JPH11218928A - Photosensitive material for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive material for forming the lithographic printing plate developable in water and eliminating the need for post-treatment after image forming, such as wet developing processing or rubbing treatment. SOLUTION: This photosensitive material for the lithographic printing plate is provided with a photosensitive recording layer containing an infrared absorber and the hydrolysis and condensation product of the compound represented by the formula: (R<2> )l (R<3> )3-l -Si-L-(SO3 R<1> )m in which R<1> is an alkyl or aryl or cyclic imido group; each of R<2> and R<3> is, independently, an alkyl or aryl group; L is a di- or tri-valent organic bonding group: (l) is 0, 1, or 2; and (m) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate which can be used as a positive type lithographic printing plate precursor. Among these, a lithographic printing plate can be directly made by various lasers such as visible light and infrared light based on digital signals. The present invention relates to a photosensitive lithographic printing plate capable of being subjected to water development or of being undeveloped and mounted on a printing machine for printing, and more particularly to a photosensitive lithographic printing plate suitable for production of a non-process printing plate.

[0002]

2. Description of the Related Art Conventionally, in the production of a printing plate using a PS plate,
An exposure step for imagewise exposing the photosensitive layer provided on the support, a wet development step for imagewise removing the photosensitive layer, and washing of a printing plate developed by the wet development step with water. And a post-treatment step of treating with a rinse solution containing a surfactant, gum arabic, or a desensitizing solution containing a starch derivative.

On the other hand, in the recent plate making and printing industries,
Environmental problems have arisen due to the alkaline developer waste. Further, the rationalization of the plate making operation is being promoted, and there is a need for a printing plate precursor that can be used for printing as it is after the exposure step without the need for the complicated wet development step and the post-treatment step.

As a photosensitive image-forming material suitable for producing a positive type non-process lithographic printing plate, Japanese Patent Application Laid-Open No.
No. 62 is known. This publication describes a compound having a specific carboxylic acid ester structure and having a functional group that changes from hydrophobic to hydrophilic by the action of heat or an acid. However, when this compound is used, printing is possible without performing development processing after exposure, but the printing performance such as stain resistance and printing durability is unstable, and the storage stability is insufficient. There is.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention is a photosensitive lithographic printing plate that can be developed with water or does not require special processing such as wet development processing or rubbing after image writing, particularly a photosensitive light, that is, a solid-state laser or semiconductor that emits infrared rays. An object of the present invention is to provide a photosensitive lithographic printing plate that can be directly made from digital data by recording using a laser or the like. Another object of the present invention is to provide a positive photosensitive lithographic printing plate excellent in storage stability and printing durability.

[0006]

Means for solving the above problems are as follows. That is, <1> a photosensitive lithographic printing plate having a photosensitive recording layer containing a hydrolysis-condensation product of a compound represented by the following general formula (1) and an infrared absorbent. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. <2> A photosensitive lithographic printing plate comprising a photosensitive recording layer containing a hydrolysis-condensation product of a compound represented by the following general formula (1) and a photoacid generator. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. <3> A photosensitive lithographic printing method having a photosensitive recording layer containing a hydrolysis condensation product of a compound represented by the following general formula (1) and a compound represented by the following general formula (2): Version. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. General formula (2) (R ⁴ ) _n —Si— (OR ⁵ ) _{4-n In the} general formula (2), R ⁴ and R ⁵ may be the same or different, and may be an alkyl group. Or an aryl group. n represents 0 to 2.

In the photosensitive lithographic printing plate of the present invention, the compound represented by the general formula (1) is hydrolyzed and condensed at the time of solution preparation or coating to form a resin having an SO ₃ R ¹ group at a terminal. When the resin absorbs energy such as radiation, the SO ₃ R ¹ group is decomposed. Then, the place where the SO ₃ R ¹ group is decomposed becomes imagewise hydrophilic by the heat of the heating means or the acid of the photoacid generator. For this reason, according to the photosensitive lithographic printing plate of the present invention, printing can be performed without development processing after image formation, and a desired printed matter can be obtained.
The photosensitive lithographic printing plate of the present invention has excellent printing durability.

The photosensitive lithographic printing plate of the present invention can be used for heat-sensitive recording as it is, and when a light-to-heat conversion material (infrared absorbing agent) is used, it can be used for heat-sensitive positive type unprocessed lithographic printing with infrared laser sensitivity. It can be used as an original. When a photoacid generator sensitive from the ultraviolet light region to the visible light region is used, it can be used as a positive type unprocessed lithographic printing plate sensitive to the ultraviolet light region to the visible light region.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive lithographic printing plate of the present invention will be described in detail. The photosensitive lithographic printing plate of the present invention has a photosensitive recording layer on a support, and further has other layers as necessary.

<Photosensitive Recording Layer> As a first embodiment, the photosensitive recording layer contains, as a first embodiment, a hydrolysis-condensation product of the compound represented by the general formula (1) and an infrared absorber. , And other components. Further, as a second embodiment, it contains a hydrolysis-condensation product of the compound represented by the general formula (1) and a photoacid generator.
It contains other components. Further, as a third embodiment, the composition contains a hydrolysis condensation product of the compound represented by the general formula (1) and the compound represented by the general formula (2), and further contains other compounds as necessary. Contains components.

-Compound represented by Formula (1)-The compound represented by Formula (1) is a hydrolyzable polymerizable organometallic compound. Details of the substituent in the general formula (1) are as follows. R ¹ represents an alkyl group, an aryl group, or a cyclic imide group.

-Alkyl group- Preferred examples of the alkyl group include those having 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group.
Specific examples of these include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group,
Examples thereof include 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), Alkylarylphosphonoxy group
(-OPO_Three(alkyl) (aryl)), monoalkylphosphono
Oxy group (-OPO_ThreeH (alkyl)) and its conjugate base
(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 include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group,
Phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl Groups, 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, 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 is hydrogen, the alkyl group,
The aryl group and the like are mentioned.

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.

-Aryl group- Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring, and the like. Specific examples 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. Among these, a phenyl group and a naphthyl group are preferable. The aryl group includes a heterocyclic (hetero) aryl group in addition to a carbocyclic aryl group. As the heterocyclic aryl group,
Examples thereof include a pyridyl group, a furyl group, and other quinolyl groups in which a benzene ring is condensed, a benzofuryl group, a thioxanthone group, a carbazole group, and the like having 3 to 20 carbon atoms 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.

-Cyclic imide group-Examples of the cyclic imide group include those having 4 to 20 carbon atoms such as succinimide group, phthalic acid imide group, cyclohexanedicarboxylic acid imide group and norbornene dicarboxylic acid imide group.

Among the above R ¹ , a primary or secondary alkyl group is particularly preferred in view of storage stability and thermal decomposability.

R ² and R ³ may be the same or different and represent an alkyl group or an aryl group.
R ² and R ³ may be the same or different, and those exemplified as R ¹ can be mentioned.
An alkyl group having 10 to 10 or an aryl group having 6 to 20 carbon atoms is preferred.

L represents a polyvalent organic linking group, preferably a divalent or trivalent organic linking group, having 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 1
It consists of 00 hydrogen atoms and 0-20 sulfur atoms. L
Specific examples of the linking group represented by include those constituted by combining the following structural units.

[0025]

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The polyvalent organic linking group may have a substituent. In this case, 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 phenyl group. An aryl group having 6 to 16 carbon atoms such as a naphthyl group,
A C 1-6 acyloxy group such as a hydroxyl group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, a C 1-6 carbon atom such as a methoxy group or an ethoxy group;
An alkoxy group having 2 to 7 carbon atoms, such as a halogen atom such as an alkoxy group, chlorine and bromine, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group; a cyano group; and a carbonate group such as t-butyl carbonate. Is mentioned.

L represents an integer of 0 to 2. m represents an integer of 1 or 2.

The molecular weight of the compound represented by the general formula (1) is 2,000 or less, preferably 1,000 or less. Preferred specific examples (1-1 to 1-24) of the compound represented by the general formula (1) are shown below. Note that the present invention is not limited to these specific examples.

[0029]

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[0030]

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[0031]

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[0032]

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-Compound represented by Formula (2)-The compound represented by Formula (2) is a hydrolyzable polymerizable organometallic compound. Details of the substituent in the compound represented by the general formula (2) are as follows. R ⁴ and R ⁵ may be the same or different,
Represents an alkyl group or an aryl group. n represents the integer of 0-2. When R ⁴ or R ⁵ represents an alkyl group, it preferably has 1 to 4 carbon atoms. Further, the alkyl group or the aryl group may have a substituent. The compound represented by the general formula (2) is a low molecular compound, and preferably has a molecular weight of 1,000 or less.

The compound represented by the general formula (2) includes, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, propyltrimethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. Among them, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane ,
Diphenyldiethoxysilane and the like are preferred.

In the present invention, the compounds represented by the general formula (1) may be used alone or in combination of two or more. When the compound represented by the general formula (2) is used in combination with the compound represented by the general formula (1), the compound represented by the general formula (2) may be used alone. Or two or more of them may be used in combination. The compound represented by the general formula (2) may be partially hydrolyzed and then dehydrated and condensed.

From the viewpoint of improving the storage stability of the solution of the image forming material before being applied to the substrate of the lithographic printing plate precursor, the compound represented by the general formula (2) is partially hydrolyzed. It is effective to protect an active metal hydroxyl group, for example, a silanol group (Si-OH) in an inorganic polymer formed by condensation. The protection of the silanol group is t
-It can be achieved by esterification (Si-OR) of a silanol group with a higher alcohol such as butanol and i-propyl alcohol. Specifically, it can be carried out by adding the higher alcohol to the inorganic phase. At this time, depending on the properties of the inorganic phase, the storage stability can be further improved by dehydrating the inorganic phase by, for example, heating the inorganic phase to distill off water that has been eliminated. When an acid or a base, such as hydrochloric acid or ammonia, which can serve as a reaction catalyst for the hydrolytic condensation, is present in the inorganic phase, it is generally effective to lower the concentration thereof. These can be easily performed by neutralizing the inorganic phase with a base or an acid.

In the present invention, the used amount of the compound represented by the general formula (1) (or the amount used when the compound represented by the general formula (2) is used in combination), ie, The amount of the hydrolysis-polymerizable organometallic compound used is, based on the total solid content of the photosensitive recording layer in the photosensitive lithographic printing plate,
20 to 100% by weight is preferable, and 50 to 100% by weight is more preferable.

-Hydrolysis Condensation- Next, in the present invention, when the compound represented by the general formula (1) is used in combination with the compound represented by the general formula (2), As a method for preparing an organic-inorganic composite obtained by hydrolyzing and condensing both), any known method may be used, and examples thereof include a method described in “Sol-Gel Science” (Agne Shofu). Can be

As a preferable example of the above-mentioned preparation method, the above-mentioned hydrolysis-polymerizable organometallic compound (the compound represented by the general formula (1) (this is used in combination with the compound represented by the general formula (2)) In this case, an acid (eg, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, etc.) as a reaction catalyst, particularly preferably hydrochloric acid, phosphorus An acid or alkali (for example, aqueous ammonia) is added, and
The mixture is stirred at 00 ° C, particularly preferably under reflux at 10 to 80 ° C, for 15 minutes to 6 hours, particularly preferably for 30 minutes to 5 hours, to hydrolyze and condense the hydrolyzable polymerizable organometallic compound to form the organic-inorganic composite. And the like.

-Infrared absorbing agent- When the photosensitive lithographic printing plate of the present invention is used as a lithographic printing original plate for forming an image by irradiation with infrared rays, an infrared absorbing agent is contained in the photosensitive recording layer of the photosensitive lithographic printing plate. Added.
Examples of the infrared absorber preferably used in the present invention include a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 to 1200 nm, and a wavelength of 760 to 1200 nm.
Dyes or pigments having an absorption maximum are preferred.

Examples of the dye include commercially available dyes and literatures (eg, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, Showa 45)
Known publications described in A.D., specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, metal Dyes such as a thiolate complex are exemplified. Preferred dyes include, for example, JP-A-58-12524.
No. 6, JP-A-59-84356, JP-A-59-202
No. 829, JP-A-60-78787 and the like, and methine dyes described in JP-A-58-173696, JP-A-58-181690 and JP-A-58-194595. JP-A-58-11279
No. 3, JP-A-58-224793, JP-A-59-48
187, JP-A-59-73996, JP-A-60-5
No. 2940, naphthoquinone dyes described in JP-A-60-63744, squarylium dyes described in JP-A-58-112792, British Patent No. 43
And the cyanine dyes described in U.S. Pat.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably mentioned, 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
Pyrylium compounds described in JP-A Nos. 6063 and 59-146061, 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 preferred.

Another preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes are particularly preferred.

As the pigment used as the infrared absorber, commercially available pigments and color indexes (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), “Latest Pigment Application Technology” (CMC Publishing,
1986), "Printing Ink Technology", CMC Publishing, 19
1984). Examples 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. Among these pigments, carbon black is preferred.

These pigments may be used without surface treatment, or may be used after surface treatment. As a method of the surface treatment, a method of surface coating a resin or wax,
Examples of the method include a method of attaching a surfactant and a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Examples of the surface treatment method include “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing,
1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The pigment has a particle size of 0.01 to 10
μm is preferable, and 0.05 to 1 μm is more preferable.
0.1-1 μm is particularly preferred. The particle size of the pigment,
If it is less than 0.01 μm, it is not preferable in terms of stability of the dispersion in the coating solution of the photosensitive composition, and if it exceeds 10 μm, it is not preferable in terms of uniformity of the photosensitive recording layer after coating. As a method for dispersing the pigment, a known dispersion technique used for ink production, toner production, or the like 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 of these are described in, for example, “Latest Pigment Application Technology” (CMC
Publishing, 1986).

These dyes or pigments are usually 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solids in the photosensitive recording layer of the photosensitive lithographic printing plate. In the case of a dye, 0.5 to 10% by weight is particularly preferable, and in the case of the pigment, 1.0 to 10% by weight.
Is particularly preferred. The amount of the pigment or dye added is 0.0
When the amount is less than 1% by weight, the sensitivity is lowered, and when the amount is more than 50% by weight, stains are liable to occur on the non-image portion during printing.

-Photoacid generator- In the photosensitive lithographic printing plate of the present invention, an acid is generated in an imagewise manner to react the hydrolysis-condensation product of the hydrolysis-polymerizable organometallic compound. A generator can be added. However, the hydrolysis-condensation product of the hydrolysis-polymerizable organometallic compound itself generates an acid by heat, and may exhibit a function as an acid generator. In this case, especially other acid generators There is no need to use. In the present invention, a known compound capable of generating an acid by the action of light, heat or radiation can be selected and used as the acid generator, but a photoacid generator can be preferably used.

Examples of the photoacid generator include SISc
hlesinger, Photogr.Sci.Eng., 18,387 (1974), TSBal
et al., Polymer, 21,423 (1980) and the like, and diazonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,
No. 056, JP-A-3-140,140, etc., ammonium salts, DC Necker et al., Macromolecules, 17, 2468.
(1984), CSwen et al, Teh, Proc.Conf.Rad.Curing ASI
A, p478 Tokyo, Oct (1988), U.S. Patent No. 4,069,05
No. 5,069,056, JVCrivello et al., Macromolecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,848, Iodonium salts described in JP-A-2-296,514 and the like;
V. Crivello etal, Polymer J. 17, 73 (1985), JVCrivel
lo etal. J. Org. Chem., 43, 3055 (1978), WRWatt etal,
J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J.
V. Crivello etal, Polymer Bull., 14,279 (1985), JVCr
ivello etal, Macromolecules, 14 (5), 1141 (1981), JV
Crivello etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2
877 (1979), EP 370,693, US Patent 3,902,114, EP 233,567,
Nos. 297,443 and 297,442; U.S. Pat. Nos. 4,933,377; 410,201;
9,049, 4,760,013, 4,73
Nos. 4,444 and 2,833,827, Dokoku Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and the like.
Crivello etal, Macromolecules, 10 (6), 1307 (1977), J.
V. Crivello etal, J. Polymer Sci., Polymer Chem. Ed., 1
Selenonium salts described in 7,1047 (1979), etc., CSWen eta
l, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (198
8) Onium salts such as arsonium salts described in etc.

US Pat. No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, and JP-A-61-169835. No., JP-A-61-169837
JP-A-62-258241, JP-A-62-2124
No. 01, JP-A-63-70243, JP-A-63-29
No. 8339, K. Meier et.
al, J. Rad. Curing, 13 (4), 26 (1986), TPGill et al, Inor
g.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.Res., 19
(12), 377 (1896), and organometallic / organic halides described in JP-A-2-161445, S. Hayase et al., J. Poly.
mer Sci., 25,753 (1987), E.Reichmanis et al, J.Pholyme
r Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et al.
J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetra
hedron Lett., (24) 2205 (1973), DHR Barton et al, JC
hem Soc., 3571 (1965), PMCollins et al., J. Chem. Soc.,
PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker et al., J. Am. Chem. S
oc., 110, 7170 (1988), SCBusman et al., J. Imaging Tech
nol., 11 (4), 191 (1985), HMHoulihan et al, Macormolec
ules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., C
hem.Commun., 532 (1972), S.Hayase etal, Macromolecule
s, 18, 1799 (1985), E. Reichmanis et al., J. Electrochem. S
oc., Solid State Sci. Technol., 130 (6), FMHoulihan e
tal, Macromolcules, 21, 2001 (1988), EP 029
0,750, 046,083, 156,535
Nos. 271,851, 0,388,343, U.S. Pat. Nos. 3,901,710 and 4,181,531
JP-A-60-198538, JP-A-53-133
No. 022, etc., a photoacid generator having an o-nitrobenzyl-type protecting group, M. TUNOOKA et al., Polymer Preprints Jap
an, 35 (8), G.Berner et al., J.Rad.Curing, 13 (4), WJMi
js etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.
Adachi et al, PolymerPreprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,6
No. 72, No. 044, No. 115, No. 0101, No. 122,
U.S. Pat. Nos. 4,618,564 and 4,371,60
No. 5,431,774, JP-A-64-1814
No. 3, JP-A-2-245756, Japanese Patent Application No. 3-1401
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonate described in JP-A-09-0909, etc.
Disulfone compounds described in JP-A-166544, and the like;
0-36209 (U.S. Pat. No. 3,969,118), o-naphthoquinonediazide-4-sulfonic acid halide, JP-A-55-62444 (British Patent No. 20388).
No. 01) or the o-naphthoquinonediazide compound described in Japanese Patent Publication No. 1-1935.

Other acid generators include alkyl sulfonates such as cyclohexyl citrate, cyclohexyl p-acetoaminobenzenesulfonate, cyclohexyl p-bromobenzenesulfonate, and the like. Examples thereof include an alkylsulfonic acid ester represented by the following structural formula described in Japanese Patent Application No. 9-26878.

[0052]

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Among the compounds capable of decomposing upon irradiation with light, heat or radiation to generate an acid, those which are particularly effectively used will be described below. As one of them, an oxazole derivative represented by the following general formula (PAG1) or an S-triazine derivative represented by the following general formula (PAG2) substituted by a trihalomethyl group is given.

[0054]

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The general formula (PAG1) and the general formula (PA
In G2), R ¹ represents an aryl group or an alkenyl group. These groups may further have a substituent. R
² is an aryl group, an alkenyl group, an alkyl group or -C
Representing the Y _3. These groups may further have a substituent. Y represents a chlorine atom or a bromine atom. Specific examples of the oxazole derivative represented by the general formula (PAG1) or the S-triazine derivative represented by the following general formula (PAG2) include the following compounds (PAG1-1-2 and PAG1-1).
AG2-1-5). Note that the present invention is not limited to these specific examples.

[0056]

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[0057]

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As another one, the following general formula (PAG)
3) iodonium salt represented by the following general formula (P
AG4), a sulfonium salt or a diazonium salt.

[0059]

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The general formula (PAG3) and the general formula (PA
In G4), Ar ¹ and Ar ² represent an aryl group. The aryl group may have a substituent. 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,
Examples include a mercapto group and a halogen atom.

R ³ , R ⁴ and R ⁵ represent an alkyl group or an aryl group, preferably an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. The alkyl group or the aryl group may have a substituent. Preferred substituents include an alkoxy group having 1 to 8 carbon atoms and 1 to 8 carbon atoms for the aryl group.
An alkyl group, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group.

[0062 Z ^- represents a counter anion, for example, BF
_{^{4 -, AsF 6 -, PF}} 6 -, SbF 6 -, Si
_{^{F 6 2-, ClO 4 -,}} CF 3 SO 3 - perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, bonded polynuclear aromatic sulfonate anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Anionic and sulfonic acid group-containing dyes are exemplified.

Further, two of R ³ , R ⁴ and R ⁵ , and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Specific examples of these include:
Compounds shown below (PAG3-1-2 and PAG4-1
To 3), but the present invention is not limited to these specific examples.

[0064]

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[0065]

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The iodonium salt represented by the general formula (PAG3) or the onium salt represented by the general formula (PAG4) is known, for example, JW Knapczyk et al.
Am. Chem. Soc., 91, 145 (1969), AL Maycok et al.,
J. Org. Chem., 35, 2532, (1970), B. Goethas et al.
Bull. Soc. Chem. Belg., 73, 546, (1964), HM Le
icester, J. Ame.Chem. Soc., 51, 3587 (1929), J.
V. Crivello etal, J. Polym. Chem. Ed., 18, 2677 (19
80), U.S. Pat. Nos. 2,807,648 and 4,24.
No. 7,473, JP-A-53-101,331 and the like.

Still another is a compound represented by the following general formula (PA)
G5) or a disulfone derivative represented by the following general formula (P
AG6).

[0068]

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The general formula (PAG5) and the general formula (PA
In G6), Ar ³ and Ar ⁴ represent an aryl group. The aryl group may have a substituent. R ⁶ represents an alkyl group or an aryl group. The alkyl group or the aryl group may have a substituent. A represents an alkylene group, an alkenylene group or an arylene group. These groups may also have a substituent. Specific examples thereof include the following compounds (PAG5-1 and PAG6-1 and PAG6-1 and PAG6-1), but the present invention is not limited thereto.

[0070]

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[0071]

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The content of these acid generators is usually 0.1 to 30% by weight, preferably 1 to 15% by weight, based on the total solids in the photosensitive recording layer of the photosensitive lithographic printing plate. . If the content is less than 1% by weight, the sensitivity may be low, and if it exceeds 15% by weight, the image strength may be reduced.

-Other Components- In the present invention, in the first embodiment, a photoacid generator can be added as another component, if necessary. In the second embodiment, an infrared absorber can be added as another component, if necessary. Further, in the third embodiment, if necessary, an infrared absorber and / or a photoacid generator can be added as other components. In the present invention, the above-mentioned components are used as needed, but if necessary, other components appropriately selected may be added. As the other components, for example, various polar group-containing organic polymers are dispersed and mixed in the organic-inorganic composite, moldability, transparency,
An organic-inorganic composition having excellent solvent resistance, heat resistance, weather resistance, and the like can be formed. This technique is known. For example, Japanese Unexamined Patent Publication (Kokai) No. 3-212451 discloses that a hydrolytic polymerizable organic compound such as tetraalkoxysilane is hydrolyzed and polymerized in the presence of a non-reactive polymer having an amide bond to form a gel. It discloses that an organic-inorganic hybrid transparent uniform body in which a non-reactive polymer having an amide bond is uniformly dispersed in a three-dimensional fine network structure of a formed metal oxide gel. Japanese Patent Application Laid-Open No. 3-56535 discloses that an oxazoline / silica gel formed by hydrolytic polymerization of an oxazoline polymer having a hydrolyzable polymerizable silyl group and a hydrolyzable polymerizable silane such as tetraalkoxysilane is gelled and shaped. A method for producing a composite molded article is disclosed. Further, JP-A-5-85860 discloses that
A transparent homogeneous organic-inorganic composite in which a non-reactive polymer having a urethane bond is uniformly dispersed in a matrix of an inorganic oxide obtained by hydrolytic polymerization of a hydrolyzable inorganic compound such as tetraalkoxysilane is disclosed. I have. As the polar group in the polar group-containing organic polymer in the present invention, various functional groups and / or functional bonding groups, for example,
A hydroxyl group, a carboxyl group, an ester group, an ether group, a carbonate group, an amide group or the like;
And a group represented by HC (O)-or> NC (O)-(hereinafter, referred to as an "amide group or other group"), a glycidyl group, a halogen group, or the like. The polymer may be a thermoplastic resin or a thermosetting resin, and may be used alone or in combination of two or more. In addition, these substituents and bonding groups may be present in either the main chain or the side chain of the polymer.

Examples of the polymer containing a hydroxyl group and the polymer derived therefrom include polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, phenol resin, methylolmelamine, and derivatives thereof (for example, acetalized products and Hexamethoxymethylmelamine); a polymer having a carboxyl group and a derivative thereof (for example, a homo- or copolymer containing an unsaturated organic acid such as poly (meth) acrylic acid, maleic anhydride, and itaconic acid, and esterified products thereof; Examples of the polymer having an ester group include homo- or copolymers containing monomers such as vinyl esters such as vinyl acetate and (meth) acrylates such as methyl methacrylate (for example, polyvinyl acetate, ethylene-vinyl acetate copolymer). Heavy Body, (meth) acrylic resin), saturated polyester, unsaturated polyester, vinyl ester resin, diallyl phthalate resin, cellulose ester, etc. Examples of the polymer having an ether group include polyalkylene oxide and polyoxyalkylene. Glycol, polyvinyl ether, silicon resin, etc. Examples of the polymer having a carbonate group include bisphenol A-type polycarbonate, etc. Examples of the polymer having an amide group and other groups include polyoxazoline and polyalkyleneimine N-. Acylated products; polyvinylpyrrolidone and derivatives thereof; polyurethane; polyurea; polyamides; polymers having burette bonds; polymers having allohanate bonds; and proteins such as gelatin.

Examples of polyoxazoline polymerization monomers include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, and 2-propyl-2.
-Oxazoline, 2-isopropyl-2-oxazoline, 2-butyl-2-oxazoline, 2-dichloromethyl-2-oxazoline, 2-trichloromethyl-2-oxazoline, 2-pentafluoroethyl-2-oxazoline, 2-phenyl -2-oxazoline, 2-methoxycarbonylethyl-2-oxazoline, 2- (4-methylphenyl) -2-oxazoline, 2- (4-chlorophenyl) -2-oxazoline and the like. The polyoxazoline may be a homopolymer,
The polyoxazoline may be a copolymer.
Species may be used alone or in combination of two or more. Here, the polyoxazoline may be a copolymer in which oxazoline is graft-polymerized to another polymer. Examples of the acyl compound of the polyalkylenimine include a polymer corresponding to the polyoxazoline, for example, a polymer having an N-acylamino group such as N-acetylamino and N-polypionylamino.

As the polyurethane, for example, a polyisocyanate (for example, tolylene diisocyanate, hexamethylene diisocyanate) and a polyol (for example,
Polyhydric alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, and glycerin;
Polyurethanes formed by reaction with polyether polyols such as diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol; polyester polyols). Polyurea includes polyisocyanates and polyamines (eg, ethylenediamine, diethylenetriamine)
The polyamide includes poly (meth) acrylamide, polyamino acid and the like. Polyamides include starburst dendrimers (DATomalia, et al., Polmer Journal,
17, 117 (1985)).

The polymer having a burette bond is a polymer formed by reacting the polyisocyanate with a compound having a urethane bond; the polymer having an allohanate bond is formed by a reaction between the polyisocyanate and a compound having a urea bond. Polymer. Examples of the polymer having a glycidyl group include an epoxy resin and a glycidyl (meth) acrylate homopolymer or copolymer. Examples of the halogen-containing polymer include polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a vinylidene chloride-based polymer, and chlorinated polypropylene. The polar group-containing organic polymer can be mixed alone with the hydrolyzable polymerizable organic metal compound, and can be used alone. However, even for other organic polymers that cannot be uniformly mixed with the hydrolysis-polymerizable organometallic compound alone, by adding a mixing aid, they can be used if they can be uniformly mixed with the hydrolysis-polymerizable organometallic compound. be able to.

[0078] These other organic polymers include
Examples include polyolefins such as polyethylene, polypropylene, and carboxyl-modified polyolefin; and styrene-based polymers such as polystyrene, styrene-acrylonitrile copolymer, and acrylonitrile-butadiene-styrene block copolymer. These may be used alone or in combination of two or more.
As the mixing aid, for example, the polar group-containing organic polymer can be used, preferably a polymer having an amide group or another group, and more preferably, polyoxazoline, polyvinylpyrrolidone and derivatives thereof are used. be able to.

When the photoacid generator has no sensitivity up to the visible range, various sensitizing dyes of the photoacid generator are used to activate the photoacid generator with respect to visible light. Can be
Examples of such sensitizing dyes include US Pat. No. 5,238,782.
Pyran dyes described above, cyanine dyes described in US Pat. No. 4,997,745, and squarium dyes described in US Pat.
76, the merocyanine dye described in JP-B-8-20732
And the like, Michler's ketone, thioxanthone, ketocoumarin dye, 9-phenylacridine and the like can be used as effective ones. In addition, bis-benzylidene ketone dyes described in US Pat. No. 4,987,230, and polycyclic aromatic compounds such as 9,10-diphenylanthracene can be used. As other components, for example, a dye having a large absorption in a 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 (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.
No. 145. The amount of these additives is 0.01 to 10% by weight based on the total solids in the photosensitive recording layer of the photosensitive lithographic printing plate.

Further, in the photosensitive recording layer of the photosensitive lithographic printing plate of the present invention, JP-A-62-251740 and JP-A-3-20851 are used in order to widen the stability under printing conditions.
No. 4, non-ionic surfactants as described in
JP-A-59-121044, JP-A-4-1314
An amphoteric surfactant as described in JP-A No. 9 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, 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 photosensitive lithographic printing plate is preferably 0.05 to 15% by weight, and more preferably 0.1 to 5% by weight.

Further, a plasticizer is added to the photosensitive recording layer of the photosensitive lithographic printing plate of the present invention, if necessary, in order to impart flexibility to the coating film. Examples of the plasticizer include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and acrylic. Oligomer or polymer of acid or methacrylic acid may be mentioned.

The photosensitive recording layer of the photosensitive lithographic printing plate of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating it on a suitable support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol,
2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, Sulfolane, γ-
Butyrolactone, toluene, water and the like. These solvents may be used alone or in combination of two or more.

The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. Further, the coating amount (solid content) on the support obtained after coating and drying is generally preferably 0.5 to 5.0 g / m ² .
Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

In the photosensitive recording layer of the photosensitive lithographic printing plate of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950. Surfactants can be added. A preferable addition amount is 0.01 to 1% by weight, and 0.05 to 0.
5% by weight is more preferred.

<Support> The support (substrate) used for the lithographic printing original plate on which the image forming material of the present invention is to be coated is a dimensionally stable plate-like material. Those used as a body are included and can be suitably used. As the support, paper, plastics (for example, polyethylene, polypropylene, polystyrene, etc.)
Laminated paper, aluminum (including aluminum alloy), zinc, iron, copper and other metal plates, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,
Examples include plastics films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films on which the above-described metals are laminated or vapor-deposited, with an aluminum plate being particularly preferred. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. As the aluminum alloy, various ones can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel is used. These compositions may contain some iron and titanium or other negligible amounts of impurities.

The support is subjected to a surface treatment as necessary, for example, the surface of the support is subjected to a hydrophilic treatment.
In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or anodizing is performed. Is preferred. Also, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate is disclosed in U.S. Pat. No. 3,181,461. As described above, an aluminum plate that has been subjected to anodizing treatment and then immersed 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.

Electrodeposition of a silicate as described in US Pat. No. 3,658,662 is also effective. These hydrophilic treatments are used not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive recording layer. It is applied to. Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, a mechanical method,
Both the chemical method and the electrochemical method are 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. The chemical method is described in Japanese Patent Application Laid-Open No. 54-31187.
The method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent Application Laid-Open Publication No. H10-157, 1988 is suitable. As the electrochemical method, a method in which alternating current electrolysis is performed in an acidic electrolyte such as hydrochloric acid, nitric acid, or a combination thereof is preferable. Among such surface roughening methods, particularly, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in Japanese Patent Application Laid-Open No. 55-137993, Is preferred because of its strong adhesion to the support. The graining by the above method is preferably performed such that the center line average roughness (Ra) 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 processing solution for the etching is usually selected from aqueous solutions of bases or acids which 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 an unnecessary film is formed on the etched surface. These etching agents have a dissolution rate of 0.3 to 40 g / m ² per minute of immersion time, when the concentration of use and the temperature are set, the dissolution rate of the aluminum or alloy used is 1 minute.
It is most preferred that this be done, but anything greater or less than this is acceptable.

The etching is performed by immersing the aluminum plate in the etching solution or by applying the etching solution to the aluminum plate, etc., and is processed so that the etching amount is 0.5 to 10 g / m ^2. Preferably. 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 desmutting treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoric 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, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulphamic acid, benzenesulfonic acid or the like or a combination of two or more thereof in an aqueous solution or non-aqueous solution when a direct current or alternating current is passed through aluminum,
An anodic oxide film can be formed on the surface of the aluminum support.

The conditions of the anodizing treatment vary depending on the electrolytic solution to be used, and thus cannot be specified unconditionally. Generally, however, 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 anodic oxidation treatments, in particular, British Patent No. 1,4
Anodizing at high current density in sulfuric acid as described in U.S. Pat. No. 3,511,6.
The method of anodizing phosphoric acid as an electrolytic bath described in the specification of Japanese Patent No. 61 is preferable. The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilization treatment, if necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181. Alkali metal silicates such as those disclosed in U.S. Pat. No. 4,461,461 and potassium fluoride hydrozirconate disclosed in JP-B-36-22063 and U.S. Pat. No. 4,153,461. There is a method of treating with polyvinyl phosphonic acid as described above.

<Other Layers> The other layers include:
An organic undercoat layer, a back coat layer and the like can be mentioned. —Organic Undercoat Layer— In the photosensitive lithographic printing plate of the present invention, it is preferable to provide an organic undercoat layer before coating the photosensitive recording layer in order to reduce the remaining photosensitive recording layer in the non-image area. Examples of the organic compound used in the organic undercoat layer include, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, organic phosphinic acid such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine Hydroxyl groups such as Selected from such as hydrochloric acid salts of amines having, in addition to using these alone or may be used as a mixture of two or more.

In addition, a high molecular compound having a structural unit such as poly (p-vinylbenzoic acid) can be used.

The organic undercoat layer can be provided by the following method. That is, water or methanol, ethanol,
A method in which a solution in which the above organic compound is dissolved in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum plate and dried, and an organic solvent such as water or methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof is used. In this method, an aluminum plate is immersed in a solution in which the organic compound is dissolved to adsorb the organic compound, and then washed with water or the like and dried to form an organic undercoat layer. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.

The solution used for this may be a basic substance such as ammonia, triethylamine or potassium hydroxide, hydrochloric acid,
The pH is adjusted with an acidic substance such as phosphoric acid,
2 can also be used. Further, a yellow dye may be added for improving the tone reproducibility of the photosensitive lithographic printing plate precursor. The coating amount after drying of the organic undercoat layer is 2 to 200 mg.
/ M ² is appropriate, and preferably 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained, and the same applies if it is greater than 200 mg / m ² .

-Backcoat layer- On the back surface of the support, a backcoat layer may be provided if necessary.
Provided. Such a back coat layer is disclosed in
Patent application title: Organic polymer compound described in JP-A-45885
Organic or inorganic metal compounds described in JP-A-6-35174
From metal oxides obtained by hydrolysis and polycondensation of
Is preferably used. These coating layers
And Si (OCH_Three)_Four, Si (OC_TwoH_Five)_Four, Si (OC_ThreeH
₇) _Four, Si (OC_FourH₉)_FourSilicon alkoxy compounds such as
Are inexpensive and readily available, and the resulting metal oxide coatings
The covering layer is particularly preferred because of its excellent hydrophilicity.

As described above, the photosensitive lithographic printing plate of the present invention can be produced. The photosensitive lithographic printing plate may be subjected to thermal image recording directly by a thermal recording head or the like, or may have a wavelength of 760 nm to 1200.
The image is exposed by a solid-state laser or a semiconductor laser that emits infrared light of nm. In the present invention, water development after thermal recording or after laser irradiation, after further performing gumming if necessary, mounting the plate in a printing machine and printing,
Alternatively, the plate may be mounted on a printing machine immediately after the thermal recording or the laser irradiation, and printing may be performed. However, it is preferable to perform the heat treatment after the thermal recording or the laser irradiation.
The conditions of the heat treatment are as follows.
It is preferable to carry out for 5 seconds to 5 minutes. By this heat treatment,
During thermal recording or laser irradiation, heat or laser energy required for recording can be reduced.

The photosensitive lithographic printing plate obtained by such a treatment can be subjected to water development, or can be directly applied to an offset printing machine or the like and used for printing a large number of sheets.

[0100]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. (Examples 1 and 2 and Comparative Example 1) [Preparation of support] After an aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, a nylon brush and a pumice stone of 400 mesh were used.
The surface was grained using a water suspension and washed well with water. This plate is immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching.
% 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 . Next, this plate was subjected to a current density of 1% using 7% H ₂ SO ₄ as an electrolyte.
After a direct current anodized film of 2.4 g / m ² at 5A / dm ^2, washed with water and dried.

[Preparation of Coating Solution for Photosensitive Recording Layer] Compound represented by Formula (1-1) or (1-2) 4 g tetraethoxysilane 4 g ········ 4 g Methanol ······· 18 g To a solution having the above composition was added 0.2 g of 1N hydrochloric acid,
The mixture was stirred at 60 ° C. for 3 hours and subjected to hydrolysis polymerization to obtain an inorganic component in a homogeneous solution. Next, 0.15 g of an infrared absorber (IR125, manufactured by Wako Pure Chemical Industries, Ltd.) was added to this solution and dissolved, and the coating solution A-1 for the photosensitive recording layer for Example 1 and the coating solution A-1 for Example 2 were dissolved. A photosensitive recording layer coating solution A-2 was obtained. In the above composition, the compound represented by the formula (1-1) is used in the photosensitive recording layer coating solution A-1, and the compound represented by the formula (1-) is used in the photosensitive recording layer coating solution A-2. The compound represented by 2) was used. Further, as Comparative Example 1, the above formula (1-1)
Or, except that the compound represented by the formula (1-2) uses a copolymer of tetrahydropyan-2-yl methacrylate and methacryloxypropyltrimethoxysilane,
A photosensitive recording layer coating liquid B-1 of Comparative Example 1 was prepared in the same manner as the photosensitive recording layer coating liquid A-1 for Example 1 and the photosensitive recording layer coating liquid A-2 for Example 2.

[Preparation of photosensitive lithographic printing original plate] Next, the obtained coating solutions A-1, A-2 and B-1 for the photosensitive recording layer were obtained.
Is coated on the support, dried at 80 ° C. for 1 minute,
An original plate for photosensitive lithographic printing [A-1], an original plate for photosensitive lithographic printing [A-2], and an original plate for photosensitive lithographic printing [B-1] were obtained.

[Stability Test] In order to examine the stability of the photosensitive lithographic printing plate, printing was carried out on a sample immediately after the preparation of the photosensitive lithographic printing plate and on a sample after storage at 75% humidity of 45 ° C. for 3 days. The meat was examined. For the measurement of the printing inking property, the film was exposed imagewise with a YAG laser emitting infrared light having a wavelength of 1064 nm, left for one day, and then printed with a printing machine (Heidelberg, Heidel SOR-M). The number of sheets to be laid was confirmed. The obtained results are shown in Tables 1 and 2 below.

[0104]

[Table 1]

[0105]

[Table 2]

(Example 3 and Comparative Example 2) [Preparation of Coating Solution for Photosensitive Recording Layer] Compound represented by the above formula (1-3) 4 g tetraethoxysilane ············ 4 g Methanol ······ 18 g In a solution consisting of the above composition 0.2 g of 1N hydrochloric acid was added to
The mixture was stirred at 60 ° C. for 3 hours and subjected to hydrolysis polymerization to obtain an inorganic component in a homogeneous solution. Next, as a photoacid generator in this solution,
0.15 g of 4- [4-{(N, N-di (ethoxycarbonylmethyl) amino) phenyl-2,9-bis-trichloromethyl-S-triazine] was added, and the mixture was stirred and mixed to obtain a homogeneous Example 3. Coating solution A-3 for photosensitive recording layer was prepared. Further, as Comparative Example 2, the compound represented by the formula (1-3) was a photosensitizer for Example 3 except that a copolymer of tetrahydropyan-2-yl methacrylate and methacryloxypropyltrimethoxysilane was used. A photosensitive recording layer coating liquid B-2 for Comparative Example 2 was prepared in the same manner as the recording layer coating liquid A-3.

[Printing durability and stain resistance test] The obtained coating solutions for the photosensitive recording layers were applied to the same support as the support obtained in Example 1 in the same manner as in Example 1. Photolithographic printing original plate [A-3] and photosensitive lithographic printing original plate [B-2]
I got The coating weight of the coating film after drying is 1.0 g / m.
^{Was 2} . The obtained photosensitive lithographic printing plate precursor [A-3]
The photosensitive lithographic printing plate precursor [B-2] was imagewise exposed to ultraviolet light using a PS plate exposure machine using a metal halide lamp as a light source. The photosensitive lithographic printing plate after exposure [A
-3] and the photosensitive lithographic printing plate precursor [B-2] at 100 ° C.
For 3 minutes to produce a photosensitive lithographic printing plate, which was then printed as it was on a printing machine (Heidelberg, Heidel SOR-M). At this time, printing was performed on a large number of sheets, and after printing 10,000 sheets, the image portion of the printed matter and the non-image portion were examined for stains. The results obtained are shown in Table 3 below.

[0108]

[Table 3]

[0109]

According to the present invention, a photosensitive lithographic printing plate which can be developed with water or which does not require special processing such as wet development or rubbing after image writing, especially a solid-state laser or semiconductor laser which emits infrared rays, etc. By recording using a lithographic printing plate, a photosensitive lithographic printing plate capable of making a plate directly from digital data can be provided. Further, according to the present invention, a positive photosensitive lithographic printing plate having excellent storage stability and printing durability can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 B41M 5/26 S

Claims (3)

[Claims] 1. A photosensitive lithographic printing plate comprising a photosensitive recording layer containing a hydrolysis-condensation product of a compound represented by the following general formula (1) and an infrared absorber. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. 2. A photosensitive lithographic printing plate comprising a photosensitive recording layer containing a hydrolytic condensation product of a compound represented by the following general formula (1) and a photoacid generator. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. 3. A photosensitive composition comprising a photosensitive recording layer containing a hydrolysis-condensation product of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Lithographic printing plate. General formula (1) (R ² ) _l (OR ³ ) _3-l -Si-L- (SO ₃ R ¹ )
_{m In the} general formula (1), R ¹ represents an alkyl group, an aryl group, or a cyclic imide group. R ² and R ³ may be the same or different and represent an alkyl group or an aryl group. L represents a divalent or trivalent organic linking group. l represents an integer of 0 to 2. m represents 1 or 2. General formula (2) (R ⁴ ) _n —Si— (OR ⁵ ) _{4-n In the} general formula (2), R ⁴ and R ⁵ may be the same or different, and may be an alkyl group. Or an aryl group. n represents the integer of 0-2.