JP2000127641A - Thermosensitive image forming material and lithographic original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosensitive image forming material which can form an image at high sensitivity by heating or heat generated by photothermal conversion and a lithographic original plate which can be produced directly from digital data by recording by using a laser or a thermal head using the image forming material, does not need a special treatment such as wet development and rubbing after image exposure, and is excellent in stain properties and printability. SOLUTION: A polymer having a functional group generating phosphonic acid, phosphinic acid, and phosphoric acid by heating is incorporated. The functional group is shown by formulas I-III. In the formulas, L is an organic group comprising a polyvalent nonmetal atom necessary to connect the functional group shown by the formulas I-III with a polymer skeleton; R is an alkyl group, an aryl group, or a cyclic imide group. Moreover, it is preferable to use a photothermal conversion substance additionally to improve sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive image forming material which can be used for a heat-sensitive recording layer of a positive type lithographic printing plate precursor, and a lithographic printing plate precursor using the same. Among them, an image forming material which can form an image by laser scanning based on a digital signal, has sufficient sensitivity to laser emitting infrared rays and thermal head recording, and is useful for forming a heat-sensitive recording layer, and A positive-working photosensitive lithographic printing plate precursor having a heat-sensitive recording layer formed by the method described above, capable of directly making a plate by laser scanning, being water-developable or being able to be directly mounted on a printing machine without being developed and printed. .

[0002]

2. Description of the Related Art Conventionally, in the production of a printing plate using a PS plate,
After the exposure step, a wet development process for removing the photosensitive layer provided on the support surface in an image-like manner, or the developed printing plate is washed with water or a surfactant-containing rinse. And a post-treatment step of treating with a desensitizing solution containing a liquid, gum arabic and a starch derivative.

On the other hand, in the plate making and printing industries in recent years, environmental problems have arisen because the developing waste solution is alkaline. Further, plate making operations have been rationalized, and there has been a demand for a printing plate precursor that does not require the above-described complicated wet development process and can be used for printing as it is after exposure. After image formation, as a lithographic printing plate precursor that does not require wet development processing, using a film obtained by sulfonating polyolefins as a plate material, and changing the hydrophilicity of the surface by thermal writing, no development processing is required Forming a plate material is disclosed in JP-A-5-77574 and JP-A-4-12.
No. 5,189, US Pat. No. 5,187,047 and JP-A-6
No. 2,195,646. In this system, an image is formed by desulfonating a sulfone group present on the surface of a photosensitive material by thermal writing. Development processing is not required, but it has a drawback that a harmful gas is generated at the time of writing.

US Pat. No. 5,102,771, US Pat. No. 5,22
No. 5,316 discloses a photosensitive material in which a polymer having an acid-sensitive group in a side chain is combined with a photoacid generator, and a non-developing system is proposed. Since the generated acid is a carboxylic acid, this plate material has a low degree of hydrophilicity, is easily stained, and has disadvantages such as poor durability of the plate material and poor clarity of a printed image.

As a radiation-sensitive image-forming material suitable for the production of a positive type unprocessed lithographic printing plate, Japanese Patent Application Laid-Open No. Hei 7-1 which uses a specific carboxylic acid ester as an image-forming material
The thing described in 86562 is known. According to the image forming material described in this publication, a water-developable lithographic printing plate giving a satisfactory printed matter can be obtained, but when the energy at the time of exposure is low, the image forming material near the support is completely However, since the image forming material could not be completely removed without being hydrophilized, the printed matter tended to be stained.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-sensitive image-forming material capable of forming an image with high sensitivity by heating or heat generated by photothermal conversion, and a heat-sensitive image-forming material. By using forestry for the recording layer and recording with a laser or thermal head that emits infrared light, it is possible to make plates directly from digital data,
Another object of the present invention is to provide a lithographic printing plate precursor that does not require special processing such as wet development processing or rubbing after image exposure and has excellent stain resistance and printing durability. Another object of the present invention is to provide a novel thermosensitive image-forming material having excellent sensitivity to thermal recording containing a novel polymer obtained from a monomer having a functional group capable of generating phosphonic acid by heating. It is to be.

[0007]

The above object is achieved by the present invention described below. That is, the heat-sensitive image forming material of the present invention is characterized by containing a polymer compound having a functional group that generates phosphonic acid, phosphinic acid, and phosphoric acid by heating. Here, it is preferable that the heat-sensitive image forming material further contains a light-to-heat conversion material. Further, the lithographic printing plate precursor according to the invention is characterized in that a heat-sensitive recording layer containing a polymer compound having a functional group that generates phosphonic acid, phosphinic acid, and phosphoric acid by heating is provided on a support. . Here, in a preferred embodiment, the functional groups that generate phosphonic acid, phosphinic acid, and phosphoric acid by heating are functional groups represented by general formulas (1), (2), and (3), respectively.

[0008]

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(In the formula, L represents an organic group comprising a polyvalent nonmetal atom necessary for linking the functional groups represented by the general formulas (1) to (3) to the polymer skeleton, and R represents each of Independently, an alkyl group, an aryl group, or a cyclic imide group is shown.) In the present invention, a functional group capable of generating phosphonic acid, phosphinic acid, or phosphoric acid by heating is hereinafter referred to as a phosphonic acid generating functional group. And the polymer compound having this functional group is referred to as a phosphonic acid-generating polymer compound.

According to the heat-sensitive image-forming material of the present invention, it contains a high molecular compound which has a functional group capable of generating a strong acid such as phosphonic acid by heating in a molecule and changes to hydrophilic by heating efficiently. In addition, it is possible to form an image with high sensitivity by heat due to exposure. By adding a photothermal conversion agent to this polymer compound, the thermal efficiency is further improved, and the sensitivity can be increased. Further, the lithographic printing plate precursor according to the present invention can form an image with high sensitivity when the layer composed of the polymer compound is hydrophilized image-wise by a predetermined heating means. The printed matter is solubilized by water and does not remain on the support, so that stains on the printed matter are remarkably improved. Further, since the image portion has strong adhesion to the support, a heat-sensitive image forming material having excellent printing durability can be provided.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the polymer compound having a specific functional group contained in the photosensitive image forming material of the present invention will be described. This polymer compound is preferably a polymer compound which is hydrophobic and changes to hydrophilic under the influence of phosphonic acid or the like generated by heating. Here, hydrophilic means water-soluble (completely soluble in water). ), Pseudo-water-soluble (meaning amphipathic, macro-soluble in water but micro-containing non-soluble part), water-swelling (swelling in water but not soluble) Which means that they dissolve in water or swell in water under normal use conditions. The polymer compound according to the present invention is characterized in that the main chain or the side chain has a functional group that generates phosphonic acid, phosphinic acid, and phosphoric acid by heating. Specifically, the functional group is preferably a functional group represented by the general formulas (1), (2), and (3). Among them, those having a functional group represented by the general formula (1) are particularly preferable from the viewpoint of easy synthesis. The polymer compound having a functional group represented by the general formula (1) is a novel compound which is not known for application to a thermosensitive image forming material.

In the general formula (1), L represents an organic group comprising a polyvalent nonmetallic atom necessary for linking the functional group represented by the general formula (1) to the polymer skeleton, and R represents each of Independently, it represents an alkyl group, an aryl group, or a cyclic imide group.

When R in the general formula (1) represents an alkyl group, preferred examples of the alkyl group include C 1 -C 1.
20 linear, branched or cyclic alkyl groups. Specific examples of these include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl. Group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group,
Examples thereof include a neopentyl group, a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and 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 preferable.

The alkyl group may have a substituent.
Good. Examples of the substituent in the substituted alkyl group
Represents monovalent nonmetallic atomic groups except hydrogen, and is preferred.
Examples include halogen atoms (-F, -Br, -Cl,
-I), hydroxyl group, alkoxy group, aryloxy
Group, mercapto group, alkylthio group, arylthio group,
Alkyldithio group, aryldithio group, amino group, N-
Alkylamino group, N, N-diarylamino group, N-
Alkyl-N-arylamino group, acyloxy group,
Rubamoyloxy group, N-alkylcarbamoyloxy
Group, N-arylcarbamoyloxy group, N, N-dia
Alkylcarbamoyloxy group, N, N-diarylcal
Bamoyloxy group, N-alkyl-N-arylcarba
Moyloxy group, alkyl sulfoxy group, aryl sulf
Oxy, acylthio, acylamino, N-alkyl
Luacylamino group, N-arylacylamino group, urea
Id group, N'-alkylureido group, N ', N'-dia
Alkyl ureido group, N'-aryl ureido group, N ',
N'-diarylureido group, N'-alkyl-N'-
Arylureido group, N-alkylureido group, NA
Reelureido group, N'-alkyl-N-alkyluree
An id group, an N'-alkyl-N-arylureido group,
An N ', N'-dialkyl-N-alkylureido group,
An N ', N'-dialkyl-N-arylureido group,
N′-aryl-N-alkylureido groups, N′-ali
-N-arylureido group, N ', N'-diary
Ru-N-alkylureido group, N ', N'-diaryl
-N-arylureido group, N'-alkyl-N'-a
Reel-N-alkylureido group, N'-alkyl-
N'-aryl-N-arylureido group, alkoxy
Carbonylamino group, aryloxycarbonylamino
Group, N-alkyl-N-alkoxycarbonylamino
Group, N-alkyl-N-aryloxycarbonylamino
Group, N-aryl-N-alkoxycarbonylamino
Group, N-aryl-N-aryloxycarbonylamino
Group, formyl group, acyl group, carboxyl group, alkoxy
Cicarbonyl group, aryloxycarbonyl group, carbamo
Yl group, N-alkylcarbamoyl group, N, N-dial
A kill carbamoyl group, an N-aryl carbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, sulfo group (—SO_ThreeH) and both
Role base group (hereinafter referred to as sulfonato group), alkoxys
Ruphonyl group, aryloxysulfonyl group, sulfinamo
Yl group, N-alkylsulfinamoyl group, N, N-di
Alkylsulfinamoyl group, N-arylsulfina
Moyl group, N, N-diarylsulfinamoyl group, N
-Alkyl-N-arylsulfinamoyl group, sulf
Amoyl group, N-alkylsulfamoyl group, N, N-
Dialkylsulfamoyl group, N-arylsulfamo
Yl group, N, N-diarylsulfamoyl group, N-A
Alkyl-N-arylsulfamoyl group, phosphono group
(-PO_ThreeH _Two) And its conjugated base group (hereinafter referred to as phospho
A dialkylphosphono group (-PO)._Three(al
kyl)_Two), A diarylphosphono group (—PO_Three(ary
l)_Two), An alkylarylphosphono group (—PO_Three(alky
l) (aryl)), monoalkylphosphono group (-PO_ThreeH (a
lkyl)) and its conjugated base group (hereinafter referred to as alkylphospho
A monoarylphosphono group (-PO group)._Three
H (aryl)) and its conjugated base group (hereinafter referred to as arylphos)
Phonato group), phosphonooxy group (-OPO_Three
H_Two) And its conjugated base group (hereinafter referred to as phosphonatoxy)
Group)), a dialkylphosphonooxy group (-OPO
_Three(alkyl)_Two), Diarylphosphonooxy group (—OP
O_Three(aryl)_Two), Alkylarylphosphonooxy group
(-OPO_Three(alkyl) (aryl)), monoalkylphosphono
Oxy group (-OPO_ThreeH (alkyl)) and its conjugated base group
(Hereinafter referred to as alkylphosphonatooxy group), mono
Arylphosphonooxy group (-OPO_ThreeH (aryl))
And its conjugated base group (hereinafter, arylphosphonatooxy)
Group), cyano group, nitro group, aryl group, alk
And an alkynyl group.

Specific examples of the aryl group as a substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl,
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, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl And the like.

Similarly, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and the like. The acyl group is represented by (G ¹ CO-)
Wherein G ¹ includes hydrogen, the alkyl group, the aryl group, and the like.

Among these substituents, halogen atoms (-F, -Br, -Cl, -I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, 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 group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N- Dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, phosphono, phosphonate, dialkylphosphono, diarylphosphono, monoalkylphosphono, alkylphospho Preferred are a sodium group, a monoarylphosphono group, an arylphosphonato group, a phosphonooxy group, a phosphonatoxy group, an aryl group and an alkenyl group.

Preferred specific examples of the substituted alkyl group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthio, and the like. Methyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, 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, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphono Butyl group,
Methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl 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 And the like.

When R in the general formula (1) represents an aryl group, preferred examples of the aryl group include, for example, 1
And a benzene ring and a 5-membered unsaturated ring forming a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, Examples include a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are preferable. Also,
The aryl group includes a heterocyclic (hetero) aryl group in addition to a carbocyclic aryl group. Examples of the heterocyclic aryl group include, for example, a pyridyl group, a furyl group, a quinolyl group in which another benzene ring is fused, a benzofuryl group,
3 to 2 carbon atoms such as a thioxanthone group and a carbazole group
0 and 1 to 5 heteroatoms.

The aryl group may have a substituent. Examples of the substituted aryl group include those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on a ring-forming carbon atom in the aryl group. Preferred examples of the substituent include those exemplified as the substituent in the alkyl group, the substituted alkyl group, and the substituted alkyl group.

Preferred examples of the substituted aryl group include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, 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, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, A carbamoylphenyl group, an N-methylcarbamoylphenyl group,
N, N-dipropylcarbamoylphenyl 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, diethylphosphono Phenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methyl Allylphenyl group, 2
-Methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

When R represents a cyclic imide group, examples of the cyclic imide group include those having 4 to 20 carbon atoms such as a succinimide group, a phthalic imide group, a cyclohexanedicarboxylic imide group and a norbornenedicarboxylic imide group. No.

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.

[0024]

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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.

In the general formula (2), R and L have the same meanings as the functional group represented by the general formula (1). Preferred examples of R in the general formula (2) include the same as those exemplified in the general formula (1).

In the general formula (3), R and L have the same meanings as those represented by the general formula (1). Preferred examples of R in the general formula (3) include the same as those exemplified in the general formula (1).

Preferred examples of the monomer having a functional group represented by the general formulas (1) to (3) are shown below as exemplified monomers (1) to (35), but the present invention is not limited thereto. It is not something to be done.

[0029]

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[0030]

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[0031]

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[0032]

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The high molecular compound having a phosphonic acid-generating functional group in the main chain or side chain may be a homopolymer containing the above-mentioned monomer or a homopolymer containing the above-mentioned monomer, as long as it is in a range showing the film-forming properties and other characteristics required for the present invention. Copolymers of two or more kinds may be used, and copolymers of these monomers with other copolymerizable monomers may be used. In the present invention, a polymer compound more preferably used is a copolymer obtained by radical polymerization of the above monomer and another known monomer.

Other monomers used in the copolymer include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride Known monomers such as acid and maleic imide are also included. Acrylic esters, methacrylic esters, acrylamides,
Specific examples of methacrylamides, vinyl esters, and styrenes include the compounds described above. Of these monomers, particularly preferably used are acrylic esters having 20 or less carbon atoms, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, and acrylonitrile. is there.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

When combined with another monomer, the amount of the monomer having a phosphonic acid-generating functional group is preferably 5% by weight or more based on the total amount of the monomer components.
More preferably, it is% by weight.

The phosphonic acid-generating polymer compound according to the present invention can be produced by a known method. For example, it can be obtained by the method described in Polymer Chemistry Experimental Method (edited by the Society of Polymer Science, published by Tokyo Chemical Dojinsha). These phosphonic acid-generating polymer compounds may be any of a random polymer, a block polymer, and a graft polymer,
It is preferably a random polymer, which is appropriately selected depending on the polymerization method.For example, di-t-butyl peroxide, peroxides such as benzoyl peroxide, persulfates such as ammonium persulfate, azobisisobutyronitrile and the like It is synthesized by radical polymerization using a polymerization initiator such as an azo compound. As the polymerization method, solution polymerization, emulsion polymerization, suspension polymerization and the like are required.

Suitable solvents used for synthesizing these polymer compounds include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more. As the radical polymerization initiator used when synthesizing the thermosensitive polymer compound used in the present invention,
Known compounds such as an azo initiator and a peroxide initiator can be used.

The degree of polymerization of these phosphonic acid-generating polymer compounds is not particularly limited, and the molecular weight is preferably 2000 or more, more preferably 5000 to 300,000. Yes,
The number average molecular weight is preferably 800 or more, and more preferably in the range of 1,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

The heat-sensitive image-forming material of the present invention comprises the above-mentioned polymer compound as a main component, and furthermore, in accordance with the use of the image-forming material, within a range that does not impair the properties of the polymer compound. Various additives can be used in combination.

In the present invention, it is preferable to use a photothermal conversion material together with the phosphonic acid-generating polymer compound from the viewpoint of improving sensitivity. Here, the photothermal conversion material is
It is a compound that absorbs light and generates heat.
Preferably, there is a light absorption region in the infrared region of 750 to 1200 nm, which indicates light / heat conversion ability in light in this wavelength range. Specifically, it absorbs light in this wavelength region and absorbs heat. Various types of pigments or dyes generated can be used. 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. In particular,
Azo dye, metal complex salt azo dye, pyrazolone azo dye, anthraquinone dye, phthalocyanine dye, carbonium dye, quinone imine dye, methine dye, cyanine dye,
Dyes such as metal thiolate complexes are exemplified.

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-9-202829 and JP-A-60-78787;
JP-A-58-181690, JP-A-58-194
No. 595, etc .;
Naphthoquinone dyes described in JP-A-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc. JP-A-58-112
792 and the cyanine dyes described in British Patent No. 434,875.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranyl compounds, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used. Another preferred example of the dye is U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described in the specification as formulas (I) and (II) can be mentioned. 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)
Annual Publication), “Latest Pigment Application Technology” (CMC Publishing, 1986)
Pigments described in "Printing Ink Technology", CMC Publishing, 1984). Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. 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 surface treatment, or may be used after 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)
"Printing ink technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferred in terms of the stability of the heat-sensitive image forming material in the coating solution, and when it exceeds 10 μm, it is not preferred in terms of the uniformity of the image recording layer after coating.
As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Dispersers include ultrasonic dispersers, sand mills, attritors, pearl mills, super mills, ball mills, impellers, dispersers, KD mills, colloid mills, dynatrons,
Examples include 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 based on the total solid content of the image forming material of the present invention.
It can be added in an amount of preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 1.0 to 10% by weight for pigments. If the amount of the pigment or the dye is less than 0.01% by weight, the sensitivity is lowered. If the amount exceeds 50% by weight, the non-image area is apt to be stained during printing.

In order to produce a lithographic printing plate precursor using the heat-sensitive image-forming material of the present invention, a heat-sensitive recording layer made of the image-forming material may be formed on a suitable support. At this time, in forming the heat-sensitive recording layer coating liquid, various additives other than the phosphonic acid-generating polymer compound may be included as necessary as long as the effects of the present invention are not impaired.

In the heat-sensitive recording layer coating solution of the lithographic printing plate precursor according to the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to enhance stability under printing conditions.
Non-ionic surfactants described in JP-A-59-121044, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 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, Daiichi Kogyo Co., Ltd.). The addition amount of the nonionic surfactant and the amphoteric surfactant is 0.05% in the total solid of the heat-sensitive recording layer coating solution.
-15% by weight, more preferably 0.1-5% by weight.

The heat-sensitive recording layer of the lithographic printing plate precursor according to the present invention comprises:
Usually, it can be produced by dissolving each of the above components in a solvent and applying the solution on a suitable support. As the solvent used here, 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, dimethoxyethane, methyl lactate, ethyl lactate, N,
Examples include, but are not limited to, 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. As a method of applying, various methods can be used, for example, bar coater application, spin coating,
Examples include spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. In the heat-sensitive recording layer of the lithographic printing plate of the present invention, a surfactant for improving coatability, for example, JP-A-62-1
A fluorine-based surfactant as described in JP-A-70950 can be added. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the heat-sensitive recording layer.

In the heat-sensitive recording layer used in the present invention,
The polymer compound can be used in a proportion of 50 to 90% by weight, preferably 70 to 90% by weight of the total solids. When the addition amount is less than 50% by weight, the printed image becomes unclear, and when the addition amount exceeds 90% by weight, image formation by laser exposure cannot be sufficiently performed.

The following compounds may be mentioned as constituents other than the polymer compound of the heat-sensitive recording layer used in the lithographic printing plate precursor according to the invention.

[Acid generator] When the lithographic printing plate of the present invention is used as a lithographic printing plate precursor for forming an image by irradiation with infrared rays, or when used as a lithographic printing plate precursor for forming an image by irradiation of ultraviolet rays to visible light. It is desirable to add a compound capable of generating an acid by light or heat (hereinafter, referred to as an acid generator) to the heat-sensitive recording layer of the lithographic printing plate.

In the present invention, the following known compounds can be selected and used as the acid generator that can be used in combination with the polymer compound. For example, SISchlesinge
r, Photogr.Sci.Eng., 18,387 (1974), TSBal etal, Poly
diazonium salts described in mer, 21,423 (1980), etc., U.S. Pat.Nos. 4,069,055 and 4,069,056, JP-A-3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201.
No., JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17,7
3 (1985), JVCrivello et al. J. Org. Chem., 43, 3055 (1
978), WRWatt et al, J. Polymer Sci., Polymer Chem. E
d., 22, 1789 (1984), JVCrivello etal, Polymer Bul
l., 14,279 (1985), JVCrivello etal, Macromorecules,
14 (5), 1141 (1981), JVCrivello etal, J. PolymerSc
i., Polymer Chem. Ed., 17, 2877 (1979), EP 370,6
No. 93, U.S. Patent 3,902,114, European Patent No. 233,567
Nos. 297,443 and 297,442; U.S. Pat.No.4,933,37
No. 7, No. 410,201, No. 339,049, No. 4,760,013,
Nos. 4,734,444 and 2,833,827, Dokoku Patent No. 2,904,62
Nos. 6, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), JVCrivello etal, J. PolymerSci., Po
selmerium salts described in lymer Chem. Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing ASIA, p.
478 Tokyo, Oct (1988) etc., onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837,
JP-A-62-58241, JP-A-62-212401, JP-A-63-702
No. 43, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al., Inorg.Chem., 19, 3007 (1980), D. Astruc, Ac
c. Chem. Res., 19 (12), 377 (1896), organometallics / organic halides described in JP-A-2-14145, etc., S. Hayase eta
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al.
J.Pholymer Sci., Polymer Chem.Ed., 23,1 (1985), QQ
Zhu etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit e
tal, Tetrahedron Lett., (24) 2205 (1973), DHRBarton
etal, J. Chem Soc., 3571 (1965), PMCollins etal, JC
hem.SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Te
trahedron Lett., (17), 1445 (1975), JWWalker etal
J. Am. Chem. Soc., 110, 7170 (1988), SCBusman et al., JI
maging Technol., 11 (4), 191 (1985), HMHoulihan eta
l, Macormolecules, 21,2001 (1988), PMCollins etal,
J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase eta
l, Macromolecules, 18, 1799 (1985), E. Reichmanis et al.
J.Electrochem.Soc., Solid State Sci.Technol., 130
(6), FMHoulihan et al, Macromolcules, 21, 2001 (1988)
, European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.
Nos. 710, 4,181,531, JP-A-60-198538, JP-A-60-198538
53-133022, etc., a photoacid generator having a 0-nitrobenzyl type protecting group, M. TUNOOK et al., Polymer Preprint
s Japan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), W.
J. Mijs et al., Coating Technol., 55 (formerly a photoacid generator with a protecting group, M. TUNOOK et al., Polym 697), 45 (1983), Akz
o, H. Adachi etal, Polymer Preprints, Japan, 37 (3),
European Patent Nos. 0199,672, 84515, 199,672,
044,115, 0101,122, U.S. Pat.No. 4,618,564,
4,371,605, 4,431,774, JP-A-64-18143,
JP-A-2-245756, compounds that generate sulfonic acid upon photolysis, such as iminosulfonates described in Japanese Patent Application No. 3-140109, and disulfone compounds described in JP-A-61-166544. JP-A-50-36209 (U.S. Pat.
No. 969118) and o-naphthoquinonediazide-4.
-Sulfonic acid halides, described in JP-A-55-62444 (UK Patent No. 2038801) or JP-B-1-1
An o-naphthoquinonediazide compound described in No. 1935 can be exemplified.

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.

[0057]

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In the present invention, the polymer compound having a phosphonic acid-generating functional group in the main chain or side chain itself has a function as a thermal acid generator, so that it is not necessary to use another acid generator in combination. Can also form an image.

Among the compounds which decompose upon irradiation with light, heat or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0060]

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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.

[0062]

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[0063]

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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:

[0065]

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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 the aryl group, and a substituent for the alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0068] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, Si 2 F 2 -, ClO 4 -, CF 3 SO 3 -
Perfluoroalkanesulfonate anion; pentafluorobenzenesulfonate anion, naphthalene-1
-Bonded polynuclear aromatic sulfonic acid anions such as sulfonic acid anions; anthraquinone sulfonic acid anions; sulfonic acid group-containing dyes, and the like, but are not limited thereto.

Further, two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

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

[0071]

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[0072]

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The above 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), A.
L. Maycok et al., J. Org.Chem., 35, 2532, (1970),
B. Goethas etal, Bull. Soc. Chem. Belg., 73, 546,
(1964), HM Leicester, J. Ame. Chem. Soc., 51, 3
587 (1929), JV Crivello etal, J. Polym. Chem. E
d., 18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101,
No. 331 and the like.

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

[0075]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ⁶Is replaced or not
It represents a substituted alkyl group or an aryl group. A may be replaced
Represents an unsubstituted alkylene group, alkenylene group, arylene
Represents a group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0077]

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[0078]

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The content of these acid generators is usually from 0.1 to 30% by weight, more preferably from 1 to 15% by weight, based on the total solid content of the image-forming material of the present invention. If it is less than 0.1%, the effect of addition cannot be obtained, and if it is more than 15%, the image strength may be reduced.

[Sensitizing Dye] When the acid generator has no sensitivity in the ultraviolet to visible range, various acid generators are sensitized to activate the acid generator with respect to light in the ultraviolet to visible range. Dyes are used. Examples of such sensitizing dyes include US523878
2, pyranium dyes described in US4997745, squarium dyes, merocyanine dyes described in US5262276, pyrylium dyes described in Japanese Patent Publication No. 8-20732, Michler's ketone, thioxantone,
Ketocoumarin dyes, 9-phenylacridine and the like can be used as effective ones. In addition, US49
Bisbenzylidene ketone dyes described in 87230 and polycyclic aromatic compounds such as 9,10-diphenylanthracene can be used. As other components, for example,
Dyes having large absorption in the visible light region can be used as colorants for images.

More specifically, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 60
3. Oil black BY, oil black BS, oil black T-505 (orient Chemical Industry Co., Ltd.)
Manufactured), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42
535), ethyl violet, rhodamine B (CI1
45170B), malachite green (CI4200
0), methylene blue (CI52015) and the like, or JP-A-62-293247, Japanese Patent Application No. 7-335.
145. The amount of addition is 0.01 to 10% by weight based on the total solid content of the image forming material of the present invention.

[Others] Further, a plasticizer may be added to the heat-sensitive recording layer of the lithographic printing plate of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And a polymer.

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

In the lithographic printing plate precursor according to the present invention, the support (substrate) to which the coating solution for the heat-sensitive recording layer is to be applied is a plate-like material having good dimensional stability, and has been used as a support for a printing plate. Any known materials can be suitably used. Examples of such a support include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), eg, a metal plate such as aluminum (including aluminum alloy), zinc, iron, copper, etc., eg, diacetate. Cellulose, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, etc. Although a vapor-deposited paper or a plastic film is included, 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, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, or 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 heat-sensitive lithographic printing plate precursor, the surface of the support is subjected to a hydrophilic treatment prior to coating the photosensitive / thermosensitive layer. In the case of a support having a metal, particularly aluminum surface, a graining treatment, sodium silicate,
It is preferable that a surface treatment such as an immersion treatment in an aqueous solution of potassium fluoride zirconate or a phosphate, or an anodization treatment is performed. Also, U.S. Pat.
No. 066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, and an anodizing treatment of an aluminum plate as described in US Pat. No. 3,181,461. After immersion, an immersion treatment in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment is, for example, phosphoric acid,
A current is passed using an aluminum plate as an anode in an electrolytic solution of an inorganic acid such as 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 these salts alone or in combination of two or more. It is implemented by doing.

As the surface treatment, US Pat.
Electrodeposition of silicate as described in US Pat. No. 8,662 is also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive / thermosensitive composition provided thereon,
This is performed to improve the adhesion to the photosensitive layer. 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.
Further, 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, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface-roughening methods, a surface-roughening method combining mechanical surface-roughening and electrochemical surface-roughening as described in JP-A-55-137993 is particularly preferred. Is preferred because of its strong adhesion to the support. The graining by the method as described above has a center line surface roughness (Ha) of 0.3 to 1.0 μm on the surface of the aluminum plate.
It is preferable that the application is performed in such a range as follows. 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 zinc, chromium, cobalt, nickel, and copper, are not preferable because they form an unnecessary film on the etched surface. In these etching agents, the dissolution rate of the aluminum or alloy to be used is determined by the immersion time 1 at the setting of the working concentration and temperature.
Most preferably from minute per 0.3 g / m ² from being carried out so as to become 40 g / m ^2, but no problem even well below or above this.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution, or by applying an 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. The acid used for desmut treatment is
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. These etchants, use concentration, in the setting of temperature, most preferably the rate of dissolution of aluminum or alloy used is performed as consisting of immersion time 1 minute per 0.3 g / m ² to 40 g / m ² It may be higher or lower than this.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution, or by applying an 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. The acid used for desmut treatment is
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 applied to 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 support 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 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 1-10
0V and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, British Patent No. 1,4
Anodizing at high current density in sulfuric acid as described in U.S. Pat.
The method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 661 is preferable. Roughened as above,
Further, the anodized aluminum plate may be subjected to a hydrophilization treatment as necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181,461.
Alkali metal silicates such as those disclosed in US Pat.
There is a method of treating with potassium fluoride zirconate disclosed in Japanese Patent No. 3 and polyvinyl phosphonic acid as disclosed in US Pat. No. 4,153,461.

[0092] If necessary, a back surface may be provided on the back surface of the support.
A light coat is provided. On the back of the support,
First, a back coat is provided. With such a back coat
The organic polymerization described in JP-A-5-45885
And organic and organic compounds described in JP-A-6-35174.
Are obtained by hydrolysis and polycondensation of inorganic metal compounds.
A coating layer made of a metal oxide is preferably used. This
Of these coating layers, Si (OCH_Three)_Four, Si (OC_TwoH_Five)
_Four, Si (OC_ThreeH₇) _Four, Si (OC_FourH₉)_FourSuch as silicon
Of the alkoxy compound is inexpensive and readily available, and
Metal oxide coating layer is particularly preferred because of its excellent hydrophilicity.
New As described above, the layer (a) is sequentially formed on the support,
(B) The lithographic printing plate precursor of the present invention is formed by forming a layer.
Can be manufactured.

Next, a method of making a lithographic printing plate precursor will be described. The lithographic printing plate precursor is directly subjected to image-wise thermal recording by, for example, a thermal recording head (thermal head), or is image-exposed by a solid-state laser or semiconductor laser that emits infrared light having a wavelength of 760 nm to 1200 nm. Image exposure by a visible light laser emitting visible light of 400 nm to 760 nm,
Image exposure is performed by a light source that emits ultraviolet light or visible light. The lithographic printing plate precursor that has been image-exposed can be subjected to water development after exposure, gumming if necessary, and then printing can be performed by mounting the plate on a printing machine. It is also possible to mount the plate on a printing press and perform printing. That is, in the plate making method using the lithographic printing plate precursor according to the 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 condition of the heat treatment is 80 ° C.
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.

[0095]

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 Phosphonic Acid-Generating Polymer Compound) Synthesis of Monomer (1) 20 g of 4-bromomethylstyrene and 18 g of trimethyl phosphite were placed in a 100 ml three-necked flask and heated at 180 ° C. while bubbling with nitrogen. Allowed to react for hours. After the reaction, the residue was purified by column chromatography using silica gel to obtain 21 g of Exemplary Monomer (1) having the above structure.

Synthesis of Monomers (2) and (3) Except that triethyl phosphite and triisopropyl phosphite were used in place of trimethyl phosphite, the exemplified monomers (1) were synthesized in the same manner as in the synthesis of monomer (1). 2) and (3) were synthesized.

Synthesis of Monomer (4) 14 g of phosphorus trichloride and 30 g of cyclohexanol were added to 100
The mixture was placed in a 3-ml three-necked flask and stirred. While cooling with ice, 24 g of pyridine was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, poured into 500 ml of water, extracted with ethyl acetate, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 32 g of tricyclohexyl phosphite. next,
32 g of the obtained tricyclohexyl phosphite and 20 g of 4-bromomethylstyrene were placed in a 100 ml three-necked flask, and reacted under heating at 1800 ° C. for 6 hours while bubbling with nitrogen. After the reaction, the residue was purified by column chromatography using silica gel to obtain 29 g of Exemplified Monomer (4).

Synthesis of Monomers (5) to (13) Monomers (5) to (13) were synthesized in the same manner as in the synthesis of monomer (4) except that the corresponding alcohols were used instead of cyclohexanol. .

Synthesis of Monomer (33) 50 g of N- (2-bromoethyl) phthalimide and 41 g of trimethyl phosphite were placed in a 200 ml three-necked flask.
The reaction was carried out under heating at 180 ° C. for 6 hours while bubbling with nitrogen. After the reaction, unreacted trimethyl phosphite was distilled off under reduced pressure to obtain 46 g of dimethyl phthalimidoethylphosphonate having a structure represented by the following formula.

[0101]

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Next, 40 g of dimethyl phthalimidoethylphosphonate and 500 ml of ethanol were placed in a 1-liter three-necked flask and stirred. Thereafter, 10 g of hydrazine-hydrate and 200 ml of ethanol were slowly dropped using a dropping funnel, and the mixture was stirred for 10 hours. After the reaction, the reaction product was poured into water and extracted with ethyl acetate. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to give
15 g of dimethyl-aminoethylphosphonate were obtained.

[0103]

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Next, 10 g of the obtained dimethyl 2-aminoethylphosphonate, 83 g of magnesium oxide, 150 g of water
m1 was placed in a 500 ml three-necked flask and stirred. While cooling with ice, 9 g of methacrylic acid chloride and 40 ml of dioxane were slowly added dropwise using a dropping funnel, and the mixture was stirred as it was in an ice bath for 2 hours. After returning to room temperature,
After stirring for an hour, hydrochloric acid was added to make the mixture acidic, and the mixture was extracted with ethyl acetate. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of the monomer (33). Thereafter, purification was performed by column chromatography using silica gel to obtain 14 g of the monomer (33).

Synthesis of Monomers (15) to (25) Monomers (15) to (25) were prepared in the same manner as in the synthesis of monomer (14) except that the corresponding phosphite was used in place of trimethyl phosphite. 25) was synthesized.

Synthesis of Polymer Compound (1) In a 200 ml three-necked flask, 20 g of the monomer (1) and 40 g of methyl ethyl ketone were placed, and the mixture was heated at 65 ° C. under a nitrogen stream.
0.29 g of azobisdimethylvaleronitrile was added.
After stirring at the same temperature for 5 hours, the solvent was distilled off under reduced pressure to obtain a solid. The polymer was found to have a weight average molecular weight of 12,000 by GPC (polystyrene standard). This was designated as polymer compound (1).

Synthesis of Polymer Compounds (2) to (35) A polymer compound (2) to (35) was prepared in the same manner as the synthesis method of the polymer compound (1) except that the monomers shown in Table 1 were used instead of the monomer (1). 2) to (35) were obtained. Table 1 shows the average molecular weights of the polymer compounds (2) to (35).

[0108]

[Table 1]

(Examples 1 to 8) Preparation of support A 0.30 mm thick aluminum plate (material 1050) was washed with trichloroethylene and degreased, and then a nylon brush and a 400 mesh pumice water-water suspension were used. The surface was grained and washed well with water. 45 ℃
Was etched by dipping in a 25% aqueous sodium hydroxide solution for 9 seconds, washed with water, and further dipped in 2% HNO ₃ for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . The plate is then baked with 7% H ₂ SO
₄ a current density of 15A / dm ² with 3 g / m ² as an electrolyte
, And then washed with water and dried.

Next, in the following solution [A], eight kinds of solutions [A-1] to [A-8] were prepared by changing the type of the phosphonic acid-generating polymer compound used as shown in Table 2.
Each of the solutions was applied to the treated aluminum plate and dried at 100 ° C. for 2 minutes to form a heat-sensitive recording layer to obtain lithographic printing original plates [A-1] to [A-8]. The coating amount of the subsequent heat-sensitive recording layer was 1.0 g / m ² .

Solution [A] Polymer (Table 2) 1.0 g Infrared absorbing agent (NK-3508, manufactured by Japan Photographic Dye Laboratories Co., Ltd.) 0.15 g Fluorinated surfactant (MegaFac F-177, Dainippon) Ink Chemical Industry Co., Ltd.) 0.06 g Methyl ethyl ketone 27 g

[0112]

[Table 2]

The obtained lithographic printing original plates [A-1] to [A
-8] was exposed with a YAG laser emitting infrared light having a wavelength of 1064 nm. After the exposure, printing was performed without any development processing using 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. In each case, good prints without stains on the non-image areas were obtained.

[0114]

[Table 3]

(Examples 9 to 14 and Comparative Example 1) In the following solution [B], six kinds of solutions [B-1] to [B-6] were prepared by changing the type of the polymer compound as shown in Table 4. Was prepared. Each of the solutions was applied to the undercoated aluminum plate support used in Examples 1 to 8, dried at 100 ° C. for 2 minutes to provide a heat-sensitive recording layer, and a lithographic printing plate precursor [B-
1] to [B-6] were obtained. The coated amount of the heat-sensitive recording layer after drying was 1.4 g / m ² . As a comparative example, in the following solution [B], a carboxylic acid-generating polymer compound (R-1) having the following structure in place of the polymer of the present invention was used.
A solution [B'-1] was prepared in the same manner as described above, and the lithographic printing plate precursor [B'-1] was prepared in the same manner as described above.
I got

Solution [B] Polymer (Table 4) 0.6 g Infrared absorber NK-2268 0.15 g (manufactured by Nippon Sensitive Dyestuff Research Institute Co., Ltd.) Megafac F-177 0.06 g (Dainippon Ink & Chemicals, Inc.) Co., Ltd., fluorinated surfactant) Methyl ethyl ketone 27 g

[0117]

[Table 4]

[0118]

Embedded image

(Stability test) The obtained planographic printing plate precursors [B-1] to [B-6] and [B'-1] were heated at a temperature of 40.
The print inking property after storage for 3 days under high temperature and high humidity conditions of 70 ° C. and a humidity of 70% was examined. In the measurement of the printing inking property, the film was exposed to a semiconductor laser emitting infrared light having a wavelength of 830 nm, and printed with a Heidel KOR-D machine without performing development processing. At this time, the number of sheets until the arrival at the start of printing was checked. Table 5 shows the results. As is evident from Table 5, it was found that a stable printing state can be obtained with an extremely small number of sheets.

[0120]

[Table 5]

(Examples 15 to 22 and Comparative Example 2)
In the solution [B], eight kinds of solutions [B-7] to [B
-14], and planographic printing plate precursors [B-7] to [B-14] were obtained in the same manner as in Example 9. Also, as a comparative example, a solution [B′-1] was prepared in the same manner as described above, except that the carboxylic acid-generating polymer compound (R-1) was used instead of the polymer in the present invention. An original plate [B'-1] was obtained and used as Comparative Example 2. (Printing durability test) The obtained lithographic printing plate precursor [B-7] ~
[B-14] and [B'-1] were exposed with a semiconductor laser emitting infrared light having a wavelength of 830 nm, and printed with a Heidel KOR-D machine without performing development processing. At this time, 1000
The density of the ink in the image area at the time of printing 2,000 sheets, 5,000 sheets, and 5,000 sheets was visually evaluated. As evident in Table 6 below,
The ink density remained high after printing 5,000 sheets. In comparison between Examples 15 to 20 and Examples 21 and 22, it was found that those using the polymer compound having a functional group represented by the general formula (1) were particularly excellent.

[0122]

[Table 6]

(Example 21) In the above solution [A],
A solution [E-1] was prepared in the same manner as in Example 1 except that the infrared absorber NK-3580 was not added as a light-to-heat conversion material. Using this solution, a lithographic printing plate precursor [E-1] was prepared in the same manner as in Example 1. The obtained lithographic printing plate precursor [E-1] was printed with a thermal head using a word processor “Shoin” (manufactured by Sharp Corporation), and evaluated using the same printing machine as in the examples. Stained prints were obtained after printing 1,000 sheets and after printing 10,000 sheets.

[0124]

According to the present invention, by applying a novel polymer having a functional group generating phosphonic acid, an image can be formed with high sensitivity by heat generated by heating or photothermal conversion. By using an image forming material and this heat-sensitive image forming material for the heat-sensitive recording layer and recording using various thermal heads such as a laser emitting infrared rays, a heat-sensitive printer, and a heat-sensitive facsimile, it is possible to make a plate directly from digital data. In addition, a lithographic printing plate precursor can be provided which does not require any special processing such as wet development processing or rubbing after image exposure, has clear printed images, and has particularly good durability during printing.

Claims (4)

[Claims] 1. The method according to claim 1, wherein the heating comprises heating of the phosphonic acid, phosphinic acid,
A heat-sensitive image-forming material containing a polymer compound having a functional group that generates phosphoric acid. 2. The heat-sensitive image forming material according to claim 1, further comprising a light-to-heat conversion material. 3. A lithographic printing plate precursor comprising a support and a heat-sensitive recording layer containing a polymer compound having a functional group capable of generating phosphonic acid, phosphinic acid and phosphoric acid by heating. 4. The functional group that generates phosphonic acid, phosphinic acid, and phosphoric acid by heating is a functional group represented by general formulas (1), (2), and (3), respectively. A lithographic printing plate precursor according to item 3. Embedded image (Wherein, L represents an organic group comprising a polyvalent nonmetallic atom necessary for connecting the functional groups represented by the general formulas (1) to (3) to the polymer skeleton, and Rs each independently represent It represents an alkyl group, an aryl group, or a cyclic imide group.)