloride,
Cyclohexanone, methyl ethyl ketone, acetone,
Ethanol, propanol, butanol, ethanol
Tylene glycol monomethyl ether, ethylene glycol
Monoethyl ether, 2-methoxyethyl acetate
1-methoxy-2-propanol, 1-methoxy-
2-propyl acetate, N, N-dimethylformami
N, N-dimethylacetamide, dimethylsulfoxide
Sid, toluene, ethyl acetate, methyl lactate, ethyl lactate
Etc. These solvents may be used alone or in combination of two or more.
You may mix on top. (A) Specific alkaline water soluble compound of the present invention
The product is a mass average molecular weight, preferably 40,000 or more
More preferably, it is in the range of 80,000 to 180,000.
The If it is less than 80,000, the cured film strength is insufficient, exceeding 180,000.
As a result, developability deteriorates. Also, (A) specific according to the present invention
The polymer compound may contain unreacted monomers.
Yes. In this case, the proportion of monomer in the polymer compound
Is preferably 15% by mass or less. The polymer compound according to the present invention is used alone.
Also, two or more kinds may be mixed and used. The general formula
(1), (2), other height not having the group represented by (3)
You may mix and use a molecular compound. In this case, other high
The molecular compound is 50% by mass or less in the polymer compound.
Preferably, it is 10 mass% or less. Image recording of the present invention
The content of the specific polymer compound (A) contained in the material is
About 5 to 95% by mass in form, preferably about 40 to
90% by mass. If the content is too low, record
The layer strength is insufficient and the printing durability tends to decrease.
If it is too close, it may affect image formation and may reduce image quality.
Which is not preferable. The (A) specific alkali according to the present invention will be described below.
Representative synthetic examples of soluble polymers and specific polymer compounds
The present invention is not limited to these examples.
Yes. (Synthesis example) 1) Synthesis of polymer compound (1) (Synthesis Example 1) 500ml three-necked flask with condenser and stirrer
To Suko, 240 ml of 1-methoxy-2-propanol
And heated to 70 ° C. Exemplified compounds under nitrogen flow
(M-4) 30.9 g, benzyl methacrylate 74.
0g, Methacrylic acid 12.1g, V-65 (Wako Pure Chemicals
0.870 g of 1-methoxy-2-propanol 2
A 40 ml solution was added dropwise over 2.5 hours. In addition, 7
The reaction was performed at 0 ° C. for 2 hours. The reaction mixture was cooled to 0 ° C.
Then, 56.7 g of triethylamine was added dropwise with stirring.
And let it react for 12 hours while gradually raising the temperature to room temperature.
It was. The reaction mixture was cooled to 0 ° C. and then stirred with 5M.
  Add HCl dropwise until the pH of the reaction mixture is 6 or less.
It was. The reaction solution was poured into 5 L of water to precipitate a polymer. This
This is filtered, washed and dried to obtain the polymer compound (1).
It was. From the NMR spectrum, all the groups derived from (M-4)
It was confirmed that it was converted to an acrylic group. Police
Gel permeation chromatography using len as standard
The mass average molecular weight is measured by the Raffy method (GPC).
As a result, it was 97,000. 2) Synthesis of trunk polymer compound (1) 1000ml three-necked fan with condenser and stirrer
To Lasco, add 175 g of 1-methoxy-2-propanol.
And heated to 70 ° C. Methacrylic acid 6 under nitrogen flow
9.7 g, t-butyl methacrylate 69.7 g, V-
59 (manufactured by Wako Pure Chemical Industries) 0.673 g of 1-methoxy-2-
175 g of propanol solution was added dropwise over 2.5 hours
It was. Furthermore, it was made to react at 70 degreeC for 2 hours. Cool to room temperature
Then, it was poured into 3 L of water to precipitate a polymer. this
Is filtered, washed and dried, and the trunk polymer compound (1) 8
3.0 g was obtained. Gel par with polystyrene as standard
By the Miation Chromatography Method (GPC)
As a result of measuring the mass average molecular weight, it was 121,000.
It was. The acid value measured by titration is 2.30 meq /
g. 3) Synthesis of polymer compound (2) (Synthesis example)
2) 1000ml three-necked fan with condenser and stirrer
In LASCO, 80 g of the trunk polymer compound (1) and p
-Put 1 g of methoxyphenol, dimethyl sulfoxide
After dissolving in 320 g, using a dropping funnel, 1,8
-Diazabicyclo [5.4.0] -7-undecene 4
8.0 g was dripped. After stirring at room temperature for 30 minutes,
19.5 g of bromoethyl methacrylate was added dropwise, and 60
Stir at 8 ° C. for 8 hours. After cooling to room temperature, in 3 L of water
The polymer was precipitated. This is filtered, washed and dried.
It dried and 72g of polymer compounds (2) were obtained. polystyrene
Gel permeation chromatograph using as standard substance
As a result of measuring the mass average molecular weight by the GPC method (GPC)
As a result, it was 128,000. Also measured by titration
The acid value was 1.01 meq / g. Trunk polymer compound
Difference between acid value of (1) and acid value of polymer compound (2) and H
  NMR confirmed the structure shown in Table 1 below.
It was. 4) Synthesis of polymer compound (3) (Synthesis example)
3) 1000ml three-necked fan with condenser and stirrer
To Lasco, 80 g of the trunk polymer compound (1), p-meth
Add 1 g of xylphenol and dimethyl sulfoxide 320
After being dissolved in g, 1,8-dia is added using a dropping funnel.
Zabicyclo [5.4.0] -7-undecene 48.0g
Was dripped. After stirring for 30 minutes at room temperature, p-chloromethyl
16.0 g of styrene styrene was added dropwise and stirred at 60 ° C. for 8 hours.
did. After cooling to room temperature, it is poured into 3 L of water to give a polymer
Was precipitated. This is filtered, washed, dried, and polymerized
81.2 g of Compound (3) was obtained. Polystyrene as standard
Gel permeation chromatography method (G
PC) and the mass average molecular weight was measured.
5,000. The acid value measured by titration is
It was 1.02 meq / g. Of trunk polymer compound (1)
Difference between acid value and acid value of polymer compound (3) and H NMR
As a result, the structure shown in Table 1 was confirmed. 5) Synthesis of polymer compound (4) (Synthesis example)
4) 2000ml three-necked fan with condenser and stirrer
750 g of 1-methoxy-2-propanol was added to Lasco.
And heated to 70 ° C. Allyl methacrylate in a nitrogen stream
Rate 88.3 g, methacrylic acid 9.0 g, benzyl ester
Tacrylate 74.0 g, V-59 (manufactured by Wako Pure Chemical Industries)
679 g of 1-methoxy-2-propanol 750 g dissolved
The liquid was added dropwise over 2 hours and a half. 2 o'clock at 70 ° C
It was made to react between. After cooling to room temperature, throw it into 3 L of water.
The polymer was precipitated. This is filtered, washed and dried
As a result, 150.0 g of a polymer compound (4) was obtained. Police
Gel permeation chromatography using len as standard
The mass average molecular weight is measured by the Raffy method (GPC).
As a result, it was 132,000. Also measured by titration.
The determined acid value was 1.00 meq / g. (Synthesis Examples 5 to 17) Similar to Synthesis Examples 1 to 4
Change the monomer type and composition ratio,
Molecular compounds (5) to (17) were synthesized. These polymerizations
The mass average molecular weight of the body is measured by the same method as in Synthesis Examples 1 to 4
did. (A) obtained by the above synthesis method
The soluble resins are shown in the following Tables 1 to 4 in terms of the structure and weight of the structural units.
Shown in total molar ratio, and also shows the measured mass average molecular weight
(Polymer Compound 1 to Polymer Compound 17). [0058] [Table 1][0059] [Table 2][0060] [Table 3][0061] [Table 4] [(B) Photothermal conversion agent] Image recording material of the present invention
The material emits heat mode exposure, typically infrared
Uses a photothermal conversion agent because recording is performed with a laser.
It is essential. A photothermal conversion agent absorbs light of a predetermined wavelength.
It has a function of converting into heat. Occurred at this time
Due to heat, component (C) described later, that is, (B) photothermal change
The heat mode exposure of light of a wavelength that can be absorbed by the replacement agent
Compounds that generate dicarls decompose and generate radicals
The As a photothermal conversion agent used in the present invention
Absorb the light energy radiation used for recording and heat
There is no particular limitation on the absorption wavelength range as long as it is a substance that generates oxygen.
Can be. Preferred for use in the present invention
Photothermal converters are compatible with readily available high power lasers.
From the viewpoint, it has an absorption maximum at a wavelength of 760 nm to 1200 nm.
Infrared absorbing dye or pigment. Examples of the dye include commercially available dyes and “dye”.
"Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1968)
Known materials described in the literature can be used. concrete
Azo dyes, metal complex azo dyes, pyrazolone azo dyes
, Naphthoquinone dye, anthraquinone dye, phthalose
Anine dye, carbonium dye, quinone imine dye,
Chin dye, cyanine dye, squarylium dye, piliri
Um salt, metal thiolate complex, oxonol dye, dii
Such as monium dye, aminium dye, croconium dye, etc.
Dyes. Preferred dyes include, for example, JP-A-5.
8-125246, JP 59-84356, JP
Sho 59-202829, JP-A 60-78787, etc.
Cyanine dyes described in JP-A-58-1736
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent No. 94595, JP-A-5
8-112793, JP-A-58-224793, Special
No. 59-48187, JP-A-59-73996,
JP-A-60-52940, JP-A-60-63744
Naphthoquinone dyes described in JP-A-58-1
Squarylium dyes described in No. 12792, etc.
Cyanine dyes described in British Patent 434,875
Can. US Pat. No. 5,156,938
The near-infrared absorption sensitizer described above is also preferably used.
Substituted aryl radicals as described in allowed 3,881,924.
Nzo (thio) pyrylium salt, JP-A 57-142645
No. (US Pat. No. 4,327,169)
Nthiapyrylium salt, JP 58-181051 A
58-220143, 59-41363, 59
-84248, 59-84249, 59-14
6063 and 59-146061
Pyrylium compounds, described in JP-A-59-216146
Cyanine dyes described in US Pat. No. 4,283,475
Pentamethine thiopyrylium salt, etc.
No. 514, No. 5-19702
Umum compounds are also preferably used. Another preferred example of the dye is rice.
In Japanese Patent No. 4,756,993, formula (I),
Name near-infrared absorbing dyes listed as (II)
You can. Of these dyes, particularly preferred
Cyanine dyes, phthalocyanine dyes, oxonol
Dyes, squarylium pigments, pyrylium salts, thiopyri
Examples thereof include a lithium dye and a nickel thiolate complex. The
In addition, dyes represented by the following general formulas (a) to (e)
Is preferable because of its excellent photothermal conversion efficiency.
The cyanine dye represented by (a) is a polymerizable composition of the present invention.
High polymerization activity and stable when used in
It is most preferable because of its excellent property and economy. [0069] Embedded image In general formula (a), X¹Is a hydrogen atom, halo
Gen atom, -NPh₂, X²-L¹Or the group shown below
Represent. Where X²Indicates an oxygen atom or a sulfur atom
And L¹Is a hydrocarbon group having 1 to 12 carbon atoms, hetero
Aromatic rings with atoms, carbon atoms containing heteroatoms 1
-12 hydrocarbon groups are shown. Here, heteroatoms and
Represents N, S, O, a halogen atom, or Se. [0071] Embedded image R¹And R²Are each independently
A hydrocarbon group having 1 to 12 molecules is shown. Storage of recording layer coating solution
From stability, R¹And R²Is charcoal with 2 or more carbon atoms
It is preferably a hydride group, and further R¹And R²What is
Bonded together to form a 5-membered or 6-membered ring
Is particularly preferred. Ar¹, Ar²Are the same or different
Aromatic hydrocarbons that may have a substituent
Indicates the basis. Preferred aromatic hydrocarbon groups include ben
Zen ring and naphthalene ring are mentioned. Also preferred
As the substituent, hydrocarbon having 12 or less carbon atoms
Group, halogen atom, alkoxy having 12 or less carbon atoms
Groups. Y¹, Y²Are the same or different
And may have a sulfur atom or 12 or fewer carbon atoms
A dialkylmethylene group; R^Three, R^FourAre the same
May be the same or different, and may have a substituent.
A hydrocarbon group having 20 or less carbon atoms is shown. Preferred position
As the substituent, an alkoxy group having 12 or less carbon atoms,
A carboxyl group and a sulfo group are mentioned. R^Five, R⁶, R
⁷And R⁸Can be the same or different,
Indicates a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms
The From the availability of raw materials, a hydrogen atom is preferred. Ma
Za^-Represents a counter anion. However, R¹~ R⁸of
When any of the sulfo groups is substituted, Za^-Is
unnecessary. Preferred Za^-Storage stability of recording layer coating solution
Characteristics, halogen ion, perchlorate ion, tetrafur
Oroborate ion, hexafluorophosphate ion
And sulfonate ions, particularly preferably
Perchlorate ion, hexafluorophosphate ion
And aryl sulfonate ions. In the present invention, it can be suitably used.
Specific examples of the cyanine dye represented by the general formula (a)
In addition to the following examples, Japanese Patent Application No. 11-31062
Paragraph Nos. [0017] to [0019]
Paragraph No. [001] of application 2000-224031
2] to [0038], Japanese Patent Application No. 2000-2111147
Described in paragraph numbers [0012] to [0023] of the booklet
Can be mentioned. [0075] Embedded image [0076] Embedded image[0077] Embedded image [0078] Embedded imageIn the general formula (b), L represents the number of conjugated carbon atoms.
Represents 7 or more methine chains, and the methine chains have a substituent.
The substituents may be bonded together to form a ring structure
May be. Zb⁺Indicates a counter cation. Preferred versus
Thion includes ammonium, iodonium, sulfo
Ni, phosphonium, pyridinium, alkali metal
Thion (Ni⁺, K⁺, Li⁺) And the like. R⁹~
R¹⁴And R¹⁵~ R²⁰Are independently of one another hydrogen atom or halogen
Atom, cyano group, alkyl group, aryl group, alkeni
Group, alkynyl group, carbonyl group, thio group, sulfoni
Selected from the group consisting of
Selected substituents, or two or three of these
Represents the combined substituents, bonded together to form a ring structure
May be. Here, in the general formula (b), L is conjugated charcoal.
Representing a methine chain of 7 atoms and R⁹~ R¹⁴And
And R¹⁵~ R²⁰Are all readily available that represent hydrogen atoms.
From the viewpoint of properties and effects. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (b) include
Can be mentioned as examples. [0081] Embedded image [0082] Embedded image In the general formula (c), Y^ThreeAnd Y^FourIt
Respectively, oxygen atom, sulfur atom, selenium atom, or tellurium source
Represents a child. M represents a methine chain having 5 or more conjugated carbon atoms.
R^{twenty one}~ R^{twenty four}And R^{twenty five}~ R²⁸Are the same
May be different, hydrogen atom, halogen atom, cyano
Group, alkyl group, aryl group, alkenyl group, alkini
Group, carbonyl group, thio group, sulfonyl group, sulfi group
Represents a nyl group, an oxy group or an amino group. In the formula, Z
a^-Represents a counter anion, Z in the general formula (a)
a^-It is synonymous with. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (c) include the following:
Can be mentioned as examples. [0085] Embedded image[0086] Embedded image In the general formula (d), R²⁹Or R³¹Each
Each independently a hydrogen atom, an alkyl group, or an aryl group
Show. R³³And R³⁴Each independently represents an alkyl group or a substituent
An oxy group or a halogen atom is shown. n and m are each
Each independently represents an integer of 0 to 4. R²⁹And R³⁰Or
R³¹And R³²May be bonded to each other to form a ring.
R²⁹And / or R³⁰Is R³³And again R³¹and/
Or R³²Is R³⁴To form a ring.
And R³³Or R³⁴R is present when there are multiple ³³Mutual
Rui or R³⁴They may be bonded to each other to form a ring.
X²And X^ThreeEach independently represents a hydrogen atom, an alkyl group, or
Or an aryl group, X²And X^ThreeAt least one of
Represents a hydrogen atom or an alkyl group. Q has a substituent
May be a trimethine group or a pentamethine group.
In other words, a ring structure may be formed together with a divalent organic group. Z
c^-Represents a counter anion, Z in the general formula (a)
a^-It is synonymous with. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (d) are as follows:
Can be mentioned as examples. [0089] Embedded image [0090] Embedded image In the general formula (e), R³⁵~ R⁵⁰Is that
Independently, a hydrogen atom or halogen atom which may have a substituent.
Child, cyano group, alkyl group, aryl group, alkenyl
Group, alkynyl group, hydroxyl group, carbonyl group, thio group,
Sulfonyl, sulfinyl, oxy, amino,
It shows a nium salt structure. M is two hydrogen atoms or metal
Shows atoms, halometal groups, and oxymetal groups.
The metal atoms contained include IA, IIA, II of the periodic table
IB, IVB group atoms, first, second and third period transition metals,
Lanthanoid elements, among others, copper, magnesium
Iron, zinc, cobalt, aluminum, titanium, vana
Palladium is preferred. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (e) are as follows:
Can be mentioned as examples. [0093] Embedded image 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 pigment include black pigment, yellow face
, Orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Examples include polymer-bound dyes. Specifically, insoluble
Zo pigment, azo lake pigment, condensed azo pigment, chelate azo
Pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, key
Nacridone pigments, dioxazine pigments, isoindole
Non-based pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, firefly
Light pigments, inorganic pigments, carbon black, etc. can be used.
Of these pigments, carbon black is preferred.
is there. These pigments may be used without surface treatment.
Alternatively, a surface treatment may be applied. For surface treatment method
The method of surface coating with resin and wax, surfactant
Method of adhering, reactive substances (eg silane cups)
Ring agents, epoxy compounds, polyisocyanates, etc.)
A method of bonding to the pigment surface is conceivable. Above surface
The treatment method is "Characteristics and application of metal soap" (Shoshobo),
“Printing Ink Technology” (CMC Publishing, 1984) and
To "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Has been described. The particle size of the pigment is in the range of 0.01 μm to 10 μm.
Preferably in the range of 0.05 μm to 1 μm
More preferably, it is particularly 0.1 μm to 1 μm.
It is preferable that it exists in the range. The particle size of the pigment is 0.01μ
When less than m, the stability of the dispersion in the image recording layer coating solution
In addition, it is not preferable, and if it exceeds 10 μm, image recording
It is not preferable in terms of the uniformity of the recording layer. As a method of dispersing the pigment, ink production
And well-known dispersion techniques used for toner production, etc.
The Dispersers include ultrasonic dispersers, sand mills, and atomizers.
Lighter, Pearl mill, Super mill, Ball mill, Y
Impeller, despather, KD mill, colloid mill, da
Inatron, 3-roll mill, pressure kneader, etc.
It is. For details, see “Latest Pigment Application Technology” (CMC Publishing, 1
986). In the present invention, these photothermal conversion agents are
Only one type may be used, or two or more types may be used in combination.
However, from the viewpoint of sensitivity, the dye represented by the general formula (a)
Is most preferred, and in particular, has a diarylamino group
Most preferred are cyanine dyes. These photothermal conversion agents are contained in the recording layer composition.
In addition, 0.1 to 20% by mass of the total solid content is preferably added.
Good. If it is less than this range, exposure
Sensitivity of the change in sex is low, and the photosensitivity cannot be obtained sufficiently.
If it is too much, the uniformity and strength of the film will decrease.
Neither is preferable. These lights
The heat conversion agent may be added to the same layer as other components,
Another layer may be provided and added to it, but negative image formation
When the material is prepared, the wavelength of the recording layer is 760 nm to 120
The optical density at the absorption maximum in the range of 0 nm is 0.1
It is preferably between ˜3.0. Out of this range
The sensitivity tends to be low. The optical density is the light
It is determined by the amount of heat conversion agent added and the thickness of the recording layer.
Therefore, the predetermined optical density can be controlled by controlling both conditions.
can get. The optical density of the recording layer should be measured by a conventional method.
Can do. As a measuring method, for example, transparent or white
On a color support, the coating amount after drying is required as a lithographic printing plate.
Forming a recording layer with a thickness determined as appropriate within the required range
And measuring with a transmission optical densitometer, aluminum
A recording layer is formed on a reflective support such as
And the like. [(C) radical by heat mode exposure
Compound that produces radicals by heat mode exposure
The resulting compound (hereinafter referred to as a radical initiator as appropriate)
Is used in combination with the photothermal conversion agent (B).
Light of a wavelength that can be absorbed by the heat conversion agent, for example, an infrared laser
Energy of light and / or heat when irradiated
-Generates radicals, and (A) is soluble in specific alkalis
Polymer and (D) weight described later used in combination if desired
Polymerization of radically polymerizable compounds having compatible unsaturated groups
Refers to a compound that initiates and promotes. Here, "Heat mode
"Exposure" follows the definition in the present invention described above
And As the radical initiator, known photopolymerization cleavage can be used.
You can select and use an initiator, thermal polymerization initiator, etc.
For example, an onium salt, a trihalomethyl group
Liazine compound, peroxide, azo polymerization initiator, azide
Compound, quinonediazide, etc.
Salts are preferred because of their high sensitivity. Radicals preferably used in the present invention
Examples of compounds that generate onium salts include onium salts,
Physically, iodonium salts, diazonium salts, sulfoni
Umm salt. These onium salts are used as acid generators.
Although it also has a function, it is used in combination with the radical polymerizable compound described later
In doing so, it functions as an initiator for radical polymerization. Book
The onium salt suitably used in the invention is the following general
It is an onium salt represented by the formulas (I) to (III). [0104] Embedded image In the formula (I), Ar¹¹And Ar¹²Respectively
Independently, the number of carbon atoms which may have a substituent is 20 or less.
The lower aryl group is shown. This aryl group has a substituent
Preferred substituents in the case of halogen atom, nitro
B group, alkyl group having 12 or less carbon atoms, carbon atom number
12 or fewer alkoxy groups or 12 or fewer carbon atoms
Of the aryloxy group. Z^11-Is halogen
ON, perchlorate ion, carboxylate ion, tetrafur
Oroborate ion, hexafluorophosphate ion
And a pair selected from the group consisting of sulfonate ions
Ion, preferably perchlorate ion, hexaf
Luophosphate ion and aryl sulfonic acid
Ion. In the formula (II), Ar^{twenty one}Has a substituent
And an aryl group having 20 or less carbon atoms. Good
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less atoms, 12 or less carbon atoms
An alkoxy group having 12 or less carbon atoms
Si group, alkylamino group having 12 or less carbon atoms, carbon
Dialkylamino group having 12 or less atoms, 1 carbon atom
2 or less arylamino groups or 12 or less carbon atoms
Examples include the lower diarylamino group. Z^{twenty one-}Is Z^11-When
Represents a synonymous counter ion. In the formula (III), R³¹, R³²And R³³The
Each may be the same or different and has a substituent.
And a hydrocarbon group having 20 or less carbon atoms. Good
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less atoms, 12 or less carbon atoms
Or an aryl having 12 or less carbon atoms
An oxy group is mentioned. Z^31-Is Z^11-Counter ion synonymous with
Represents. In the present invention, it can be suitably used.
As a specific example of the onium salt, the applicant previously proposed
Paragraph No. [0 of Japanese Patent Application No. 11-310623
030] to [0033] and Japanese Patent Application 200
Paragraph Nos. [0015] to 0-160323 specification
[0046] can be mentioned. The onium salt used in the present invention is:
The maximum absorption wavelength is preferably 400 nm or less,
Furthermore, it is preferable that it is 360 nm or less. like this
By making the absorption wavelength in the ultraviolet region, lithographic printing plate
The original can be handled under white light. These onium salts are used in the entire recording layer coating solution.
0.1 to 50% by mass, preferably 0.5 to the solid content
30% by mass, particularly preferably 1-20% by mass
It can be added to the recording layer coating solution. Addition amount is 0.1
If it is less than mass%, the sensitivity will be low, and 50 mass% will be reduced.
If it exceeds, smearing occurs in the non-image area during printing. These
Only one type of nium salt may be used, or two or more types may be used together.
May be used. In addition, these onium salts
It can be added to the same layer, or another layer can be added
May be. [(D) Radical polymerizable compound] of the present invention
Image recording materials have the purpose of improving sensitivity and image formability
Thus, a radically polymerizable compound can be used in combination. This
Here, the radically polymerizable compound that can be used in combination is at least
Radical polymerization with one ethylenically unsaturated double bond.
Compound with at least terminal ethylenically unsaturated bond
Is selected from compounds having 1, preferably 2 or more
The Such compounds are widely known in the industry.
These are particularly limited in the present invention.
It can be used without any problems. These include, for example, monomers,
Repolymers, ie dimers, trimers and oligomers,
Or a mixture thereof and a copolymer thereof.
It has a morphological form. Examples of monomers and copolymers thereof include
Unsaturated carboxylic acids (eg acrylic acid, methacrylic
Acid, itaconic acid, crotonic acid, isocrotonic acid, male
Acid, etc.), its esters and amides,
Preferably, unsaturated carboxylic acid and aliphatic polyhydric alcohol
Esters with compounds, unsaturated carboxylic acids and aliphatic polyvalent compounds
Amides with amine compounds are used. Hydroxy
Nucleophilic substituents such as sil groups, amino groups and mercapto groups
Has unsaturated carboxylic esters, amides and monofunctional
Addition reaction with polyfunctional isocyanates and epoxies
Dehydration condensation with monofunctional or polyfunctional carboxylic acid
Combined reactants and the like are also preferably used. Further, an isocyanate group, an epoxy group, etc.
An unsaturated carboxylic acid ester having an electrophilic substituent or
Amides, monofunctional or polyfunctional alcohols, alcohols
Addition reaction products with amines and thiols,
Unsaturation with leaving substituents such as thiol and tosyloxy groups
Carboxylic acid esters or amides and monofunctional or polyfunctional
Substitution with functional alcohols, amines and thiols
Reactants are also suitable. As another example,
Unsaturated phosphonic acid, styrene instead of Japanese carboxylic acid
It is also possible to use a group of compounds replaced with, for example. Aliphatic polyhydric alcohol compounds and unsaturated cal
Specific examples of radically polymerizable compounds that are esters with boronic acid
Examples include acrylic acid esters, ethylene glycol
Coal diacrylate, triethylene glycol diac
Relate, 1,3-butanediol diacrylate, te
Tramethylene glycol diacrylate, propylene glycol
Recall diacrylate, neopentyl glycol dia
Chlorate, trimethylolpropane triacrease
Trimethylolpropane tri (acryloyloxy)
Propyl) ether, trimethylol ethane triacryl
Rate, hexanediol diacrylate, 1,4-silane
Chlohexanediol diacrylate, tetraethylene
Glycol diacrylate, pentaerythritol dia
Acrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, dipentae
Lithritol diacrylate, dipentaerythritol
Hexaacrylate, sorbitol triacrylate,
Sorbitol tetraacrylate, sorbitol penta
Acrylate, sorbitol hexaacrylate, tri
(Acryloyloxyethyl) isocyanurate, poly
There are ester acrylate oligomers and the like. Examples of 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, sorbitol trimethacrylate, sorbite
Tetramethyl methacrylate, bis [p- (3-methacrylic
(Luoxy-2-hydroxypropoxy) phenyl] dimethyl
Tylmethane, bis- [p- (methacryloxyethoxy
B) Phenyl] dimethylmethane. 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 Examples of crotonic acid esters include ethylene glycol.
Recall dicrotonate, tetramethylene glycol di
Crotonate, pentaerythritol dicrotonate,
Examples include sorbitol tetradicrotonate. As the isocrotonic acid ester, ethyl ester is used.
Glycol diisocrotonate, pentaerythritol
Rudiisocrotonate, sorbitol tetraisocroto
There are nates. Maleic acid esters include ethylene glycol.
Recall dimaleate, triethylene glycol dimale
, Pentaerythritol dimaleate, sorbitol te
There are trauma rates. Examples of other esters include, for example, special
Kosho 46-27926, JP-B 51-47334, JP
Aliphatic alcohol-based esthetics described in Sho 57-196231
JP-A-59-5240, JP-A-59-524
1, having an aromatic skeleton described in JP-A-2-226149
Containing an amino group described in JP-A-1-165613
What is used is also suitably used. In addition, an aliphatic polyvalent amine 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 Examples of other preferred amide monomers
The cyclohexylene described in JP-B-54-21726
The one with the structure can be given. Further, addition reaction of isocyanate and hydroxyl group
Also suitable for urethane-based addition-polymerizable compounds produced using
As a specific example, for example, Japanese Patent Publication No. 4
2 per molecule described in Japanese Patent No. 8-41708
Polyisocyanate having isocyanate groups above
The compound contains a hydroxyl group represented by the following general formula (IV)
Polymerization of 2 or more in one molecule with vinyl monomer added
Vinyl urethane compounds containing a functional vinyl group
It is. [0124]   CH₂= C (R³⁴) COOCH₂CH (R³⁵) OH General Formula (IV) In the general formula (IV), R³⁴And R³⁵Is that
It independently represents a hydrogen atom or a methyl group. Japanese Patent Laid-Open No. 51-37193, Japanese Patent
Described in No. 2-332293 and Japanese Patent Publication No. 2-16765
Urethane acrylates such as
No. 49860, Shoko Sho 56-17654, Shoko Sho 62
No. 39394 and Japanese Patent Publication No. 62-39418
Urethane compounds having a lenoxide framework are also suitable
It is. Further, JP-A 63-277653, JP
Japanese Utility Model Laid-Open No. 63-260909, Japanese Patent Application Laid-Open No. 1-105238
The amino structure or sulfide structure described in
You may use the radically polymerizable compound which has. Other examples include Japanese Patent Laid-Open No. 48-641.
83, JP-B 49-43191, JP-B 52-30
490, polyester as described in each publication
Acrylate, epoxy resin and (meth) acrylic acid
Multifunctional acrylics such as reacted epoxy acrylates
Rate and methacrylate can be raised. Also,
No.46-43946, No.1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinylphosphonic acid compounds described in JP-A-2-25493
You can also list things. In some cases, JP
A perfluoroalkyl group described in Sho 61-222048
The containing structure is preferably used. Furthermore, Japan Adhesion Association
Magazine vol. 20, no. 7, 300-308 pages (1
984) as a photo-curable monomer and oligomer
What is interposed can also be used. The radical polymerizable compound may be used alone or 2
Two or more species may be used in combination. These radically polymerizable compounds
What type of structure is used or whether it is used alone
Details of usage, such as whether to use in combination or how much to add
Can be set arbitrarily according to the performance design of the final recording material.
Can be determined. Of the radically polymerizable compound in the image recording material
As for the compounding ratio, a larger amount is advantageous in terms of sensitivity, but a larger amount
If it is too high, undesirable phase separation may occur,
Problems in the manufacturing process due to the adhesiveness of the recording layer (for example, recording
Transfer of layer components, manufacturing failure due to adhesion) or developer
This may cause problems such as precipitation. From these perspectives
Therefore, the preferable blending ratio of the radical polymerizable compound is many
The case, preferably 5 to 80% by weight, preferably
Is 20-75 mass%. In the present invention, the (A) specific alkali
Combined use of soluble polymer and (D) radical polymerizable compound
The ratio of the component (A) to the component (D) is the mass ratio
And preferably used in the range of 1: 0.05 to 1: 3.
Is in the range of 1: 0.1 to 1: 2, more preferably 1:
It is in the range of 0.3 to 1: 1.5. The radical polymerizable compound is used in oxygen.
Polymerization inhibition, resolution, fogging, refractive index change
Structure, blending, and addition from the standpoint of manufacturing, surface adhesion, etc.
The amount can be selected arbitrarily, and depending on the case, the undercoat or top
Layer construction and coating methods such as coating can also be performed. [Other components] In the image recording material of the present invention,
If necessary, various compounds other than these may be added.
You may add. For example, dyes with large absorption in the visible light range
The material can be used as an image colorant. concrete
The oil yellow # 101, oil yellow # 10
3, Oil Pink # 312, Oil Green BG, Oy
Le Blue BOS, Oil Blue # 603, Oil Black
BY, Oil Black BS, Oil Black T-50
5 (made by Orient Chemical Co., Ltd.), Victoria Pi
Pure Blue, Crystal Violet (CI4255
5), methyl violet (CI42535), ethyl
Violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue
-(CI52015), etc., and JP-A-62-229324
The dye described in No. 7 can be mentioned. Ma
Phthalocyanine pigments, azo pigments, carbon bras
Pigments such as lacquer and titanium oxide can also be suitably used.
The These colorants are used in the image area after image formation.
It is preferable to add it because it is easy to distinguish non-image areas.
Yes. The amount added is based on the total solid content of the recording layer coating solution.
The ratio is 0.01 to 10% by mass. In the present invention, the image recording material
Of radically polymerizable compounds during preparation or storage
Add a small amount of thermal polymerization inhibitor to prevent unnecessary thermal polymerization.
It is desirable to add. Suitable thermal polymerization inhibitors include
Idroquinone, p-methoxyphenol, di-t-butyl
Ru-p-cresol, pyrogallol, t-butylcateco
, Benzoquinone, 4,4'-thiobis (3-methyl
-6-tert-butylphenol), 2,2'-methylenebi
(4-methyl-6-tert-butylphenol), N-ni
Toroso-N-phenylhydroxylamine aluminum
Examples include salts. The amount of thermal polymerization inhibitor added is the total composition
About 0.01% by mass to about 5% by mass relative to the mass of
Yes. If necessary, prevent polymerization inhibition by oxygen
In order to induce higher fatty acids such as behenic acid and behenic acid amide
The surface of the recording layer is added during the drying process after applying a conductor.
May be unevenly distributed. The amount of higher fatty acid derivative added is
About 0.1% to about 10% by weight of the composition is preferred. The image recording material in the present invention is mainly composed of
As used for forming the image recording layer of lithographic printing plate precursor
However, the development conditions for such an image recording layer
In order to broaden the stability of the treatment, JP-A-62-251740
No. or JP-A-3-208514
Nonionic surfactant, JP-A-59-121044, Special
Amphoteric interfaces as described in Kaihei 4-13149
An activator can be added. As specific examples of the nonionic surfactant,
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. As specific examples of the amphoteric surfactant,
Rudi (aminoethyl) glycine, alkylpolyamino ester
Tilglycine hydrochloride, 2-alkyl-N-carboxyl
Chill-N-hydroxyethylimidazolinium betai
N-tetradecyl-N, N-betaine type (for example,
Product name Amorgen K, manufactured by Daiichi Kogyo Co., Ltd.)
The Recording of the above nonionic surfactants and amphoteric surfactants
The proportion in the layer coating solution is preferably 0.05 to 15% by mass.
More preferably, it is 0.1-5 mass%. Further, in the recording layer coating solution according to the present invention,
Is plasticized to give the film flexibility, etc.
The agent is added. For example, polyethylene glycol,
Tributyl enoate, diethyl phthalate, dibuty phthalate
, Dihexyl phthalate, dioctyl phthalate, phosphoric acid
Tricresyl, tributyl phosphate, trioctyl phosphate
, Tetrahydrofurfuryl oleate, etc.
The Planographic printing using the image recording material of the present invention
In order to produce a plate precursor, the components of the image recording material are usually used.
Together with each component required for the coating solution in a solvent
What is necessary is just to apply | coat on a suitable support body. The solvent used here and
Are ethylene dichloride, cyclohexanone,
Tyl ethyl ketone, methanol, ethanol, propano
, Ethylene glycol monomethyl ether, 1-methyl
Toxi-2-propanol, 2-methoxyethyl acetate
, 1-methoxy-2-propyl acetate, dimeth
Xiethane, methyl lactate, ethyl lactate, N, N-dimethyl
Ruacetamide, N, N-dimethylformamide, Tet
Lamethylurea, N-methylpyrrolidone, dimethylsulfur
Foxide, sulfolane, γ-butyl lactone, tolue
Water, water, etc., but are not limited to this
is not. These solvents are used alone or in combination.
The Concentration of the above components in the solvent (total solid content including additives)
Is preferably 1 to 50% by mass. Further, the description on the support obtained after coating and drying.
The coating amount (solid content) of the recording layer varies depending on the application.
Generally speaking, the printing plate precursor is 0.5 to 5.0 g.
/ M ²Is preferred. As the application amount decreases,
However, the film properties of the image recording layer are reduced.
The Various methods can be used as the coating method.
For example, bar coater coating, spin coating, spattering
Lay coating, curtain coating, dip coating, air knife
Coating, blade coating, roll coating, etc.
The The recording layer coating liquid according to the present invention has a coating property.
Surfactants for improving the quality, for example, JP-A-62-17
Fluorosurfactant as described in No. 0950
Can be added. The preferred addition amount is the total recording layer
0.01 to 1% by mass in the solid content of the material, more preferably
0.05 to 0.5% by mass. The image recording material of the present invention is mainly a lithographic plate.
Used as a recording layer for printing plate precursors. The lithographic printing plate
The master has at least a support and a recording layer and is necessary.
Depending on the case, a protective layer is further provided. Hereinafter, the lithographic printing plate
Explain the support and protective layer, which are the components of the original
The [Support] Using the image recording material of the present invention
As a support used when forming a lithographic printing plate precursor
There is no particular limitation as long as it is a dimensionally stable plate-like material,
For example, paper, plastic (eg, polyethylene,
Laminated with polypropylene, polystyrene, etc.)
Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic
Plastic film (eg cellulose diacetate, trivinegar)
Acid cellulose, cellulose propionate, cellulose butyrate
, Cellulose acetate butyrate, cellulose nitrate, polyethylene
Terephthalate, polyethylene, polystyrene, poly
Propylene, polycarbonate, polyvinyl acetal
Etc.). These are resin films and metal plates
Even a single-component sheet such as a product of two or more materials
It may be a layered body.
Nate or vapor deposited paper or plastic fill
Laminated sheets of different plastic films
included. As the support, a polyester fill is used.
Or aluminum plate is preferred, among which dimensional stability
Aluminum plates that are good and relatively inexpensive are particularly preferred.
That's right. Suitable aluminum plates are pure aluminum plates and
Alloy plate containing aluminum as a main component and containing trace amounts of foreign elements
In addition, aluminum is laminated or evaporated.
It may be a plastic film. Aluminum alloy
The foreign elements contained in silicon include silicon, iron, manganese, copper,
Gnesium, chromium, zinc, bismuth, nickel, titanium
Etc. The content of foreign elements in the alloy is at most 10% by mass
It is as follows. Aluminum particularly suitable in the present invention
Is pure aluminum but completely pure aluminum
Is difficult to manufacture due to refining technology.
It may be contained. Thus applied to the present invention
Aluminum plate is not specified for its composition.
In addition, a well-known and publicly-used aluminum plate is appropriately used.
Can be used. The thickness of the aluminum plate is
About 0.1 to 0.6 mm, preferably 0.15
0.4 mm, particularly preferably 0.2 to 0.3 mm
The Prior to roughening the aluminum plate,
If desired, for example, the surface activity to remove surface rolling oil
Degreasing treatment with an organic agent, organic solvent or alkaline aqueous solution
Is done. The roughening treatment of the surface of the aluminum plate
For example, the surface is mechanically roughened.
Method for electrochemically dissolving and roughening the surface
It is carried out by a method in which the surface is selectively dissolved. machine
Typical methods include ball polishing, brush polishing, and brass
It is possible to use a known method such as a polishing method or a buffing method.
Yes. Electrochemical roughening methods include hydrochloric acid or glass.
There is a method of performing an alternating current or direct current in an acid electrolyte. Ma
It is disclosed in JP-A-54-63902.
In other words, a method in which both are combined can also be used. The aluminum plate roughened in this way
If necessary, alkali etching treatment, neutralization treatment
Via, anodized to increase surface water retention and wear resistance
Processing can be performed. Anodizing of aluminum plate
A porous oxide film is formed as the electrolyte used for processing.
It is possible to use various types of electrolytes.
Acid, oxalic acid, chromic acid or a mixed acid thereof
The The concentration of those electrolytes depends on the type of electrolyte.
It is decided. The anodic oxidation treatment conditions depend on the electrolyte used.
However, in general, it cannot be specified.
Solution concentration is 1-80% by mass solution, liquid temperature is 5-70 ° C.,
Current density 5-60A / dm², Voltage 1-100V, electrolysis
A time range of 10 seconds to 5 minutes is appropriate. anodization
The amount of film is 1.0 g / m²The above is preferable, but more preferable
Preferably 2.0-6.0g / m²Range. Anodic acid
1.0 g / m of chemical coating²If it is less than 1, the printing durability is insufficient.
Or scratches on non-image areas of planographic printing plates
The so-called `` scratch that ink adheres to the scratched part during printing
Dirt "tends to occur. In addition, such anodizing treatment
Applied to the surface of the lithographic printing plate support,
0.01-3 g / m on the back side due to the back of the line of energy²
In general, an anodic oxide coating is formed. The hydrophilization treatment of the support surface is carried out by the above anodic oxidation.
It is given after processing and has been known for some time
A processing method is used. As such a hydrophilic treatment,
U.S. Pat. Nos. 2,714,066 and 3,181,4
61, 3,280,734 and 3,902,7
Alkali metal silicates as disclosed in publication No. 34
(For example, sodium silicate aqueous solution) method. This way
In, the support is immersed in an aqueous sodium silicate solution
Or electrolytic treatment. In addition, JP 36-22
Calcium zirconate fluoride disclosed in Japanese Patent No. 063
And U.S. Pat. Nos. 3,276,868 and 4,15.
Disclosed in US Pat. Nos. 3,461 and 4,689,272.
Treatment with polyvinyl phosphonic acid, etc.
Is used. Of these, particularly preferred in the present invention.
A new hydrophilic treatment is a silicate treatment. About silicate treatment
This will be described below. The aluminum plate treated as described above
Anodized film with 0.1-30 alkali metal silicate
% By weight, preferably 0.5 to 10% by weight, at 25 ° C.
In an aqueous solution having a pH of 10 to 13, for example, 15 to 80
Immerse at a temperature of 0.5 to 120 seconds. Alkali metal silicate water
If the pH of the solution is lower than 10, the solution will gel and from 13.0
If it is too high, the oxide film will be dissolved. Used in the present invention
Examples of alkali metal silicates include sodium silicate and silicic acid
Potassium, lithium silicate, etc. are used. Alkaline gold
Hydroxides used to increase the pH of aqueous silicate solutions
Chemicals include sodium hydroxide, potassium hydroxide, hydroxide
There is lithium fluoride. Note that the above treatment liquid is alkaline.
May contain earth metal salts or Group IVB metal salts
Yes. Alkaline earth metal salts include calcium nitrate, glass
Of strontium acid, magnesium nitrate, barium nitrate
Such as nitrates, sulfates, hydrochlorides, phosphates, acetates,
Water-soluble salts such as acid salts and borates are exemplified. IVB
Group metal salts such as titanium tetrachloride, titanium trichloride, fluoride
Titanium potassium, Titanium potassium oxalate, Titanium sulfate, Four
Titanium iodide, chlorinated zirconium oxide, zirconium dioxide
Um, zirconium oxychloride, zirconium tetrachloride
Can be mentioned. Alkaline earth metal salt
Used Group IVB metal salt alone or in combination of two or more
can do. The preferred range of these metal salts is
It is 0.01-10 mass%, and a more preferable range is 0.00.
It is 05-5.0 mass%. By silicate treatment, aluminum
Since the hydrophilicity on the surface of the nium plate is further improved,
The ink is less likely to adhere to the non-image area,
improves. On the back side of the support, a back cover is provided if necessary.
Is provided. As such a back coat, JP
Organic polymer compounds described in JP-A-5-45885 and special compounds
Organic or inorganic metal compounds described in Kaihei 6-35174
From metal oxides obtained by hydrolysis and polycondensation of products
A coating layer is preferably used. These coating layers
Si (OCH_Three)_Four, Si (OC₂H_Five)_Four, Si (O
C_ThreeH₇)_Four, Si (OC_FourH₉)_FourSilicon alkoxy etc.
Compounds are cheap and readily available, and then the metal oxidation given
A coating layer of the product is particularly preferred because of its excellent development resistance. [Protective layer] The image recording material of the present invention is applied to a lithographic mark.
When used as a printing plate precursor, exposure is usually performed in air.
Therefore, on the image recording layer containing the photopolymerizable composition,
It is preferable to provide a protective layer, which is desirable for such a protective layer.
As a characteristic, low permeability of low molecular weight compounds such as oxygen is low.
In addition, it has good light transmission for exposure and adhesion with the recording layer.
It is easy to remove in the development process after exposure.
That is, polyvinyl alcohol, polyvinylpyrroline
Don, acidic cellulose, gelatin, gum arabic,
Water-soluble with relatively excellent crystallinity such as reacrylic acid
It is common to use a polymer compound. In the image recording material of the present invention, a film type is used.
As a synthetic resin, the amount of dissolved oxygen in the film after film formation is low.
The specific polyurethane having a high oxygen barrier property from the outside
Since resin is used, images due to polymerization inhibition of oxygen, etc.
This has the advantage that the decrease in formability can be suppressed.
There is no need to provide such a protective layer,
Improves oxygen barrier from the outside and forms image, especially image
You may provide the said protective layer in order to raise intensity | strength. [Printing by planographic printing plate precursor]
The image recording material of the present invention is formed as a recording layer on the support surface.
The prepared lithographic printing plate precursor should be recorded with an infrared laser.
Can do. Also by UV lamp or thermal head
Thermal recording is also possible. In the present invention, the wavelength 76
Solid-state laser that emits infrared light from 0 nm to 1200 nm
And image exposure with a semiconductor laser is preferred.
Yes. After exposure with an infrared laser, the
The image recording material is preferably water or an alkaline aqueous solution
Developed with An alkaline aqueous solution is used as the developer.
As a developer and replenisher for the image recording material of the present invention.
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 high-grade aqueous solution (replenisher) to the developer.
Without changing the developer in the developer tank for a long time,
It is known that a large amount of lithographic printing plate precursors can be processed.
The This replenishment method is preferably applied also in the present invention.
The In the developer and replenisher, development property is promoted or suppressed.
System, dispersion of development residue, and high ink affinity in the printing plate image area
Various surfactants and organic solvents as needed
Can be added. Preferred surfactants are anions
-Based, cationic, nonionic and amphoteric surfactants
It is done. Preferred organic solvent is benzyl alcohol
Etc. Also polyethylene glycol youth
Is a derivative thereof, or polypropylene glycol or
Addition of such derivatives is also preferred. Also, Arabic, Soviet
You can also add non-reducing sugars such as rubitt and mannit
Yes. In addition, the developer and replenisher may be used as necessary.
Hydroquinone, resorcin, sulfite or sulfite water
Inorganic salt reduction of sodium and potassium salts of boric acid
Addition of organic carboxylic acid, antifoaming agent, water softener
You can also. Using the developers and replenishers described above,
The image-treated printing plate contains washing water, a surfactant and the like.
Desensitizing oil containing rinsing liquid, gum arabic and starch derivatives
After-treatment with liquid. Printing plate material for image recording material of the present invention
As a post-processing when using as
Various combinations can be used. In recent years, the plate making work has been rationalized in the plate making / printing industry.
Automatic processing machines for printing plate materials are widely used
It is used. This automatic processor generally has a developing section and a rear
An apparatus that consists of a processing unit and conveys a printing plate and each processing liquid
It consists of a tank and a spray device.
Each processing solution pumped up by the pump
-It develops by spraying from the nozzle. Ma
Recently, a submerged guide in a processing liquid tank filled with the processing liquid.
Process printing plate by dipping and transporting it with rolls
Methods are also known. In such automatic processing,
Replenish each treatment solution with a replenisher according to the processing amount, operating time, etc.
Can be processed. In addition, the electrical conductivity is
It can be sensed by the sir and automatically replenished. Ma
In addition, the so-called single-use disposal is performed with a virtually unused processing solution.
Processing methods can also be applied. The lithographic printing plate obtained as described above is
Applying desensitized gum as desired, then use in printing process
Lithographic printing plates with even higher printing durability
If so, a burning process is performed. Lithographic printing plate
If you are burning, before the burning
-2518, 55-28062, JP 62-3
1859 and 61-159655.
It is preferable to treat with a surface-conditioning liquid as described above. As the method, the surface conditioning liquid is soaked.
Apply on a lithographic printing plate with a sponge or absorbent cotton,
Apply the printing plate by dipping it in a vat filled with surface-adjusting liquid.
The method and application by an automatic coater are applied. Ma
After application, use a squeegee or squeegee roller to
Uniform application amount gives better results
The The coating amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m.²
(Dry mass) is appropriate. A lithographic stamp with a surface-adjusting solution applied
The plate is dried if necessary before the burning process.
Sir (for example, sold by Fuji Photo Film Co., Ltd.)
Burning processor: BP-1300) etc.
Heated to warm. In this case, the heating temperature and time
180-300 depending on the type of ingredients forming
The range of 1 to 20 minutes is preferable in the range of ° C. A lithographic printing plate that has been burned is necessary.
Depending on the situation, water washing, gumming, etc. have been performed as appropriate.
Can be treated with water-soluble polymer compounds, etc.
If the surface preparation liquid contained is used, do not gum it.
So-called desensitizing treatment can be omitted. Through such processing, the image recording of the present invention is performed.
The planographic printing plate obtained from the recording material is used for offset printing machines, etc.
It is used for printing a large number of sheets. [0166] EXAMPLES The present invention will be described below as synthesis examples, examples and comparative examples.
Therefore, the present invention will be described in more detail.
It is not limited. [Examples 1 to 6, Comparative Examples 1 to 3] (Preparation of support) 99.5% or more of aluminum and F
e 0.30%, Si 0.10%, Ti 0.02
%, JIS A1050 alloy containing 0.013% Cu
The molten metal was cleaned and cast. For cleaning process
Removes unnecessary gases such as hydrogen in the melt.
Gas treatment and ceramic tube filter treatment
It was. The casting method was a DC casting method. Solidified board thickness 50
An ingot of 0mm is chamfered 10mm from the surface, intermetallic compound
Homogeneous at 550 ° C for 10 hours to prevent coarsening
The treatment was performed. Then, hot rolled at 400 ° C and continuous
Cold rolling after intermediate annealing at 500 ° C for 60 seconds in an annealing furnace
To obtain a rolled aluminum plate having a plate pressure of 0.30 mm.
It was. Cold rolling by controlling the roughness of the rolling roll
The subsequent centerline average surface roughness Ra was controlled to 0.2 μm.
Then tension leveler to improve flatness
I went to. Next, a surface treatment for forming a lithographic printing plate support is carried out.
I did it. First, remove the rolling oil on the aluminum plate surface
For 30 seconds at 50 ° C with 10% sodium aluminate aqueous solution
Perform degreasing treatment, 30% sulfuric acid aqueous solution at 50 ° C for 30 seconds
Neutralization and smut removal treatment were performed. Next, the adhesion between the support and the recording layer is improved.
And the surface of the support in order to give water retention to the non-paint rear part
A so-called graining treatment was performed to roughen the surface. 1%
45% aqueous solution containing nitric acid and 0.5% aluminum nitrate
Indirect while keeping the temperature at ℃ and flowing the aluminum web into the aqueous solution
Current density 20A / dm due to power supply cell², Duty
Anode-side electricity quantity of 240 C / dm with an alternating waveform with a ratio of 1: 1
²Electrolytic graining was performed by giving 10% after that
Etching with sodium aluminate aqueous solution at 50 ° C for 30 seconds
And neutralize with 30% aqueous sulfuric acid at 50 ° C for 30 seconds.
A mat removal treatment was performed. Furthermore, wear resistance, chemical resistance and water retention are improved.
In order to form an oxide film on the support by anodic oxidation.
Made. Uses 20% sulfuric acid aqueous solution at 35 ° C as electrolyte
Indirect power feeding while carrying the aluminum web through the electrolyte
14 A / dm depending on the cell²Electrolytic treatment with direct current
2.5g / m²An anodic oxide film was prepared. Thereafter, hydrophilicity as a non-image portion of the printing plate is obtained.
To secure it, silicate processing was performed. Processing is No. 3
Keep 1.5% aqueous solution of sodium carbonate at 70 ° C
It was carried so that the contact time was 15 seconds, and further washed with water.
The amount of Si deposited is 10 mg / m ²Met. By the above
Ra (center line surface roughness) of the formed support is 0.25 μm.
Met. (Formation of recording layer) The following recording layer coating solution 1 was prepared.
To the aluminum support obtained as described above.
Apply using a wire bar, 11 with a hot air dryer
The recording layer is formed by drying at 5 ° C. for 45 seconds.
Got a version. The coating amount after drying is 1.2 to 1.3 g / m²of
It was within the range. [0173] <Recording layer coating solution 1>   Alkali-soluble polymer: component (A) (compound described in Table 5, amount described in Table 5 )   Infrared absorber “IR-1”: Component (B) 0.10 g   -Radical initiator “S-1”: component (C) 0.45 g   Radical polymerizable compound: component (D) (compound described in Table 5, amount described in Table 5 )   ・ Victoria Pure Blue Naphthalenesulfonic Acid 0.04g   ・ Fluorosurfactant 0.0 lg       (Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)   ・ P-methoxyphenol 0.001g   ・ Methyl ethyl ketone 9.0g   ・ Methanol 10.0g   1-methoxy-2-propanol 8.0g [0174] [Table 5] It should be noted that a) used in the examples of the present invention.
Lucari soluble polymer was obtained by the above synthesis example
(A) A specific alkali-soluble polymer,
The structural unit of the alkali-soluble polymer used in the comparative example
This is shown below. [0176] Embedded imageSimilarly, examples and comparisons in the present invention
Specific examples of (B) infrared absorber used in the examples are shown below.
The [0178] Embedded image Similarly, examples and comparisons in the present invention
Specific examples of the (C) radical initiator used in the examples are shown below.
The [0180] Embedded image Similarly, examples and comparisons in the present invention
Specific examples of the (D) radical polymerizable compound used in the examples are as follows.
Shown below. [0182] Embedded image (Exposure) Each lithographic printing plate precursor obtained in the previous period
With a water-cooled 40W infrared semiconductor laser
At the Trendsetter 3244VFS manufactured by o
Power 6.5W, outer drum rotation speed 81rpm, plate surface energy
Ghee 188mJ / cm², Resolution 2400 dpi
And exposed. (Development processing) After exposure, Fuji Photo Film
Development using an automatic processor Stablon 900NP manufactured by KK
I managed. As the developer, the following (D-1) is charged, and the following
(D-2) was used as a replenisher. The development bath temperature is 30
The processing was carried out at 12 ° C. for 12 seconds. At this time, the replenisher is
The electric conductivity of the developer in the developing bath of the dynamic developing machine becomes constant.
Was automatically adjusted while adjusting. Also finish
Is a 1: 1 water of FN-6 manufactured by Fuji Photo Film Co., Ltd.
Diluent was used. <Developer (D-1)>   ・ Potassium hydroxide 3g   ・ Potassium bicarbonate 1g   ・ Potassium carbonate 2g   ・ Sodium sulfite 1g   ・ Polyethylene glycol mononaphthyl ether 150g   ・ Dibutyl naphthalenesulfonic acid sodium salt 50g   ・ Ethylenediaminetetraacetic acid tetrasodium salt 8g   ・ 785g water [0185] <Developer (D-2)>   ・ Potassium hydroxide 6g   ・ Potassium carbonate 2g   ・ Sodium sulfite 1g   ・ Polyethylene glycol mononaphthel ether 150g   ・ Dibutyl naphthalenesulfonic acid sodium salt 50g   ・ Hydroxyethanediphosphonic acid potassium salt 4g   ・ Silicon TSA-731 0.1g               (Toshiba Silicone Co., Ltd.)   ・ Water 786.9g [Evaluation of printing durability] Next, Komori Corporation
Printing was performed using Lislon, a printing machine manufactured by Ron Co., Ltd. this
How many sheets can be printed with sufficient ink density
The printing durability was evaluated by visual observation. Previous result
This is also shown in Table 5. [Evaluation of scratch resistance] The recording layer was applied.
The scratch resistance of the lithographic printing plate precursor was evaluated. Machine
As a container, Scratching made by HEIDON
Using TESTER HEIDON-14, scratching needle
As a 0.4mmR diamond needle, changing the load on the needle
The surface of the recording layer at a speed of 400 mm / min.
I scratched it. The original plate after scratching is subjected to the development process described above.
The magnitude of the load in which the remaining film was visually observed was evaluated.
The greater the load, the less likely the scratch film will form and the greater the scratch resistance.
It will be excellent. The results are also shown in Table 5. that's all,
As is apparent from Table 5, the image recording material of the present invention was used as a recording layer.
The lithographic printing plate precursors of Examples 1 to 6 used as
Comparative Example 1 using a known alkali-soluble polymer outside the range
Compared to ~ 3, excellent printing durability and scratch resistance are achieved.
I understand that In addition, the exposure
No bralation was seen. [Examples 7 to 10, Comparative Examples 4 to 5] Examples
The same aluminum used in 1-6 and Comparative Examples 1-3
On the film support, apply the coating solution for the undercoat layer shown below,
It dried for 30 seconds in 80 degreeC atmosphere. The dry coating amount is 1
0 mg / m²Met. (Coating solution for undercoat layer) A compound having the following composition was mixed to prepare an undercoat layer coating solution.   ・ 2-aminoethylphosphonic acid 0.5g   ・ Methanol 40g   ・ Pure water 60g (Formation of recording layer) Recording layer coating liquid shown below
2 on the support on which the undercoat layer is formed.
And dried at 115 ° C for 45 seconds with a hot air dryer.
The lithographic printing plate precursor was obtained by drying. The coating amount after drying is as follows:
2 to 1.3 g / m²It was in the range. [0190] <Recording layer coating solution 2>   Alkali-soluble polymer: component (A) (compound described in Table 6, amount described in Table 6 )   Infrared absorber “IR-2”: component (B) 0.08 g   ・ Radical initiator “S-2”: Component (C) 0.30 g   Radical polymerizable compound: component (D) (compound described in Table 6, amount described in Table 6 )   ・ Victoria Pure Blue Naphthalenesulfonic Acid 0.04g   ・ Fluorine-based surfactant 0.01g       (Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)   ・ 0.001 g of N-nitroso-N-phenylhydroxylamine aluminum   ・ Methyl ethyl ketone 9.0g   ・ Methanol 10.0g   1-methoxy-2-propanol 8.0g [0191] [Table 6](Exposure) The obtained lithographic printing plate precursor was cooled with water.
Creo T equipped with a 40W infrared semiconductor laser
output 6.5 at rendsetter 3244VFS
W, outer drum rotation speed 81 rpm, plate surface energy 18
8mJ / cm², Resolution, resolution 2400 dpi
And exposed. (Development processing) After exposure, Fuji Photo Film
Development using an automatic processor Stablon 900NP manufactured by KK
I managed. The developer is Fuji Photo Fiber for both the feed and replenishers.
A 1: 8 water dilution of DP-4 manufactured by Rum Co., Ltd. was used. developing
The bath temperature was 30 ° C. and the development time was 12 seconds. This
At this time, the replenisher is used for the electrical transfer of the developer in the developing bath of the automatic processor.
It was automatically added while adjusting the conductivity to be constant.
The finisher is F made by Fuji Photo Film Co., Ltd.
A 1: 1 water dilution of N-6 was used. [Evaluation of printing durability and stain resistance]
Each of the printing plate precursors is stored at 60 ° C. for 3 days, and
Store at 45 ° C, humidity 75% RH for 3 days and force aging
After, similar to Examples 1-6 and Comparative Examples 1-3
The printing durability and stain resistance were evaluated. . The result
This is also shown in Table 6. As is apparent from Table 6, the image of the present invention
Lithographic plates of Examples 7 to 10 using an image recording material as a recording layer
The printing plate precursor is known alkali-soluble outside the scope of the present invention.
Compared with Comparative Examples 4 to 5 using a polymer, stains on the non-image area are also observed.
It has excellent printing durability and is stored at high temperature and high humidity.
After that, the printing durability and stain resistance of the non-image area are not deteriorated.
It was found to be excellent in qualitative. [Examples 11 to 15, Comparative Examples 6 to 7] Implementation
The same aluminum as used in Examples 1-6 and Comparative Examples 1-3
The following recording layer coating solution 3 is prepared on the aluminum support, and
Apply to the luminium support using a wire bar and warm air
Lithographic printing plate after drying for 45 seconds at 115 ° C. in a dry dryer
I got the original version. The coating amount after drying is 1.2 to 1.3 g / m²
It was in the range. <Recording layer coating solution 3>   -High molecular compound (compound described in Table 7, amount described in Table 7)   ・ Infrared absorber “IR-3” 0.10 g   ・ Radical initiator "S-1" 0.50g   ・ Victoria Pure Blue Naphthalenesulfonic Acid 0.04g   ・ Fluorine-based surfactant 0.01g         (Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)   ・ Methyl ethyl ketone 9.0g   ・ Methanol 10.0g   1-methoxy-2-propanol 8.0g [0196] [Table 7](Exposure) The obtained lithographic printing plate precursor is cooled with water.
Creo T equipped with a 40W infrared semiconductor laser
With a rendsetter 3244VFS, output 9W,
External drum rotation speed 210rpm, plate surface energy 100
mJ / cm², Exposure at a resolution of 2400 dpi
It was. (Development processing) After exposure, Fuji Photo Film
Development processing using an automatic processor Stablon 900N manufactured by Co., Ltd.
did. The developer is Fuji Photo Fiber for both the feed and replenishers.
A 1: 1 water dilution of DN-3C manufactured by Rum Co., Ltd. was used. Present
The temperature of the image greedy bath was 30 ° C. Also finisher
Is a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd.
The liquid was used. [Evaluation of printing durability and scratch resistance]
Printing was performed using an Idelberg SOR-KZ press. This
When printing, how many sheets should be printed with sufficient ink density
The printing durability was evaluated by measuring whether it was possible. Example 1
Evaluation for scratch resistance as in -6 and Comparative Examples 1-3
went. As is apparent from Table 7, the image recording of the present invention
Lithographic printing of Examples 11 to 15 using the material as a recording layer
The plate precursor is a known alkali-soluble high content outside the scope of the present invention.
Compared with Comparative Examples 6 to 7 using a child, excellent printing durability and durability
It can be seen that scratch properties are achieved. [0200] According to the present invention, a solid that emits infrared rays.
By recording with laser and semiconductor laser
Directly from digital data such as computers
Yes, when used for the recording layer for lithographic printing plate precursors,
Form high-intensity, high-quality images without causing
Negative prints that can be made and achieve excellent printing durability
An image recording material can be provided.

Claims (1)

(A) The following general formulas (1), (2),
At least one of the structural units represented by (3),
A polymer compound that is soluble or swells in water or an aqueous alkaline solution, (B) a photothermal conversion agent, and (C) (B) a photothermal conversion agent, comprising 0.1 mol% or more and less than 30 mol% And a compound that generates radicals by heat mode exposure of light having a wavelength that can be absorbed, and is capable of forming an image by heat mode exposure. [Chemical 1] (In the formula, A ¹ , A ² and A ³ each independently represents an oxygen atom, a sulfur atom or —N (R ²¹ ) —, and R ²¹ represents an alkyl group which may have a substituent. G ¹ , G ² and G ³ each independently represents a divalent organic group, X and Z each independently represent an oxygen atom, a sulfur atom or —N (R ²² ) —, and R ²² has a substituent. And Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent,-
N (R ²³⁾ - represents, R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a monovalent organic group. )