JP2000039708A - Lithographic printing master plate and production of lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing master plate which can be made by scanning exposure in a short time, which enables production of a lithographic printing plate having excellent hydrophilicity in a non-picture part, excellent strength in a picture part, excellent contamination resistance and printing durability as printing performance, and which is suitable for plate making process by a developing method in a printing machine, and to provide a method to suppress practical problems on the printing master plate such as remaining film which is caused by shortage of thermal reaction near the supporting body. SOLUTION: This lithographic printing master plate has a layer containing (a) a hydrophobic polymer compd. having functional groups in the side chains which change from hydrophobic to hydrophilic by heat and having hydrophilic functional groups, and (b) a light-absorbing agent which absorbs laser light to convert into heat, on a supporting body having a hydrophilic surface. In the producing method of a lithographic printing plate, the master plate is exposed to laser light to form an image and then the exposed part in the recording layer is removed in a printing machine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type lithographic printing plate precursor having a hydrophobic (hereinafter also referred to as lipophilic) layer (image forming layer) on a support having a hydrophilic surface.
More specifically, a lithographic printing plate precursor capable of performing plate making by scanning exposure based on a digital signal and being water-developable, or capable of being directly mounted on a printing machine without being developed and printed, and its lithographic plate The present invention relates to a method for producing a lithographic printing plate using a printing plate precursor.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area for receiving ink during a printing process and a hydrophilic non-image area for receiving fountain solution. Conventionally, as such a lithographic printing plate precursor, a PS plate in which a lipophilic photosensitive resin layer is provided on a hydrophilic support is widely used. As a plate making method, usually, after mask exposure through a lith film,
The non-image area is dissolved and removed with a developer. The desired printing plate was obtained by this method. In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and various new image output methods compatible with such digitization techniques have been put to practical use. It has become. Along with this, computer-to-plate technology that scans actinic radiation having a high directivity such as laser light in accordance with digitized image information and directly manufactures a printing plate without passing through a lithographic film has been desired. It is an important technical problem to obtain a printing plate precursor adapted to this.

On the other hand, the plate making process in the conventional PS plate is as follows.
The fact that a step of dissolving and removing non-image areas after exposure is indispensable, and such an additional wet treatment is indispensable is another problem that has been desired to be improved over the prior art. is there. Particularly in recent years, consideration for the global environment has become a major concern of the entire industry. The simplification of processing, dry processing, and non-processing are becoming more desirable than ever, both from the viewpoint of such environmental aspects and the rationalization of processes associated with the aforementioned digitization. .

[0004] From such a viewpoint, the following method has been proposed as one of the methods for eliminating the conventional processing steps. That is, using a photosensitive layer capable of removing the non-image portion of the printing plate precursor in a normal printing process, without performing a developing process, after exposure, developing on a printing machine to obtain a final printing plate. It is a way to get. The method of making a lithographic printing plate by such a method is called an on-press development method. Specifically,
For example, a method of using a photosensitive layer soluble in a fountain solution or an ink solvent, a method of mechanically removing the photosensitive layer by contact with an impression cylinder or a blanket cylinder in a printing press, and the like are mentioned. However, a major problem with the on-press development method is that the printing plate is not completely fixed even after exposure, so for example, the plate is completely shielded from light and / or kept under constant temperature conditions until it is mounted on a printing machine. It was necessary to take an inefficient method of doing so.

On the other hand, as a method of manufacturing a printing plate by scanning exposure, a solid-state laser such as a semiconductor laser or a YAG laser has recently become available at a low cost. The methods used have become promising. In the high power density exposure system using these high power lasers, various phenomena different from the photoreaction used in the conventional photosensitive material system for low to medium power density exposure can be used. Specifically, structural changes such as phase changes and morphological changes can be used in addition to chemical changes. Usually, a recording method using such high power density exposure is called heat mode recording. In high power density exposure systems,
The light energy absorbed by the photosensitive material is converted into heat,
This is because it is believed that the generated heat causes a desired phenomenon.

A great advantage of such a heat mode recording method is that fixing of an image after exposure is not essential. That is, the phenomenon used for image recording of the heat mode photosensitive material is as follows.
Fixation of the image after exposure is not essential, since exposure to light of normal intensity and under normal environmental temperatures do not occur substantially. Therefore, for example, if a plate is made by an on-press development method using a photosensitive layer which is insolubilized or solubilized by heat mode exposure, development (removal of non-image portions) can be performed for an arbitrary time after image exposure, even if exposed to ambient light. A system is possible in which the image obtained does not change even after exposure. Therefore, according to the heat mode recording, it is possible to obtain a lithographic printing plate precursor that is desirable for the above-described on-press development system.

[0007] As one of the preferable methods for producing a lithographic printing plate based on heat mode recording, a hydrophobic image forming layer is provided on a hydrophilic support, and the image is subjected to heat mode exposure in the form of an image. A method has been proposed in which the dispersibility is changed and, if necessary, the non-image areas are removed by wet development.
As an example of such an original plate, for example, Japanese Patent Publication No. 46-279
No. 19 discloses an original plate in which a recording layer having improved solubility by heat and exhibiting a so-called positive action, specifically a recording layer having a specific composition such as a saccharide or a melamine formaldehyde resin, is provided on a hydrophilic support. A method for obtaining a printing plate by performing heat mode recording is disclosed.

However, none of the disclosed recording layers has sufficient heat sensitivity, so that the heat mode scanning exposure sensitivity has been extremely insufficient. In addition, hydrophobicity before and after exposure /
Practical problems also include hydrophilic discrimination, that is, a small change in solubility. With such a small discrimination, it is almost impossible to make an on-press development type plate making.

Further, another problem of the conventional heat mode positive type original plate is that a residual film remains on a non-image portion. That is, it was necessary to improve the solubility change in the vicinity of the support in the recording layer due to exposure was smaller than that in the vicinity of the recording layer surface. In the heat mode positive mold,
Since the generation of heat at the time of heat mode exposure is based on the light absorption of the light absorbing agent in the recording layer, the amount of heat generation is large on the recording layer surface and small near the support. For this reason, the degree of hydrophilization of the recording layer near the support is relatively low. As a result, a hydrophobic residual film may often occur in an exposed portion where a hydrophilic surface is to be provided. Such a residual film in the non-image area causes a problem that it is easily stained in printing performance. In particular, when a metal support having high thermal conductivity such as Al, which is preferable in terms of printability, is used, the problem of a residual film is remarkable because the heat diffusion further hinders a temperature rise near the support. . In order to obtain sufficient hydrophilicity near the substrate, extremely large exposure energy was required, or post-treatment such as heating after exposure had to be performed.

[0010] As a method for improving the adverse effects caused by heat diffusion to the support at the time of exposure in such a heat mode printing plate,
For example, JP-A-52-37104 and JP-A-52-1
No. 18417 proposes a method of providing a layer of aluminum oxide having a certain thickness or more on the surface of a support to reduce thermal diffusion. Although this method is effective, it is inadequate and does not eliminate the residual film of the heat mode positive printing plate.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to make a plate by scanning exposure in a short time, to have excellent hydrophilicity in a non-image area, excellent strength in an image area, stain resistance in printing performance, and printing durability. Another object of the present invention is to provide a lithographic printing plate precursor from which a heat mode positive type lithographic printing plate excellent in quality can be manufactured. Another object is to provide a lithographic printing plate precursor suitable for on-press development type plate making. Another object of the present invention is to provide a method for solving a practical problem caused by lack of thermal reaction near a support, such as a residual film, for a heat mode positive printing plate precursor. is there.

[0012]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by using the following lithographic printing plate precursor, and have completed the present invention. That is, the present invention provides (a) a hydrophobic polymer compound having a functional group that changes from hydrophobic to hydrophilic by heat and a hydrophilic functional group on a side chain on a support having a hydrophilic surface; A) a lithographic printing plate precursor having a layer containing a light absorber capable of absorbing laser light and converting it into heat, and exposing the lithographic printing plate precursor imagewise by laser exposure, and then recording the exposed area A method for producing a lithographic printing plate, characterized in that the layer is removed on a printing press.

According to the lithographic printing plate precursor of the present invention, in the exposed portion, the polarity conversion applied to the image forming layer (changes from hydrophobic to hydrophilic by heat) due to heat generated by photothermal conversion after exposure. The polarity conversion functional group of the polymer compound changes from hydrophobic to hydrophilic, and the polarity conversion polymer compound also changes from hydrophobic to hydrophilic. As a result, the polarity conversion polymer compound that has been hydrophilized is solubilized in a fountain solution or the like, and is removed from the support to form a lithographic printing plate.

Here, the polarity conversion polymer compound used in the lithographic printing plate precursor of the present invention is slightly hydrophilic in advance because it has a hydrophilic functional group in a side chain.
Therefore, even when only a small part of the polarity conversion functional group changes to hydrophilic, the polarity conversion polymer compound also changes to hydrophilic and can be removed from the printing plate. Therefore, even in the vicinity of the substrate of the image forming layer where the polarity conversion of the polarity conversion functional group is relatively unlikely to occur, the polarity conversion polymer compound is sufficiently hydrophilic, so that the sensitivity is improved and stains may be generated on printed matter. Disappears. Therefore, according to the lithographic printing plate precursor of the present invention, even when the laser exposure is performed at a relatively high speed, the non-image portion is not stained.

As such a polarity conversion functional group, functional groups represented by the following general formulas (1) to (5) are very suitable because they have excellent heat sensitivity and high hydrophilicity after polarity conversion. It is.

[0016]

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(Wherein L is a polyvalent chain composed of nonmetallic atoms)
Represents a linking group, R^TwoIs an alkyl group, an aryl group, an alkenyl
A alkynyl group or a cyclic imide group;^Three, R^Four
Is an alkyl, aryl, alkenyl or alkynyl
R^FiveIs an alkyl group, an aryl group, an alkenyl
Group, alkynyl group or -SO_Two-R¹²And R⁶, R
⁷And R⁸Each independently represents an alkyl group, an aryl group,
A alkenyl group or an alkynyl group,⁹And R^TenWithin
Is hydrogen, the other is hydrogen, an alkyl group, an aryl group,
Represents an alkenyl group or an alkynyl group,¹¹Is alkyl
A alkenyl group or an alkynyl group;¹²Is al
A kill group, an aryl group, an alkenyl group or an alkynyl group
Represents, R⁶, R⁷And R⁸Any two or three of
May form a ring with⁹And R¹¹Or R^TenAnd R¹¹In ring
May be formed. )

As the hydrophilic functional group, the functional groups represented by the following general formulas (6) to (19) are very suitable because they do not hinder the hydrophilicity and the on-press developability of the lithographic printing plate precursor.

[0019]

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(Wherein L is a polyvalent linkage comprising a nonmetallic atom)
M represents a counter cation; ¹, R^Two, R^Three, R^Four
Are each independently hydrogen, an alkyl group, an aryl group,
X represents a counter anion; represents a alkenyl group or an alkynyl group;
You. )

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The lithographic printing plate precursor according to the present invention comprises (a) a polarity-converting polymer compound and (b) a support having a hydrophilic surface.
It has a layer (hereinafter also referred to as an image forming layer) containing a light absorbing agent (hereinafter also referred to as a light-to-heat converting agent). [Image forming layer] The "image forming layer" used in the present invention refers to a layer containing a polarity conversion polymer compound, a photothermal conversion agent and the like described below.

[Polarity Converting Polymer Compound] The polarity converting polymer compound used in the present invention is, as described above, a hydrophobic group having a functional group that changes from hydrophobic to hydrophilic by heat and a hydrophilic functional group in the side chain. Is a hydrophilic polymer compound. This change
When heat is applied by photothermal conversion at the time of laser exposure, a polymer compound that does not show affinity such as dissolving or swelling in water at room temperature becomes one of the polarity conversion functional groups of side chains due to heat. It is necessary that the degree of change is such that part or all change to show an affinity such as dissolution or swelling with water.

The process in which the polarity conversion functional group of the side chain of the polarity conversion polymer compound changes from hydrophobic to hydrophilic by heat is as follows: the originally hydrophobic side chain functional group reacts by heat to change to hydrophilic. There are two processes that can be considered as a process and a process in which the originally hydrophobic side chain functional group is decomposed by heat and loses the hydrophobic functional group to change to hydrophilicity. The former process of reacting with heat to change to hydrophilicity includes the process of changing the hydrophobic functional group to hydrophilic by reacting with other functional groups inside the polymer by heat, and the process of changing the hydrophobic functional group to the outside of the polymer. A process in which the compound is changed to hydrophilic by reacting with other compounds by heat is considered, and the process may be changed to hydrophilic by a process in which two of these compounds are combined.

In the above-mentioned processes, from the viewpoint of reactivity,
A process in which the originally hydrophobic side chain functional group is decomposed by heat and loses the hydrophobic functional group to change to hydrophilicity is preferable. Further, in the present invention, it is more preferable that all the polarity conversion functional groups on the side chains of the polarity conversion polymer compound change to hydrophilic, but the polarity conversion polymer compound dissolves or swells in water. There is no particular limitation as long as the affinity is exhibited to the extent that the affinity is exhibited, and not all of them need to be changed to hydrophilic in consideration of the effects of the hydrophilic functional groups described later. Preferred examples of the functional group that changes from hydrophobic to hydrophilic by heat include functional groups represented by the following general formulas (1) to (5).

[0025]

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In the formula, L is a polyvalent link composed of a nonmetallic atom.
R represents a group^TwoIs an alkyl group, an aryl group, an alkenyl
A alkynyl group or a cyclic imide group;^Three, R^FourIs
Alkyl, aryl, alkenyl or alkynyl
R represents a group^FiveIs an alkyl group, an aryl group, an alkenyl
Group, alkynyl group or -SO_Two-R¹²And R⁶, R ⁷
And R⁸Each independently represents an alkyl group, an aryl group,
A alkenyl group or an alkynyl group,⁹And R^TenWithin
Is hydrogen, the other is hydrogen, an alkyl group, an aryl group,
Represents an alkenyl group or an alkynyl group,¹¹Is alkyl
A alkenyl group or an alkynyl group;¹²Is al
A kill group, an aryl group, an alkenyl group or an alkynyl group
Represents, R⁶, R⁷And R⁸Any two or three of
May form a ring with⁹And R¹¹Or R^TenAnd R¹¹In ring
May be formed.

When R ^{1 to} R ¹¹ represent an alkyl group, the alkyl group may be a straight-chain alkyl group having 1 to 20 carbon atoms,
Examples include branched and cyclic alkyl groups. Specific examples thereof include a methyl group, an ethyl group, a propyl group,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl,
Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, Examples thereof include a 2-norbornyl group. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

When R ^{1 to} R ¹¹ represent a substituted alkyl group,
As the substituent, a monovalent nonmetallic atomic group other than hydrogen is used. As a preferred example, a halogen atom (—F,
-Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group,
Arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkylamino, N-arylamino, N, N-diarylamino, N-alkyl-N-arylamino Group,
Acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N,
N-diarylcarbamoyloxy group, N-alkyl-
N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', An N'-dialkylureido group, an N'-arylureido group, an N ', N'-diarylureido group,
N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-
Arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N- Arylureido group,
An N ′, N′-diaryl-N-alkylureido group,
An N ′, N′-diaryl-N-arylureido group,
N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group,
N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO
₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N-
Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N −
Arylsulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) , dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono Group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (aryl)) and its conjugate base group (hereinafter, arylphosphonate) Onato referred to as group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), Zia Reel phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and the like conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H
(aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group and the like.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group,
Examples thereof include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group. Examples of the alkenyl group include a vinyl group, 1
-Propenyl group, 1-butenyl group, cinnamyl group, 2-
Examples thereof include a chloro-1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
Examples of R ¹² in the acyl group (R ¹² CO—) include hydrogen and the above-described alkyl and aryl groups.

Of these substituents, an even more preferred one is a halogen atom (-F, -Br, -Cl,-
I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-
Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group , N, N-dialkylcarbamoyl, N-arylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulfo, sulfonato, sulfamoyl,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphono Examples thereof include an oxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue excluding any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. , Preferably having 1 to 12 carbon atoms
, A branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group,
Methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyloxymethyl, benzoyloxymethyl, N-cyclohexylcarbamoyl Oxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group,
-Oxopropyl, carboxypropyl, methoxycarbonylethyl, allyloxycarbonylbutyl, chlorophenoxycarbonylmethyl, carbamoylmethyl, N-methylcarbamoylethyl, N, N
-Dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N
-Ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl)
Sulfamoyloctyl group, phosphonobutyl group, phosphonohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-
Methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2- Butynyl group, 3-butynyl group and the like.

When R ^{1 to} R ⁹ and R ¹¹ represent an aryl group, the aryl group is one in which one to three benzene rings form a condensed ring, or a benzene ring and a five-membered unsaturated ring are condensed. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. And a naphthyl group is more preferred. The aryl group includes a heterocyclic (hetero) as well as the carbocyclic aryl group.
Aryl groups are included. As the heterocyclic aryl group,
Those containing 3 to 20 carbon atoms and 1 to 5 heteroatoms such as a pyridyl group, a furyl group, a quinolyl group in which a benzene ring is condensed, a benzofuryl group, a thioxanthone group and a carbazole group are used.

When R ^{1 to} R ⁹ and R ¹¹ represent a substituted aryl group, the substituted aryl group may be a monovalent nonmetallic atom excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. Those with groups are used. Preferred examples of the substituent include the above-mentioned alkyl group, substituted alkyl group and those described above as the substituent for the substituted alkyl group.

Preferred specific examples of such substituted aryl groups are biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethyl Methylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group,
Methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylamino Phenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoyl Phenyl group, N
-(Methoxyphenyl) carbamoylphenyl group, N-
Methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group,
N-tolylsulfamoylphenyl group, N-methyl-N
-(Phosphonophenyl) sulfamoylphenyl group,
Phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1 -Propenylmethyl, 2-butenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl, 3-butynylphenyl and the like.

R ^{1 to} R ¹¹ represent an alkenyl group, a substituted alkenyl group [—C (R ¹³ ) ＝ C (R ¹⁴ ) (R ¹⁵ )], an alkynyl group, or a substituted alkynyl group [—C≡C (R ¹⁶ )], A monovalent nonmetallic atomic group can be used as R ^{13 to} R ¹⁶ . Preferred examples of R ^{13 to} R ¹⁶ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Specific examples thereof include those described above. More preferred substituents for R ¹³ to R ¹⁶ include a hydrogen atom, a halogen atom and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples of the alkenyl group, the substituted alkenyl group, the alkynyl group and the substituted alkynyl group include a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, and a 1-methyl-1-propenyl group. , 2-methyl-1-propenyl group, 2-methyl-1
-Butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, propynyl group, phenylethyl group and the like.

When R ¹ represents a cyclic imide group, examples of the cyclic imide include those having up to 4 to 20 carbon atoms such as succinimide, phthalimide, cyclohexanedicarboxylic imide and norbornenedicarboxylic imide. . Among the above, particularly preferred as R ¹ are an alkyl group, a substituent alkyl group and a cyclic imide group. Of the above, particularly preferred as R ² , R ³ , R ⁴ , and R ¹¹ are an alkyl group substituted with an electron-withdrawing group such as halogen, cyano, and nitro; and an electron-withdrawing group such as halogen, cyano, and nitro. An aryl group substituted with a functional group; and a secondary or tertiary branched alkyl group. R ⁵ ~
Preferred as R ⁹ is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and preferred as R ¹⁰ is an alkyl group or a substituted alkyl group, among R ⁵ , R ⁶ and R ⁷ A ring is formed by any two or three of the above, and R ⁸ and R ¹⁰ or R ⁹ and R ¹⁰
Is a case where a ring is formed.

The polyvalent linking group consisting of a nonmetallic atom represented by L means 1 to 60 carbon atoms, 0 to 10 carbon atoms.
Up to nitrogen atoms, 0 to 50 oxygen atoms, 1
From 100 to 100 hydrogen atoms and 0 to 20 sulfur atoms. More specific linking groups include those constituted by combining the following structural units.

[0038]

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When the polyvalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 6 carbon atoms such as a phenyl group and a naphthyl group.
Up to 16 aryloxy, hydroxyl, carboxyl, sulfonamide, N-sulfonylamido, acetoxy, acyloxy having 1 to 6 carbon atoms, methoxy, 1 to 6 carbon atoms such as ethoxy A halogen atom such as an alkoxy group, chlorine and bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group, and a carbonic acid such as t-butyl carbonate. An ester group or the like can be used.

Next, the hydrophilic functional group will be described. The hydrophilic functional groups suitable for the present invention are represented by the following general formulas (6) to (6).
It is a functional group represented by (19).

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In the formula, L is a polyvalent linking group comprising a nonmetallic atom
And M represents a counter cation; ¹, R^Two, R^Three, R^FourIs
Each independently represents hydrogen, an alkyl group, an aryl group,
X represents a cation group or an alkynyl group, and X represents a counter anion.
The polyvalent linking group comprising a nonmetal atom represented by L is 1
From up to 60 carbon atoms, from 0 to 10 nitrogen
Atom, 0 to 50 oxygen atoms, 1 to 100
Up to hydrogen atoms and 0 to 20 sulfur atoms
It consists of More specific linking groups include
Composed of a combination of the following structural units
Can be mentioned.

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When the polyvalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon atom having 6 carbon atoms such as a phenyl group and a naphthyl group.
To 16 aryl groups, hydroxyl groups, carboxyl groups,
C1-C6 acyloxy groups such as sulfonamide groups, N-sulfonylamido groups, and acetoxy groups; C1-C6 alkoxy groups such as methoxy groups and ethoxy groups; halogens such as chlorine and bromine. An atom, a methoxycarbonyl group, an ethoxycarbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a cyclohexyloxycarbonyl group, a cyano group, a carbonate group such as t-butyl carbonate, or the like can be used.

The counter cation represented by M is an ion having a positive charge, and forms an ion pair with a negative charge in the hydrophilic functional group. Therefore, the counter cation represented by M exists in the same number as the number of moles of the negative charge existing in the hydrophilic functional group in the polarity conversion polymer compound. More specific counter cations include metal cations, ammonium ions, phosphonium ions and the like. Specific examples of metal ions include Li ⁺ , Na ⁺ , K ⁺ , Mg2 ⁺ , Ca2 ⁺ , Ti2 ⁺ , V2 ⁺ , and Cr2 ⁺ .
²⁺ , Mn2 ⁺ , Fe2 ⁺ , Fe3 ⁺ , Co2 ⁺ , Co3 ⁺ , Ni2 ⁺ , Cu ⁺ , C
u ²⁺ , Ag ⁺ , Pb ²⁺ , Sn ²⁺ , Zn ²⁺ , Al ^{3+ and the} like,
The present invention is not limited to these. Specific examples of the ammonium ion include the following, but the present invention is not limited thereto.

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[0047]

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[0048]

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Specific examples of the phosphonium ion include the following, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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When R ^{1 to} R ⁴ represent an alkyl group, an aryl group, an alkenyl group or an alkynyl group, specific examples of these substituents include those described above. The counter anion represented by X is an anion having a negative charge, and forms an ion pair with a positive charge in the hydrophilic functional group. Therefore, the counter anion represented by X is present in the same number of moles as the positive charge existing in the hydrophilic functional group in the polarity conversion polymer compound.

As a more specific counter anion, F^-, C
l^-, Br^-, I^-, OH^-, CN^-, SO_Four ^2-, HSO_Four ^-, SO_Three ^2-, HS
O_Three ^-, NO_Three ^-, CO_Three ^2-, HCO_Three ^-, PF₆ ^-, BF_Four ^-, ClO_Four ^-, Cl
O_Three ^-, ClO_Two ^-, ClO ^-, BrO_Four ^-, BrO_Three ^-, BrO_Two ^-, BrO^-, I
O_Four ^-, IO_Three ^-, IO_Two ^-, IO^-, Sulfonate anion, carvone
Acid anions, phosphonate anions, phosphate anions, etc.
No. Specific examples of the sulfonate anion include:
The following are examples, but the present invention is not limited to these.
It is not something to be done.

[0055]

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[0056]

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The following are specific examples of the carboxylate anion, but the present invention is not limited thereto.

[0058]

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[0059]

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Specific examples of the phosphonate anion include the following, but the present invention is not limited thereto.

[0061]

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The following are specific examples of the phosphate anion, but the present invention is not limited thereto.

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Specific examples of the monomer having a functional group which changes from hydrophobic to hydrophilic by heat, which is suitably used for synthesizing the polarity conversion polymer compound of the present invention, are shown below.

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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Specific examples of a monomer having a hydrophilic functional group, which is suitably used for synthesizing the polarity conversion polymer compound of the present invention, are shown below.

[0074]

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[0075]

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The polarity-converting polymer compound of the present invention has a functional group which changes from hydrophobic to hydrophilic by heat on at least a part of its side chain, and has a hydrophilic functional group on at least a part of its side chain. There is no particular limitation as long as it has a group, and the side chain may have a functional group that changes from hydrophobic to hydrophilic by heat or a functional group other than a hydrophilic functional group. Therefore, even if it is a copolymer with a monomer having a functional group other than a functional group or a hydrophilic functional group that changes from hydrophobic to hydrophilic by heat,
It can be suitably used as long as the effects of the present invention are not hindered. Examples of the monomer having such a side chain include the following monomers.

Other monomers used in the copolymer include acrylic esters, acrylamides, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, maleic amides, and maleic imides. , Itaconic anhydride, itaconic esters, itaconic amides, itaconic imides, crotonic esters, crotonic amides, fumaric esters, fumaric amides, mesaconic esters, mesaconic amides Α, β-unsaturated lactones, α, β
-Unsaturated lactams, unsaturated hydrocarbons, vinyl ethers, vinyl esters, α, β-unsaturated ketones, styrenes, cyclic ethers, cyclic sulfides, cyclic amines, cyclic disulfides, aldehydes, Cyclic acetals, lactones, lactams, cyclic carbonates, cyclic ureas, cyclic urethanes, cyclic acid anhydrides,
Known monomers such as spiro orthocarbonates, spiro orthoesters, and acrylonitrile are exemplified.

Specific examples of the acrylates include:
Methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec-
Or t-) butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acryle DOO, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N- (n- or i-) propylacrylamide, N- (n-, i-, sec- or t-) Acrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N -(Tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N
-Phenylacrylamide, N-hydroxyethyl-N
-Methylacrylamide and the like.

Specific examples of methacrylates include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i
-, Sec- or t-) butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxy Phenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

Specific examples of methacrylamides include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N- (n- or i-) propyl methacrylamide, N- (n-, i-, sec. -Or t
-) Methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacrylamide, N-phenyl methacrylamide, N-tolyl methacrylamide,
N- (hydroxyphenyl) methacrylamide, N-
(Sulfamoylphenyl) methacrylamide, N-
(Phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of crotonic esters include:
Methyl crotonate, ethyl crotonate, (n- or i-) propyl crotonate, (n-, i-, sec-
Or t-) butyl crotonate, pentyl crotonate, hexyl crotonate, heptyl crotonate, octyl crotonate, nonyl crotonate, decyl crotonate, amyl crotonate, 2-ethylhexyl crotonate, dodecyl crotonate, chloroethyl crotonate , 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 5-hydroxypentyl crotonate, cyclohexyl crotonate, allyl crotonate, trimethylolpropane monocrotonate, pentaerythritol monocrotonate, benzyl crotonate, methoxy benzyl crotonate , Chlorobenzylcrotonate, hydroxybenzylcrotonate, hydroxyphenethylcrotonate, dihydroxyphenethylcrotonate Bok, furfuryl crotonate, tetrahydrofurfuryl crotonate, phenyl crotonate, hydroxyphenyl crotonate, chlorophenyl crotonate, sulfamoyl phenyl crotonate, 2- (hydroxyphenyl carbonyloxy) ethyl crotonate, and the like.

Specific examples of crotonamides include crotonamide, N-methylcrotonamide, N-ethylcrotonamide, N- (n- or i-) propylcrotonamide, N- (n- , I-, sec- or t
-) Crotonic acid amide, N-benzyl crotonic acid amide, N-hydroxyethyl crotonic acid amide, N-phenyl crotonic acid amide, N-tolyl crotonic acid amide,
N- (hydroxyphenyl) crotonamide, N-
(Sulfamoylphenyl) crotonamide, N-
(Phenylsulfonyl) crotonamide, N- (tolylsulfonyl) crotonamide, N, N-dimethylcrotonamide, N-methyl-N-phenylcrotonamide, N-hydroxyethyl-N-methylcrotonamide, etc. Is mentioned.

Specific examples of maleic esters include:
Dimethyl maleate, diethyl maleate, di (n- or i-) propyl maleate, di (n-, i-maleate)
-, Sec- or t-) butyl, diphenyl maleate, diallyl maleate, monomethyl maleate, monoethyl maleate, mono (n- or i-) propyl maleate, mono (n-, i-, sec- Or t
-) Butyl, dibenzyl maleate, monobenzyl maleate, methyl ethyl maleate, methyl propyl maleate, ethyl propyl maleate and the like.

Specific examples of maleic amides include maleic amide, N-methylmaleamide, N-ethylmaleamide, N- (n- or i-) propylmaleamide, N- (n- , I-, sec- or t
-) Butylmaleamide, N-benzylmaleamide, N-hydroxyethylmaleamide, N-
Phenylmaleamide, N-tolylmaleamide, N- (hydroxyphenyl) maleamide, N
-(Sulfamoylphenyl) maleamide, N-
(Phenylsulfonyl) maleamide, N- (tolylsulfonyl) maleamide, N, N-dimethylmaleamide, N-methyl-N-phenylmaleamide, N-hydroxyethyl-N-methylmaleamide, N-methylmaleic acid monoamide, N-ethylmaleic acid monoamide, N, N-dimethylmaleic acid monoamide, N-methyl-N'-ethylmaleic acid amide, N-methyl-N'-phenylmaleic acid amide and the like can be mentioned. .

Specific examples of maleic imides include maleimide, N-methylmaleimide, N-ethylmaleimide, N- (n- or i-) propylmaleimide, N- (n- , I-, sec- or t
-) Butylmaleimide, N-benzylmaleimide, N-hydroxyethylmaleimide, N-
Phenylmaleimide, N-tolylmaleimide, N- (hydroxyphenyl) maleimide, N
-(Sulfamoylphenyl) maleimide, N-
(Phenylsulfonyl) maleimide, N- (tolylsulfonyl) maleimide and the like.

Specific examples of itaconic esters include:
Dimethyl itaconate, diethyl itaconate, di (n- or i-) propyl itaconate, di (n-, i
-, Sec- or t-) butyl, diphenyl itaconate, diallyl itaconate, monomethyl itaconate, monoethyl itaconate, mono (n- or i-) propyl itaconate, mono (n-, i-, sec- itaconate) Or t
-) Butyl, dibenzyl itaconate, monobenzyl itaconate, methylethyl itaconate, methylpropyl itaconate, ethylpropyl itaconate and the like.

Specific examples of itaconamides include itaconamide, N-methylitaconamide, N-ethylitaconamide, N- (n- or i-) propylitaconamide, N- (n -, I-, sec- or t
-) Butyl itaconamide, N-benzyl itaconamide, N-hydroxyethyl itaconamide, N-
Phenylitaconamide, N-tolylitaconamide, N- (hydroxyphenyl) itaconamide, N
-(Sulfamoylphenyl) itaconamide, N-
(Phenylsulfonyl) itaconamide, N- (tolylsulfonyl) itaconamide, N, N-dimethylitaconamide, N-methyl-N-phenylitaconamide, N-hydroxyethyl-N-methylitaconamide, N-methylitaconic acid monoamide, N-ethylitaconic acid monoamide, N, N-dimethylitaconic acid monoamide, N-methyl-N'-ethylitaconic acid amide, N-methyl-N'-phenylitaconic acid amide and the like can be mentioned. .

Specific examples of itaconic imides include itaconimide, N-methylitaconimide, N-ethylitaconimide, N- (n- or i-) propylitaconimide, N- (n- , I-, sec- or t
-) Butyl itaconimide, N-benzyl itaconimide, N-hydroxyethyl itaconimide, N-
Phenylitaconimide, N-toluitaconimide, N- (hydroxyphenyl) itaconimide, N
-(Sulfamoylphenyl) itaconimide, N-
(Phenylsulfonyl) itaconimide, N- (tolylsulfonyl) itaconimide and the like.

Specific examples of fumaric esters include dimethyl fumarate, diethyl fumarate and di (n-fumarate).
Or i-) propyl, fumarate di (n-, i-, sec)
-Or t-) butyl, diphenyl fumarate, diallyl fumarate, monomethyl fumarate, monoethyl fumarate, mono (n- or i-) propyl fumarate, mono (n-, i-, sec- or t-) fumarate ) Butyl, dibenzyl fumarate, monobenzyl fumarate, methylethyl fumarate, methylpropyl fumarate, ethylpropyl fumarate and the like.

Specific examples of fumaric acid amides include fumaric acid amide, N-methyl fumaric acid amide, N-ethyl fumaric acid amide, N- (n- or i-) propyl fumaric acid amide, N- (n-, i- -, Sec- or t-) butyl fumaric acid amide, N-benzyl fumaric acid amide, N-hydroxyethyl fumaric acid amide, N-phenyl fumaric acid amide, N-tolyl fumaric acid amide, N- (hydroxyphenyl) fumaric acid amide, N- (sulfamoylphenyl) fumaric acid amide, N- (phenylsulfonyl) fumaric acid amide, N- (tolylsulfonyl) fumaric acid amide, N, N-dimethyl fumaric acid amide, N-methyl-N
-Phenyl fumaric acid amide, N-hydroxyethyl-N
-Methyl fumaric acid amide, N-methyl fumaric acid monoamide, N-ethyl fumaric acid monoamide, N, N-dimethyl fumaric acid monoamide, N-methyl-N'-ethyl fumaric acid amide, N-methyl-N'-phenyl fumaric acid amide, etc. No.

Specific examples of the mesaconate esters include:
Dimethyl mesaconate, diethyl mesaconate, di (n- or i-) propyl mesaconate, di (n-, mesaconate)
i-, sec- or t-) butyl, diphenyl mesaconate, diallyl mesaconate, monomethyl mesaconate, monoethyl mesaconate, mono (n- or i-) propyl mesaconate, mono (n-, i-, sec -Or t
-) Butyl, dibenzyl mesaconate, monobenzyl mesaconate, methylethyl mesaconate, methylpropyl mesaconate, ethylpropyl mesaconate and the like.

Specific examples of mesaconic amides include mesaconic amide, N-methyl mesaconic amide, N-ethyl mesaconic amide, N- (n- or i-) propyl mesaconic amide, N- (n-, i-, sec- or t
-) Butyl mesaconamide, N-benzyl mesaconamide, N-hydroxyethyl mesaconamide, N-
Phenyl mesaconic amide, N-tolyl mesaconic amide, N- (hydroxyphenyl) mesaconic amide, N
-(Sulfamoylphenyl) mesaconic amide, N-
(Phenylsulfonyl) mesaconamide, N- (tolylsulfonyl) mesaconamide, N, N-dimethylmesaconamide, N-methyl-N-phenylmesaconamide, N-hydroxyethyl-N-methylmesaconamide , N-methyl mesaconic acid monoamide, N-ethyl mesaconic acid monoamide, N, N-dimethyl mesaconic acid monoamide, N-methyl-N'-ethyl mesaconic acid amide, N-methyl-N'-phenyl mesaconic amide and the like. .

Specific examples of styrenes include styrene,
Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include iodostyrene, fluorostyrene, carboxystyrene, and the like.

Specific examples of α, β-unsaturated lactones include the following compounds.

[0096]

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Specific examples of the α, β-unsaturated lactams include the following compounds.

[0098]

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Specific examples of the unsaturated hydrocarbons include the following compounds.

[0100]

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Specific examples of vinyl ethers include the following compounds.

[0102]

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Specific examples of vinyl esters include the following compounds.

[0104]

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Specific examples of the α, β-unsaturated ketones include the following compounds.

[0106]

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Specific examples of the cyclic ethers include the following compounds.

[0108]

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Specific examples of the cyclic sulfides include the following compounds.

[0110]

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Specific examples of the cyclic amines include the following compounds.

[0112]

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Specific examples of cyclic disulfides include the following compounds.

[0114]

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Specific examples of aldehydes include the following compounds.

[0116]

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Specific examples of the cyclic acetal include the following compounds.

[0118]

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Specific examples of lactones include the following compounds.

[0120]

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Specific examples of lactams include the following compounds.

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Specific examples of the cyclic carbonates include the following compounds.

[0123]

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Specific examples of the cyclic ureas include the following compounds.

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Specific examples of the cyclic urethanes include the following compounds.

[0127]

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Specific examples of the cyclic acid anhydrides include the following compounds.

[0129]

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Specific examples of spiro orthocarbonates include the following compounds.

[0131]

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Specific examples of spiro ortho esters include the following compounds.

[0133]

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The proportion of the monomer having a functional group which changes from hydrophobic to hydrophilic by heat used in the synthesis of the polarity conversion polymer compound of the present invention is preferably from 10 to 95% by weight, more preferably from 40 to 90% by weight. Is more preferred. If the proportion of the monomer having a functional group that changes from hydrophobic to hydrophilic by heat is less than 10% by weight, the degree of polarity conversion by heat is too small, and the difference in hydrophilicity between the image area and the non-image area is small. The image becomes blurred. On the other hand, if the content is more than 95% by weight, sufficient hydrophilicity cannot be obtained in the vicinity of the substrate in the heating portion of the image forming layer, so that the non-image portion is stained during printing. The monomer having a functional group that changes from hydrophobic to hydrophilic by heat may be used alone or in combination of two or more.

The proportion of the monomer having a hydrophilic functional group used for synthesizing the polarity conversion polymer compound used in the present invention is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight.
Is more preferred. If the proportion of the monomer having a hydrophilic functional group is less than 5% by weight, sufficient hydrophilicity cannot be obtained in the vicinity of the substrate in the heating section of the image forming layer.
Non-image areas are stained during printing. Also, if the content is more than 50% by weight, the polymer becomes a polymer compound having high hydrophilicity from the beginning, so that the unheated portion is easily removed at the time of printing.
The image becomes unclear or the printing durability deteriorates. As the monomer having a hydrophilic functional group, only one kind may be used, or two or more kinds may be mixed and used.

In the case of using another copolymerizable monomer as the third component for the synthesis of the polarity conversion polymer compound used in the present invention, the ratio of the third copolymerizable other monomer is as follows. Any ratio can be used as long as a monomer having a functional group which changes from hydrophobic to hydrophilic by heat and a monomer having a hydrophilic functional group are used in a preferable ratio. As the third component, another copolymerizable monomer, only one type may be used, or 2
More than one kind may be mixed and used. Hereinafter, specific examples of the polarity conversion polymer compound used in the present invention will be shown. However, the present invention is not limited to these.

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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The weight-average molecular weight of the polarity-converting polymer compound used in the lithographic printing plate precursor according to the invention, measured by GPC, is preferably 2,000 or more, more preferably 5,000 to 300,000. The number average molecular weight is preferably 800 or more, more preferably 1000 to 2
The range is 50,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 1.1.
The range is 10. These polymer compounds may be any of a random polymer, a block polymer, a graft polymer and the like, but are preferably random polymers.

Solvents used for synthesizing the polarity conversion polymer compound used in the present invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, and the like.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N
-Dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents can be used alone or in combination of two or more.

As the radical polymerization initiator used when synthesizing the polarity conversion polymer compound used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used. Examples of the cationic polymerization initiator used when synthesizing the polarity conversion polymer compound used in the present invention include perchloric acid, fluorosulfonic acid, trifluoromethanesulfonic acid, 12-molybdophosphoric acid, and 12-tungstophosphoric acid. And super-strong acid esters such as methyl trifluoromethanesulfonate and methyl fluorosulfonate; super-strong acid anhydrides such as trifluoromethanesulfonic anhydride and fluorosulfonic anhydride; PF ₅ , Sb
F _5, BF ₃ and the like Lewis _{acids, Et 3 OSbF 6, Et 3} OB
Oxonium salts such as F ₄ , Ph ₃ CPF ₆ , Ph ₂ CHCl
+ AgSbF _{6 and} other carbenium salts, PhCOCl + A
GSbF ₆ oxocarbenium salts such as, 1,3-dioxolan-2-ylium hexafluoroantimonate and di oxacarbenium salts, benzyl-p-cyanopyridinium hexafluoroantimonate, (p-methoxybenzyl)-p- Known compounds such as thermal latent initiators such as cyanopyridinium hexafluoroantimonate, iodonium salts such as diphenyliodonium hexafluoroantimonate, and sulfonium salts such as triphenylsulfonium hexafluoroantimonate can be used. The polarity conversion polymer compound used in the present invention may be used alone or as a mixture of several types.

The image-forming layer used in the present invention may be composed of the polarity-converting polymer compound alone, or may be, if necessary, combined with the polarity-converting polymer compound within a range not to impair the effects of the present invention. It may be composed of components. The polarity conversion polymer compound can be used in a proportion of 50 to 95% by weight, preferably 70 to 95% by weight of the total solids in the image forming layer. When the addition amount is less than 50% by weight, the image strength becomes weak and the printing durability is lowered. If the addition amount exceeds 95% by weight, image formation cannot be sufficiently performed due to heating by a thermal head or the like or photothermal conversion by laser exposure.

The following compounds may be mentioned as constituents other than the polarity conversion polymer compound of the image forming layer used in the present invention.

(Light Absorbing Agent) When the lithographic printing plate precursor of the invention is used as a lithographic printing plate precursor for forming an image by laser exposure, a light absorbing agent is added to the image forming layer of the lithographic printing plate precursor. I do. The light absorber preferably used in the present invention is a dye or pigment that effectively absorbs light having a wavelength of 760 to 1200 nm. More preferably, the wavelength 7
It is a dye or pigment having an absorption maximum at 60 to 1200 nm. As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, and dyes such as metal thiolate complexes.

Preferred dyes are described in, for example, JP-A-58-1983.
125246, JP-A-59-84356, JP-A-5-84356
Cyanine dyes described in JP-A Nos. 9-202829 and 60-78787;
696, JP-A-58-181690, JP-A-58-181
Methine dyes described in publications such as 194595,
JP-A-58-112793, JP-A-58-22479
No. 3, JP-A-59-48187, JP-A-59-739
No. 96, JP-A-60-52940, JP-A-60-63
Naphthoquinone dyes described in publications such as 744;
Examples include squarylium dyes described in JP-A-58-112792 and cyanine dyes described in British Patent No. 434,875.

The near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used.
Substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 142645 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt disclosed in
No. 181051, No. 58-220143, No. 59-4
Nos. 1363, 59-84248, 59-8424
No. 9, No. 59-146063, No. 59-146061
Pyrylium-based compounds described in Japanese Patent Application Laid-open No.
No. 9-216146, cyanine dyes described in U.S. Pat. No. 4,283,475, pentamethine thiopyrylium salts, and Japanese Patent Publication Nos. 5-135514 and 5-1.
A pyrylium compound disclosed in JP 9702 is also preferably used.

As another preferred example of the dye, the compounds represented by formulas (I) and (I) are described in US Pat. No. 4,756,993.
Mention may be made of near-infrared absorbing dyes described under I). Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used. The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment,
Red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment,
Metal powder pigments and other polymer-bound dyes can be used.
Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. Methods of surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo)
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. When the particle size of the pigment is less than 0.01 μm, it is not preferable in terms of the stability of the dispersion in the coating solution of the photosensitive composition, and when it exceeds 10 μm, the uniformity of the image recording layer after coating is lowered. Is not preferred. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the composition of the image forming layer of the lithographic printing plate precursor according to the invention. Is particularly preferably 0.5 to 10% by weight, and in the case of a pigment, 1.0 to 10% by weight can be particularly preferably added. When the amount of the pigment or dye added is 0.
When the amount is less than 01% by weight, the sensitivity is lowered, and when the amount exceeds 50% by weight, stains are apt to occur in the non-image area during printing.

(Acid Generator) When the lithographic printing plate precursor according to the present invention is used as a lithographic printing plate precursor for forming an image by laser exposure, light or heat is applied to the image forming layer of the lithographic printing plate precursor. It is desirable to add a compound that generates an acid (hereinafter, referred to as an acid generator). However, the above-mentioned polarity conversion polymer compound itself generates an acid by heat, and sometimes exhibits a function as an acid generator. In such a case, an image can be obtained without using another acid generator in particular. An acid generator is not required as it can be formed.

As the acid generator used in the present invention, the following known compounds can be selected and used. For example, SI Schlesinger, Photogr. Sci. Eng., 1
8, 387 (1974), TSBa1 etal., Polymer, 21, 423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, ammonium salts described in JP-A-3-140,140 and the like, DCNecker et al., Macromolecule
s, 17, 2468 (1984), CSwen et al., Teh, Proc. Conf.
Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in publications such as JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1
988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514 and the like,

JVCrivello et al., Polymer J. 17, 73
(1985), JVCrivello et al., J. Org.Chem., 43, 3055.
(1978), WRWatt et al., J. Polymer Sci., Polymer C
hem. Ed., 22, 1789 (1984), JVCrivello etal., Poly
mer Bull., 14, 279 (1985), JVCrivello etal, Macro
morecules, 14 (5), 1141 (1981), JVCrivello etal.,
J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979)
, EP 370,693, U.S. Patent 3,902,114, EP 233,567, 297,443, 297,442, U.S. Patents 4,933,377, 410,201, 339,049, 4,76
No. 0,013, 4,734,444, 2,833,827, German Patent No.
2,904,626, 3,604,580, 3,604,581, and the like, and sulfonium salts described in JVCrivello et al., Macr.
omorecules, 10 (6), 1307 (1977), JVCrivello etal.,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (197
9) etc., selenonium salts, CSwen et al., Teh, Pr
oc. Conf. Rad. Curing ASIA, p478 Tokyo, 0ct (1988)
Onium salts such as arsonium salts described in U.S. Pat.
3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835
No., JP-A-61-169837, JP-A-62-58241, JP-A-62-58241
212401, JP-A-63-70243, organic halogen compounds described in JP-A-63-298339 and the like,

K. Meier et al., J. Rad. Curing, 13 (4), 26
(1986), TPGill et al., Inorg.Chem., 19, 3007 (198
0), D. Astruc, Acc. Chem. Res., 19 (12), 377 (189
6), organometallic / organic halides described in JP-A-2-14145 and the like, S. Hayase et al., J. Polymer Sci., 25,
753 (1987), E. Reichmanis et al., J. Po1ymer Sci., Po
1ymer Chem. Ed., 23, 1 (1985), QQZhu et al., J. P.
hotochem., 36, 85, 39,317 (1987), B. Amit et al., T
etrahedron Lett., (24) 2205 (1973), DHRBarton
tal., J. Chem Soc., 3571 (1965), PM Collins et al.,
J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinsteine
tal, Tetrahedron Lett., (17), 1445 (1975), JWWalk
er etal., J. Am. Chem. Soc., 110, 7170 (1988), SCB
usman etal., J. Imaging Technol., 11 (4), 191 (1985)
, HM Houlihan et al., Macromolecules, 21, 2001 (198
8), PMCollins et al., J. Chem. Soc., Chem. Commu
n., 532 (1972), S. Hayase etal., Macromolecules, 1
8, 1799 (1985), E. Reichmanisetal., J. Electrochem.
Soc., So1id State Sci. Technol., 130 (6), FMHouli
han etal., Macromolcules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,8
No. 51, No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,1
81,531, JP-A-60-198538, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022 and the like,

M. TUNOOKA et al., Polymer Preprints Jap
an, 35 (8), G. Bermer et al., J. Rad, Curing, 13 (4), W.
J. Mijs etal, Coating Technol., 55 (697)., 45 (198
3), Akzo, H. Adachi et al., Polymer Preprints, Japa
n, 37 (3), EP 0199,672, EP 84515, EP 199,
Nos. 672, 044,115, 0101,122, U.S. Pat.
No. 8,564, 4,371,605, 4,431,774, JP-A-64-18
No. 143, JP-A-2-245756, compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonates and the like described in JP-A-61-166544, and the like. Disulfone compounds described in the gazettes, JP-A-50-36209
(U.S. Pat.No. 3,969,118) o-Naphthoquinonediazide-4-sulfonic acid halide described in JP-A-55-62444
(British Patent No. 2038801)
An o-naphthoquinonediazide compound described in JP-A-35 can be mentioned.

Other acid generators include cyclohexyl citrate, alkyl sulfonate such as cyclohexyl p-acetoaminobenzenesulfonate, cyclohexyl p-bromobenzenesulfonate, and the like. An alkylsulfonic acid ester represented by the following structural formula described in Japanese Patent Application No. 9-26878 can be used.

[0162]

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Among the compounds which decompose upon irradiation with light, heat or radiation to generate an acid, those which are particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
S-triazine derivative represented by 2),

[0164]

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In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —CY ₃ .
Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0166]

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[0167]

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(2) An iodonium salt represented by the following formula (PAG3), a sulfonium salt represented by the following formula (PAG4), or a diazonium salt.

[0169]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom for an aryl group, and an alkyl group for an alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z ^- represents a counter anion.
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si ₂ F ₂ ⁻ , Cl
Perfluoroalkanesulfonic acid anions such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ ; bonded polynuclear aromatic sulfonic acid anions such as pentafluorobenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion; anthraquinonesulfonic acid anion; sulfonic acid group Dyes and the like are included, but are not limited thereto. Also, R ³ , R ⁴ and R
Two and Ar ¹ of ^5, Ar ² may be combined through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0174]

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[0175]

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The above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knap
czyk etal, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al., J. Org.Chem., 35, 2532 (1970), B. G.
oethas etal, Bull. Soc. Chem. Belg., 73, 546 (196
4), HM Leicester, J. Am. Chem. Soc., 51, 3587 (1
929), JV Crivello et al, J. Polym. Chem. Ed., 1
8, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101,331.
Can be synthesized by the method described in Japanese Patent Publication No.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0178]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

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[0181]

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The content of these acid generators is usually 0.1 to the total solid content of the image forming layer of the lithographic printing plate precursor according to the invention.
It is 1 to 30% by weight, more preferably 1 to 15% by weight.

(Sensitizing dye) When the acid generator has no sensitivity from the ultraviolet region to the visible region, various acid generators are used to activate the acid generator with respect to light in the ultraviolet region to the visible region. Sensitizing dyes are used. Examples of such sensitizing dyes include pyran dyes described in US Pat. No. 5,238,782, cyanine dyes described in US Pat. No. 4,997,745, and squarylium dyes, and US Pat. ,
No. 262,276, a merocyanine dye, a pyrium dye described in JP-B-8-20732,
In addition, Michler's ketone, thioxanthone, ketocoumarin dye, 9-phenylacridine and the like can be used as effective ones. In addition, U.S. Pat.
No. 987,230, a polycyclic aromatic compound such as a bisbenzylidene ketone dye and 9,10-diphenylanthracene can be used.

As other components, for example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 6
03, Oil Black BY, Oil Black BS, Oil Black T-505 (orient chemical industry)
Manufactured), Victoria Pure Blue, Crystal Violet (CI. 42555), Methyl Violet (C.I.
I. 42535), ethyl violet, rhodamine B
(CI. 145170B), malachite green (CI. 42000), methylene blue (CI.
2015) and the like, or dyes described in JP-A-62-293247 and Japanese Patent Application No. 7-335145. The addition amount is 0.01 to 0.01% based on the total solids of the image forming layer of the lithographic printing plate precursor according to the invention.
10% by weight.

(Surfactant) In the image forming layer of the lithographic printing plate precursor according to the present invention, JP-A No. 62-251740 and JP-A No. 3-1740 are used in order to enhance stability under printing conditions.
Nonionic surfactants as described in JP 08514, JP-A-59-121044,
An amphoteric surfactant as described in JP-A-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N
-Carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.)
And the like. The proportion of the nonionic surfactant and amphoteric surfactant in the total solids of the image forming layer is 0.0%.
It is preferably from 5 to 15% by weight, more preferably from 0.1 to 5% by weight.
% By weight.

(Others) Further, a plasticizer may be added to the image forming layer of the lithographic printing plate precursor according to the invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl fuclate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate,
An oligomer or polymer of trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid, or the like is used.

The image forming layer of the lithographic printing plate precursor according to the invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution on a suitable support. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate,
Examples include, but are not limited to, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene, water and the like. . These solvents are used alone or as a mixture. When preparing a coating solution, the concentration of the above-mentioned components of the image forming layer (total solid content including additives) in the solvent is preferably 1 to 50% by weight.

As the method of coating, various known methods can be used. For example, bar coating, spin coating, spray coating, curtain coating, dip coating,
Examples include air knife application, blade application, roll application, and the like. In the image forming layer of the lithographic printing plate precursor according to the invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant as described in JP-A-62-170950 is used. Can be added. The preferred addition amount is 0.01 to 0.01% based on the total solid content of the image forming layer.
1% by weight, and more preferably 0.05 to 0.5% by weight.

The coating amount (solid content) of the image forming layer obtained after coating and drying varies depending on the intended use, but for a general lithographic printing plate precursor, it is preferably 0.5 to 5.0 g / m ² , 0.5-1.5 g / m < ² > is more preferable.

[Support] The support (substrate) used for the lithographic printing plate precursor on which the image forming layer of the present invention is to be coated is a plate-like material having good dimensional stability. Any known materials used as a support can be suitably used. As such a support, paper, paper laminated with plastics (for example, polyethylene, polypropylene, polystyrene, etc.), for example, a metal plate such as aluminum (including aluminum alloy), zinc, iron, copper, etc., for example, Plastic films such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Is laminated or vapor-deposited on paper or a plastic film, but an aluminum plate is particularly preferable. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used. For example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel is used. It is acceptable for these alloy compositions to contain some negligible amount of impurities in addition to some iron and titanium.

The support is subjected to a surface treatment as required.
For example, when preparing a lithographic printing plate precursor, the surface of the support is subjected to a hydrophilic treatment prior to applying the image forming layer. In the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or anodizing is performed. Is preferred. No. 2,714,06.
No. 6, as described in U.S. Pat. No. 6,181,461, an aluminum plate immersed in an aqueous solution of sodium silicate and then anodized as described in U.S. Pat. No. 3,181,461. After immersion in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more electrolytic solutions. It is carried out by passing a current through an aluminum plate as an anode.

As the surface treatment, US Pat.
Electrodeposition of silicate as described in JP-A-8,662 is also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent a harmful reaction with the photosensitive / thermosensitive composition provided thereon and to adhere to the photosensitive layer. It is performed to improve the performance. Prior to roughening the aluminum plate by graining, the surface may be subjected to a pretreatment, if necessary, to remove rolling oil on the surface or to expose a clean aluminum surface. Usually, for removing rolling oil etc.
Solvents such as trichlene, surfactants and the like are used.
In order to expose a clean surface, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the like.
A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in JP-A-54-31187 is suitable. As the electrochemical method, an acidic electrolytic method such as hydrochloric acid, nitric acid or a combination thereof is used. A method of performing AC electrolysis in a liquid is preferable. Among such surface roughening methods, in particular,
A surface roughening method which combines mechanical surface roughening and electrochemical surface roughening as described in JP-A-5-137933 is preferred because the adhesive force of the oil-sensitive image to the support is strong. The graining by the above-described method is preferably performed in a range where the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μm. The aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary coatings on the etched surface. Most preferably, these etching agents are used so that the dissolution rate of the aluminum or alloy to be used is 0.3 to 40 g / m ² per one minute of immersion time at the setting of the working concentration and temperature. It can be higher or lower,

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution, or by applying the etching solution to the aluminum plate.
The treatment is preferably performed so as to be in the range of 10 to 10 g / m ² . As the etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. As the acid used for the desmut treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is passed through aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like or a combination of two or more thereof, the aluminum is supported. An anodized film can be formed on the body surface.

The anodizing treatment conditions cannot be generally determined because they vary depending on the electrolytic solution to be used. However, generally, the concentration of the electrolytic solution is 1 to 80% by weight and the liquid temperature is 5 to 70%.
° C, current density 0, 5-60 amps / dm ² , voltage 1 ~
A range of 100 V and an electrolysis time of 30 seconds to 50 minutes is appropriate. Among these anodizing treatments, in particular, the method of anodizing at high current density in sulfuric acid described in British Patent No. 1,412,768 and US Pat.
The method of anodic oxidation using phosphoric acid as an electrolytic bath described in Japanese Patent No. 1,661 is preferable. The aluminum plate which has been roughened as described above and further anodized may be subjected to a hydrophilization treatment, if necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181. , 46
No. 1 discloses an alkali metal silicate, for example, an aqueous solution of sodium silicate or JP-B-36-22.
There is a method of treating with potassium fluoride zirconate disclosed in U.S. Pat. No. 063 and polyvinyl phosphonic acid as disclosed in U.S. Pat. No. 4,153,461.

[Other Layers] A back coat is provided on the back surface of the support, if necessary. Such a back coat comprises an organic polymer compound described in JP-A-5-45885 and a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in JP-A-6-35174. A coating layer is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ )
₄ , Si (OC ₃ H ₇ ) ₄ , silicon alkoxy compounds such as Si (OC ₄ H ₉ ) ₄ are easily available at a low cost, and the metal oxide coating layer obtained therefrom is particularly preferable because of its excellent hydrophilicity. .

[Plate making method] Next, a plate making method of the lithographic printing plate precursor will be described. The lithographic printing plate precursor is, for example, directly subjected to image-wise thermal recording by a thermal recording head or the like, or image-exposed by a solid-state laser or semiconductor laser emitting infrared light having a wavelength of 760 to 1200 nm, or a wavelength of 400 to 760 nm. Image exposure with a visible light laser that emits visible light, or image exposure with a light source that emits ultraviolet light or visible light. The lithographic printing plate precursor that has been image-exposed may be subjected to water development after exposure and, if necessary, gumming, and then the plate may be mounted on a printing machine for printing. Immediately after exposure (without passing through the developing step), printing can be performed by mounting the plate on a printing press. In this case, the heated portion or the exposed portion swells due to dampening water or the like, and the swelled portion is removed at the initial stage of printing to form a lithographic printing plate. That is, in the plate making method using the lithographic printing plate precursor of the present invention, the lithographic printing plate can be made without any particular development processing. The water development in the present invention refers to developing with water or a developer containing water as a main component and having a pH of 2 or more. In both the case where water development is performed and the case where development processing is not performed, it is preferable to perform heat treatment after exposure from the viewpoint of improving sensitivity during recording. The conditions of the heat treatment are 80 to
It is preferable that the heating is performed within a range of 150 ° C. for 10 seconds to 5 minutes. That is, by performing this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

The lithographic printing plate precursor of the present invention obtained by such a process is subjected to water development or directly applied to an offset printing machine or the like without going through a development step, and is used for printing a large number of sheets.

[0200]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. [Synthesis of Monomer (1)] 1-Methoxy-2-propanol: 121.2 g and pyridine: 141.6 g were placed in a 1000 ml three-necked flask and stirred for 30 minutes under ice-cooling. P-
Vinyl benzene sulfonic acid chloride: 181.7 g was added dropwise under ice cooling, and the mixture was stirred for 6 hours after completion of the addition. Pour the reaction mixture into 500 ml of ice water, extract with ethyl acetate,
Washed with saturated saline. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain an oil. The oil was purified by column chromatography using silica gel to obtain the monomer (1) as a colorless oil. The calculated values of the elemental analysis were C: 56.23% and H: 6.29%, and the actually measured values were C: 56.35% and H: 6.33%.

[Synthesis of Monomer (7)] Monomer (7) was synthesized in the same manner as monomer (1) except that 3-methacryloyloxypropanesulfonic acid chloride was used instead of p-vinylbenzenesulfonic acid chloride. . As a result of ¹ H-NMR measurement of the monomer (7), 6.12 pp
At m and 5.60 ppm, a signal attributed to hydrogen bonded to the double bond carbon of the methacryloyl group was observed, and at 3.39 ppm, a signal attributed to the methoxy group in the sulfonic ester portion was observed.

[Synthesis of Monomer (3)] 1-methoxy-2-
Monomer (3) was synthesized in the same manner as monomer (1) except that cyclohexanol was used instead of propanol. Elemental analysis: C: 63.13%, H: 6.81%
The actual measured values were C: 63.21% and H: 6.90%. [Synthesis of Monomer (10)] Monomer (10) was synthesized in the same manner as monomer (1) except that chloro [(4-vinylphenyl) methyl] sulfone was used instead of p-vinylbenzenesulfonic acid chloride. . As a result of ¹ H-NMR measurement of the monomer (10), 6.72 ppm, 5.79 pp
m, at 5.30 ppm, a signal attributed to hydrogen bonded to the double bond carbon of the vinyl group was observed, and at 4.39 ppm, a signal attributed to hydrogen bonded to the methyl carbon of the (4-vinylphenyl) methyl group was observed. As a result, a signal attributed to the methoxy group in the sulfonic acid ester portion was observed at 3.39 ppm.

[Synthesis of Monomer (87)] 2,4-Dinitrotoluene: 1.06 was placed in a 5-liter three-necked flask.
g, acrylic acid: 500 g, and dihydropyran: 488 g. Concentrated hydrochloric acid was added dropwise to this mixture while stirring under ice cooling, and the reaction mixture was heated to about 60 ° C. and stirred for 2 hours and 30 minutes. After allowing to cool to room temperature, the reaction mixture was made alkaline with sodium hydroxide and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a monomer (87). [Synthesis of Monomer (83)] Monomer (83) was synthesized in the same manner as for monomer (87) except that p-vinylbenzoic acid was used instead of acrylic acid.

[Synthesis of Polarity Converting Polymer Compound (1)]
In a 0 ml three-necked flask, 23 g of the monomer (1) and 2.1 g of sodium p-vinylbenzenesulfonate were weighed and dissolved in 50 g of dimethyl sulfoxide. 65
Azobisdimethyl valeronitrile: 0.32 g was added while stirring under a nitrogen stream at ℃. While stirring at the same temperature, azobisdimethyl valeronitrile: 0.2 every 2 hours.
16 g and 0.08 g were added, and stirring was continued for convenient 6 hours to complete the reaction. The reaction mixture was diluted with 40 g of acetone, and then diluted with 5 g of acetone.
2 liters of hexane was put into a 1 liter hollow beaker, and the diluent prepared above was added dropwise thereto with good stirring by a mechanical stirrer. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was determined by GPC to be a polymer having a weight average molecular weight of 152,000.

[Synthesis of Polarity Converting Polymer Compound (2)] A monomer (7) was used instead of the monomer (1), and potassium 3-methacryloyloxypropanesulfonate was used instead of sodium p-vinylbenzenesulfonate. Synthesized a polarity conversion polymer compound (2) in the same manner as the polarity conversion polymer compound (1). The weight average molecular weight of the obtained polymer was 19,980.

[Synthesis of Polarity Converting Polymer Compound (3)]
In a 0 ml three-necked flask, 14 g of the monomer (7) and 4.3 g of methacrylic acid were weighed and dissolved in 36 g of methyl ethyl ketone. To this solution was added 0.16 g of azobisdimethylvaleronitrile while stirring under a nitrogen stream at 65 ° C. While stirring at the same temperature, azobisdimethyl valeronitrile: 0.08 g and 0.04 g were added every two hours, and the reaction was terminated by continuously stirring for six hours. After diluting the reaction mixture with 36 g of acetone, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator.
The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was found to be a polymer having a weight average molecular weight of 120,000 by GPC.

[Synthesis of Polarity Converting Polymer Compound (4)]
In a 0 ml three-necked flask, 18.6 g of the monomer (3) and 4.4 g of p-vinylbenzoic acid were weighed, and methyl ethyl ketone: 4 g was added.
Dissolved in 0 g. To this solution, 0.32 g of azobisdimethylvaleronitrile was added while stirring under a nitrogen stream at 65 ° C. While stirring at the same temperature, azobisdimethyl valeronitrile: 0.16 g and 0.08 g were added every two hours,
The reaction was terminated by continuously stirring for 6 hours. After diluting the reaction mixture with acetone: 40 g, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was analyzed by GPC for a weight average molecular weight of 2.
It turned out to be 50,000 polymers.

[Synthesis of Polarity Converting Polymer Compound (5)]
In a 0 ml three-necked flask, 15.3 g of monomer (10) and p-
Vinyl phenol: 4.8 g was weighed and dissolved in methyl ethyl ketone: 40 g. While stirring this solution at 65 ° C. under a nitrogen stream, azobisdimethyl valeronitrile: 0.32
g was added. While stirring was continued at the same temperature, azobisdimethyl valeronitrile: 0.16 g and 0.08 g were added every two hours, and the reaction was terminated by continuously stirring for six hours. After diluting the reaction mixture with acetone: 40 g, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was found by GPC to be a polymer having a weight average molecular weight of 21,000.

[Synthesis of Polarity Converting Polymer Compound (7)] 20
In a 0 ml three-necked flask, 15.3 g of the monomer (10), 8.0 g of the monomer (3) and 2.1 g of sodium p-vinylbenzenesulfonate were weighed, and dimethylsulfoxide: 50 g was measured.
g. To this solution was added 0.16 g of azobisdimethylvaleronitrile while stirring under a nitrogen stream at 65 ° C. While stirring at the same temperature, azobisdimethyl valeronitrile: 0.08 g and 0.04 g were added every two hours, and the reaction was terminated by continuously stirring for six hours. After diluting the reaction mixture with 50 g of acetone: 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was analyzed by GPC for a weight average molecular weight of 3.
It turned out to be 50,000 polymers.

[Synthesis of Polarity Converting Polymer Compound (8)]
In a 0 ml three-necked flask, 8.4 g of the monomer (7), 4.7 g of the monomer (87) and 2.9 g of acrylic acid were weighed and dissolved in 30 g of methyl ethyl ketone. 65 ° C,
0.16 g of azobisdimethylvaleronitrile was added while stirring under a nitrogen stream. While continuing stirring at the same temperature,
Azobisdimethyl valeronitrile every 2 hours: 0.08 g
And 0.04 g were added, and stirring was continued for 6 hours to complete the reaction. After diluting the reaction mixture with 30 g of acetone, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained was determined by GPC to be a polymer having a weight average molecular weight of 40,000.

[Synthesis of Polarity Converting Polymer Compound (9)] The polarity was changed except that the monomer (83) was used instead of the monomer (1), and sodium p-vinylbenzoate was used instead of sodium p-vinylbenzenesulfonate. Polar conversion polymer compound (9) was synthesized in the same manner as conversion polymer compound (1). The weight average molecular weight of the obtained polymer was 2.050,000.

[Synthesis of Polarity Converting Polymer Compound (10)]
In a 200 ml three-necked flask, monomer (10): 15.3 g, p
-4.4 g of vinyl benzoic acid and 0.9 g of methyl acrylate were weighed and dissolved in 40 g of methyl ethyl ketone. To this solution was added 0.16 g of azobisdimethylvaleronitrile while stirring under a nitrogen stream at 65 ° C. While stirring at the same temperature, azobisdimethyl valeronitrile: 0.08 g and 0.04 g were added every two hours, and the reaction was terminated by continuously stirring for six hours. After diluting the reaction mixture with acetone: 40 g, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained is
GPC revealed that the polymer had a weight average molecular weight of 37,800.

[Synthesis of Comparative Polymer Compound (1)] 200
25.6 g of the monomer (1) was weighed and dissolved in 30 ml of methyl ethyl ketone. To this solution, 0.32 g of azobisdimethylvaleronitrile was added while stirring under a nitrogen stream at 65 ° C. While stirring was continued at the same temperature, azobisdimethyl valeronitrile: 0.16 g and 0.08 g were added every two hours, and the reaction was terminated by continuously stirring for six hours. After diluting the reaction mixture with 30 g of acetone, 2 liters of distilled water was put into a 5 liter enamel beaker, and the diluted solution prepared above was added dropwise thereto with good stirring by an agitator. The precipitated solid was separated by filtration and dried under reduced pressure for 3 days. The solid thus obtained is
GPC revealed that the polymer had a weight average molecular weight of 152,000.

[Synthesis of Comparative Polymer Compound (2)] The comparative polymer compound (2) was prepared in the same manner as the comparative polymer compound (1) except that the monomer (7) was used instead of the monomer (1). 2) was synthesized. The weight average molecular weight of the obtained polymer was 161,000.

Example 1 An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, and then its surface was grained using a nylon brush and a 400 mesh pumicetone-water suspension. Washed well with water. This plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, and further immersed in 2% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was subjected to a current density of 15 A / dm using 7% sulfuric acid as an electrolyte.
After providing a 3 g / m ² direct current anodic oxide film at ² , the sample was washed with water and dried. Further, the solution [1] prepared as described below was spin-coated at 150 rpm on the treated aluminum plate, and dried at 80 ° C. for 3 minutes to obtain a lithographic printing plate precursor [1]. The weight after drying was 1.2 g / m ² .

Solution [1]-Polarity-converting polymer compound (1) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Methyl ethyl ketone 30 g-Acetonitrile 30 g

Comparative Example 1 A lithographic printing plate precursor [2] was obtained in the same manner as in Example 1 except that the solution [2] prepared as described below was used. Weight after drying is 1.2
g / m ² .

Solution [2]-Comparative polymer compound (1) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Methyl ethyl ketone 30 g-Acetonitrile 30 g

[Example 2] A lithographic printing plate precursor [3] was obtained in the same manner as in Example 1 except that the solution [3] prepared as described below was used. Weight after drying is 1.3
g / m ² .

Solution [3]-Polarity-converting polymer compound (2) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Counter ion of Victoria Pure Blue BOH 0.1 g 05g Dye converted to 1-naphthalene-sulfonic acid-Megafac F-177 0.06g (Fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc.)-Methyl ethyl ketone 30g-Acetonitrile 30g

Comparative Example 2 A lithographic printing plate precursor [4] was obtained in the same manner as in Example 1 except that the solution [4] prepared as described below was used. Weight after drying is 1.3
g / m ² .

Solution [4] • Comparative polymer compound (2) 4.0 g • Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 g • Counter ion of Victoria Pure Blue BOH 05g Dye converted to 1-naphthalene-sulfonic acid-Megafac F-177 0.06g (Fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc.)-Methyl ethyl ketone 30g-Acetonitrile 30g

Example 3 P whose surface was corona-charged
In ET, the solution [5] prepared as described below was rotated at a rotation speed of 1
It was spin-coated at 50 rpm and dried at 80 ° C. for 3 minutes to obtain a lithographic printing plate precursor [5]. Weight after drying is 1.1 g / m
^{Was 2} .

Solution [5]-Polarity-converting polymer compound (3) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Counter ion of Victoria Pure Blue BOH 05g Dye converted to 1-naphthalene-sulfonic acid-Megafac F-177 0.06g (Fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc.)-Methyl ethyl ketone 30g-Acetonitrile 30g

Example 4 An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, and then its surface was grained with a nylon brush and a 400-mesh pumistone-water suspension. Washed well with water. This plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, and further immersed in 2% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was subjected to a current density of 15 A / dm using 7% sulfuric acid as an electrolyte.
After providing a 3 g / m ² direct current anodic oxide film at ² , the sample was washed with water and dried. Further, a solution [6] prepared as described below was coated on the treated aluminum plate with a bar, and dried at 80 ° C. for 3 minutes to obtain a lithographic printing plate precursor [6]. The weight after drying was 1.0 g / m ² .

Solution [6]-Polarity-converting polymer compound (4) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Megafax F-177 0.06 g (Large) (Nippon Ink Chemical Industry Co., Ltd., fluorine surfactant) ・ Methyl ethyl ketone 30 g ・ Acetonitrile 30 g

Example 5 P whose surface was corona-charged
In ET, the solution [7] prepared as described below was rotated at a rotation speed of 1
It was spin-coated at 50 rpm and dried at 80 ° C. for 3 minutes to obtain a lithographic printing plate precursor [7]. Weight after drying is 1.5 g / m
^{Was 2} .

Solution [7]-Polarity-converting polymer compound (5) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Acid generator 0.15 g (diphenyliodonium anthraquinone) Sulfonate) • Megafac F-177 0.06 g (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) • Methyl ethyl ketone 30 g • Acetonitrile 28 g • Water 2 g

Example 6 A lithographic printing plate precursor [8] was obtained in the same manner as in Example 1, except that the solution [8] prepared as described below was used. Weight after drying is 1.6
g / m ² .

Solution [8]-Polarity-converting polymer compound (7) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Acid generator 0.15 g (diphenyliodonium anthraquinone) (Sulfonate) ・ Dye in which counter ion of Victoria Pure Blue BOH is converted to 1 g of 1-naphthalene-sulfonic acid ・ Megafax F-177 0.06 g・ Methyl ethyl ketone 30 g ・ Acetonitrile 25 g ・ Water 5 g

Example 7 A lithographic printing plate precursor [9] was obtained in the same manner as in Example 1, except that the solution [9] prepared as described below was used instead of the solution [1]. Was.
The weight after drying was 1.5 g / m ² .

Solution [9]-Polarity-converting polymer compound (8) 4.5 g-Carbon black 0.4 g-Megafac F-177 0.06 g (Fluorine-based interface manufactured by Dainippon Ink and Chemicals, Inc.) (Activator) ・ Methyl ethyl ketone 30 g ・ Acetonitrile 30 g

Example 8 A lithographic printing plate precursor [10] was obtained in the same manner as in Example 1 except that the solution [10] prepared as described below was used. The weight after drying was 1.3 g / m ² .

Solution [10]-Polarity-converting polymer compound (9) 4.5 g-Infrared absorber IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Acid generator 0.15 g (diphenyliodonium anthraquinone) (Sulfonate) ・ Dye in which counter ion of Victoria Pure Blue BOH is converted to 1 g of 1-naphthalene-sulfonic acid ・ Megafax F-177 0.06 g 30 g of methyl ethyl ketone 30 g of acetonitrile

Example 9 A lithographic printing plate precursor [10] was obtained in the same manner as in Example 4 except that the solution [11] prepared as described below was used. The weight after drying was 1.3 g / m ² .

Solution [10]-Polarity-converting polymer compound (9) 4.5 g-Infrared absorbing agent IR-125 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 g-Counter ion of Victoria Pure Blue BOH 0.1 g 05g Dye converted to 1-naphthalene-sulfonic acid-Megafac F-177 0.06g (Fluorine-based surfactant manufactured by Dainippon Ink & Chemicals, Inc.)-Methyl ethyl ketone 30g-Acetonitrile 30g

[Evaluation Method of Original Plates of Example 1 and Comparative Example 1] The obtained lithographic printing plate precursors [1] and [2] were scanned with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 mW and a scanning speed. : 3.0 m / s
And exposure at 2.0 m / s. After exposure, Heidel KOR
-Printed as usual on a D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 1 shows the results
Shown in In the lithographic printing plate precursor [1] using the polarity-converting polymer compound having a hydrophilic group, a good printed matter having no stain on the non-image area was obtained at any scanning speed. On the other hand, in the case of the lithographic printing plate precursor [2] using the comparative polymer compound, when the scanning speed was 2.0 m / s, a good printed matter with no stain on the non-image area was obtained. At a speed of 0.0 m / s, there was slight contamination.

[0238]

[Table 1]

[Evaluation Method of Original Plates of Example 2 and Comparative Example 2] The obtained lithographic printing plate precursors [3] and [4] were scanned with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 mW and a scanning speed. : 3.0 m / s
And exposure at 2.0 m / s. After exposure, Heidel KOR
The first 30 sheets were printed with only fountain solution on a -D machine, and then printed as usual. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 2 shows the results.
In the lithographic printing plate precursor [3] using the polarity-converting polymer compound having a hydrophilic group, a good printed matter having no stain on the non-image area was obtained at any scanning speed. on the other hand,
The scanning speed of the lithographic printing plate precursor [4] is 2.0 m / s
When the scanning speed was 3.0 m / s, some stains were present, but good prints without stains on the non-image area were obtained.

[0240]

[Table 2]

[Evaluation Method of Original Plate of Example 3] The obtained lithographic printing plate precursor [5] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 m.
Exposure was performed at W and a scanning speed of 3.0 m / s. After exposure, 11
After heat treatment at 0 ° C. for 1 minute, printing was carried out as usual on a Heidel KOR-D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[Evaluation Method of Original Plate of Example 4] The obtained lithographic printing plate precursor [6] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 m.
Exposure was performed at W and a scanning speed of 3.0 m / s. After exposure, 11
After a heat treatment at 0 ° C. for 1 minute, the first 30 sheets were printed only with dampening water on a Heidel KOR-D machine, and then printed as usual. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[Evaluation Method of Original Plate of Example 5] The obtained lithographic printing plate precursor [7] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 m.
Exposure was performed at W and a scanning speed of 4.0 m / s. After exposure, 11
After heat treatment at 0 ° C. for 1 minute, printing was carried out as usual with a Heidel KOR-D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[Evaluation Method of Original Plate of Example 6] The obtained lithographic printing plate precursor [8] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm at a laser power of 360 m.
Exposure was performed at W and a scanning speed of 4.0 m / s. After exposure, 11
After a heat treatment at 0 ° C. for 1 minute, the first 30 sheets were printed only with dampening water on a Heidel KOR-D machine, and then printed as usual. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[Evaluation Method of Master Plate of Example 7] The obtained lithographic printing plate precursor [9] was irradiated with a semiconductor laser emitting infrared rays having a wavelength of 840 nm at a laser power of 360 m.
Exposure was performed at W and a scanning speed of 3.0 m / s. After exposure, printing was performed as usual on a Heidel KOR-D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter.
Table 3 shows the results.

[Evaluation Method of Original Plate of Example 8] The obtained lithographic printing plate precursor [10] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm to have a laser power of 360.
Exposure was performed at mW and a scanning speed of 2.0 m / s. After exposure, printing was performed as usual on a Heidel KOR-D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[Evaluation Method of Master Plate of Example 9] The obtained lithographic printing plate precursor [11] was irradiated with a YAG laser emitting infrared light having a wavelength of 1064 nm to have a laser power of 360.
Exposure was performed at mW and a scanning speed of 3.0 m / s. After the exposure, the first 30 sheets were printed only with dampening solution on a Heidel KOR-D machine, and then printed as usual. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 3 shows the results.

[0248]

[Table 3]

[0249]

According to the present invention, a lithographic printing plate precursor that can be developed with water or does not require special processing such as wet development or rubbing after image writing, and has higher sensitivity, In addition, it is possible to provide a lithographic printing plate precursor capable of providing a printed matter free of residual colors and stains. According to the present invention, in particular, by recording using a solid-state laser or semiconductor laser that emits infrared rays,
It is possible to provide a lithographic printing plate precursor that can be directly made from digital data.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H025 AA02 AA04 AA12 AB03 AC08 AD03 BH03 CB41 CB51 CC11 DA36 FA10 FA17 FA19 2H084 AA14 AA32 BB02 BB13 CC05 2H096 AA06 BA09 BA20 EA04 GA08 GA60 2H114 AA04 AA24 DA01 EA04

Claims (2)

[Claims] 1. On a support having a hydrophilic surface,
(A) a hydrophobic polymer compound having a functional group which changes from hydrophobic to hydrophilic by heat and a hydrophilic functional group in a side chain; and (b)
A lithographic printing plate precursor having a layer containing a light absorber capable of absorbing laser light and converting it into heat. 2. The lithographic printing plate precursor according to claim 1,
A method for producing a lithographic printing plate, comprising exposing an exposed portion recording layer on a printing machine after imagewise exposing by laser exposure.