JP2652819B2 - Photosensitive lithographic printing plate - Google Patents

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. The present invention relates to a photosensitive lithographic printing plate having a photopolymerizable or photocrosslinkable photosensitive layer with improved safety (hereinafter referred to as white light safety).

[0002]

2. Description of the Related Art There are many attempts to use a photopolymerizable composition and a photocrosslinkable composition as an image forming layer of a photosensitive layer of a photosensitive lithographic printing plate. As the photopolymerizable composition, a basic composition comprising a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in JP-B-46-32714, and disclosed in JP-B-49-34041. A composition in which unsaturated double bonds are introduced into a polymer as such a binder to improve curing efficiency,
Compositions using a novel photopolymerization initiator as disclosed in JP-B-48-38403, JP-B-53-27605 and British Patent No. 1388492 are known.

As a photocrosslinkable composition, a polymer which is crosslinked by a cycloaddition reaction is well known. As such a photocrosslinkable polymer, a polymer having a maleimide group in a side chain or an aromatic ring is used. A polymer having a cinnamyl group, a cinnamoyl group, a cinnamylidene group, or a cinnamylideneacetyl group having a photodimerizable unsaturated double bond in a side chain or a main chain is useful. In particular, a polymer having a maleimide group in the side chain and a phenylenediacrylic acid or a polyester having a cinnamic acid skeleton in a molecular chain produced by condensation of an alkyl ester thereof with a glycol have been partially commercialized with high sensitivity. I have.

However, if these photosensitive layers are used as they are because of insufficient adhesion to the aluminum support, images may be peeled off or scratched by rubbing with a brush or the like during development. Sufficient image intensity cannot be obtained, and this tendency is remarkable especially at the time of low exposure, resulting in a problem such as low sensitivity. Many attempts have been made to improve this poor adhesion. For example, JP-A-54-72104 discloses a photopolymerizable composition.
Attempts to use a negative working diazo resin as an undercoat layer as disclosed in US Pat.
JP-A-61-38943, JP-A-2-111948
And a method of adding a diazo resin to a photosensitive composition as disclosed in Japanese Patent Application No. 1-137890. As the photocrosslinkable composition, Japanese Patent Publication No. 50-7481
No., JP-A-62-78544, and Japanese Patent Application No. Hei.
No. 1, Japanese Patent Application No. 2-37786 discloses a method using a diazo resin.

However, the method of using a diazo resin in the photopolymerizable or photocrosslinkable photosensitive layer has a problem because the photosensitive wavelength range between the photopolymerization initiator or sensitizer and the diazo resin is displaced. Was. Specifically, for white fluorescent lamps,
Even when using a photopolymerization initiator or a sensitizer having no sensitivity, only the diazo resin is exposed, causing fog,
Problems such as thickening of halftone dots occurred. Furthermore, the sensitivity of the photosensitive layer could not be increased because the sensitivity of the diazo resin was low.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention provides an excellent adhesion between a support and a photosensitive layer while maintaining excellent sensitivity, photosensitive area and performance of the photosensitive layer, and furthermore, provides safety for a white fluorescent lamp. An object is to provide an excellent photosensitive lithographic printing plate.

[0007]

Means for Solving the Problems The present inventor has proposed a photolithographic printing plate in which a photopolymerizable composition is provided with a photosensitive layer comprising a photocrosslinkable composition on a support having a hydrophilic surface. It has been found that the above object can be achieved by incorporating a diazo resin having the structural unit in the photosensitive layer or the intermediate layer, and the present invention has been accomplished based on this finding.

That is, the present invention relates to a photosensitive lithographic printing plate comprising a support having a hydrophilic surface and a photosensitive layer composed of a photopolymerizable composition or a photocrosslinkable composition provided in the photosensitive layer or on the support. A photosensitive lithographic printing plate characterized in that a diazo resin obtained by the following method is contained in an intermediate layer between a body and a photosensitive layer. An oligomer is synthesized by a ring-opening polymerization reaction between a compound containing two oxirane rings in one molecule and a compound represented by the following general formula (I), and the substituent Y of the obtained oligomer is converted into an amino group. A diazo resin obtained by converting this amino group into a diazonium salt.

[0009]

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In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom;
Represents a single bond or an arbitrary divalent organic group, and Y represents an arbitrary substituent convertible to an amino group. Preferably, R ¹ ,
R ² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Y represents an alkoxy group, a chlorine atom or a bromine atom, W represents a single bond, and Y represents an acylamide group such as a formamide group, an acetamido group or a nitro group.

Hereinafter, the present invention will be described in detail. The photopolymerizable composition used in the photosensitive layer of the present invention contains, as essential components, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer. A polymerizable compound having an ethylenically unsaturated bond is a compound having at least one ethylenically unsaturated bond in its chemical structure, and may be a monomer, a prepolymer, that is, a dimer, a trimer, or another compound. Oligomers, their mixtures, and their copolymers.
Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid. Salts of unsaturated carboxylic acids include the alkali metal salts of the aforementioned acids, for example, sodium and potassium salts. Specific examples of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate,
1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Examples include dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomer. As methacrylic acid esters, tetramethylene glycol dimethacrylate, trimethylene glycol dimethacrylate,
Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, Screw-
[P- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis [p- (methacryloxyethoxy) phenyl] dimethylmethane and the like. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate, and the like. Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate and the like. As isocrotonic acid esters, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate,
And sorbitol tetraisocrotonate.
Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned esters can also be mentioned.

Specific examples of the amide of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-
Hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, see Japanese Patent Publication No. 48-417.
JP-A-08-208, in which a hydroxyl-containing vinyl monomer represented by the following general formula (II) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule, and two or more are added in one minute. And a vinyl urethane compound containing a polymerizable vinyl group. CH ₂ CC (R ³ ) COOCH ₂ CH (R ⁴ ) OH (II) (where R ³ and R ⁴ represent a hydrogen atom or a methyl group.) The photopolymerization initiator used in the present invention includes: Bicinal polyketaldonyl compounds disclosed in U.S. Pat.No. 2,367,660, α-carbonyl compounds disclosed in U.S. Pat.Nos. 2,367,661 and 2,367,670, and U.S. Pat.No. 2,448,828 Acyloin ethers disclosed in U.S. Pat.
The polynuclear quinone compounds disclosed in U.S. Pat. No. 1,758, the combination of a triarylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, and U.S. Pat. Benzothiazole compounds, U.S. Pat.No.4,239,850
Benzothiazole compound disclosed in
Trihalomethyl-s-triazine compounds, acridine and phenazine compounds disclosed in U.S. Pat.No. 3,751,259, oxadiazole compounds disclosed in U.S. Pat. Is about 0.5, based on the total weight of the photopolymerizable composition.
% By weight to about 15% by weight, preferably 2-10% by weight.

The high-molecular polymer used in the present invention is
Benzi as described in JP-B-59-44615
(Meth) acrylate / (meth) acrylic acid / necessary
Other addition polymerizable vinyl monomer copolymers;
Metak as described in JP-B-54-34327
Lylic acid / methyl methacrylate or methacrylic acid / methacrylic acid
Alkyl lylate copolymer, and other Japanese Patent Publication Nos. 58-1257
7, JP-B-54-25957, JP-A-54-927
No. 23 (meth) acrylic acid copolymer
As described in JP-A-59-53836.
Allyl (meth) acrylate / (meth) acrylic acid /
If necessary, copolymerization of other addition-polymerizable vinyl monomers
Anhydrous maleic described in JP-A-59-71048
Pentaerythritol triacrylate in acid copolymer
Or vinyl methacrylic acid added by half esterification
G / methacrylic acid / other addition polymerizable
-COOH, -PO in polymers such as
_ThreeH_Two, -SO_ThreeH, -SO_TwoNH_Two, -SO _TwoNHCO- group, acid value
50 to 200 acidic vinyl copolymers
You.

Particularly, among these, benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer copolymer and allyl (meth) acrylate / (meth) acrylic acid / optional Other addition-polymerizable vinyl monomer copolymers are preferred. These polymers can be used alone or as a mixture of two or more. The molecular weight of a high-molecular polymer can take a wide range of values depending on the type of the polymer, but in general,
5,000 to 1,000,000, preferably 10,000 to 500,000 are suitable. The amount of the polymer used is 10% to 90% by weight, preferably 30% to 85% by weight, based on the total weight of the photopolymerizable composition.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive layer.
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful, and in some cases, a dye or pigment for coloring the photosensitive layer and a pH as a printing agent.
An indicator or the like can be added. In addition, surfactants for improving coating properties (for example, JP-A-62-1709)
No. 50, No. 62-226143, U.S. Pat.
Fluorinated surfactants described in No. 1) and alkyl ethers may be added.

Further, malic acid, phosphorous acid, tartaric acid, citric acid, phosphoric acid, dipicolinic acid, polynuclear aromatic sulfonic acids and salts thereof, sulfosalicylic acid, etc. are added as necessary as stabilizers for the diazo resin. be able to. In addition, to prevent polymerization inhibition due to the effect of oxygen in the air,
A waxing agent can be added. What is used as a waxing agent is a material which is solid at room temperature but is dissolved in a coating solution and precipitates on the surface during a coating and drying process. Examples include higher fatty acids such as stearic acid and behenic acid, higher fatty acid amides such as stearic acid amide and behenic acid amide, and other higher alcohols.

In order to completely prevent the polymerization inhibition effect due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses may be provided. The method of applying such a protective layer is described in detail, for example, in U.S. Pat. No. 3,458,311 and JP-B-55-49729.

The photocrosslinkable composition of the present invention has a photocrosslinkable polymer having a photodimerizable unsaturated bond and a sensitizer as essential components. Used in the composition of the present invention,
As a photocrosslinkable polymer having a photodimerizable unsaturated bond, a maleimide group, a cinnamyl group, a cinnamoyl group,
A photosensitive polymer having a functional group such as a cinnamylidene group and a cinnamylidene acetyl group in a side chain or a main chain is exemplified.

In particular, polymers having a maleimide group in the side chain and polyester resins having a cinnamic acid skeleton in the molecular chain have relatively high sensitivity. Examples of such a polymer capable of photodimerization having a maleimide group in a side chain include JP-A-52-988 (corresponding to U.S. Pat. No. 4,079,041), German Patent 2,626,769, and European Patent 21,011.
9, European Patent 3,552 and
Angebandute Macromolecule Chemie (Dic
Angewandte Makromolekulare Chemie) 115 (198
The following general formula (III) described on pages 163 to 181 of 3):

[0022]

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Wherein R ⁵ and R ⁶ each independently represent an alkyl group having up to 4 carbon atoms, or R ⁵ and R ⁶ together form a 5- or 6-membered Or a polymer having a maleimide group in the side chain represented by the following formula:
Nos. 49-128992, 49-128993, 50-5376, 50-5377, 50-53
No. 79, No. 50-5378, No. 50-5380, No. 53-5298, No. 53-5299, No. 53-53
No. 00, No. 50-50107, No. 51-47940
No. 52-13907, No. 50-45076, No. 52-121700, No. 50-10884, No. 50
-45087, German Patent Nos. 2,349,948, 2,616,
No. 276, each having the following general formula (IV):

[0024]

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(Wherein R ⁷ represents an aromatic group, and R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group or a cyano group). Can be done. The average molecular weight of these polymers is at least 1,000, preferably from 10,000 to 100,000. These polymers have an average of two or more maleimide groups per molecule in the side chain. Among these polymers having a maleimide group in the side chain, particularly a polymer having an acid group can use alkaline water at the time of development, which is advantageous from the viewpoint of preventing pollution. The acid value of the maleimide group-containing polymer having an acid group is 2
The range is preferably from 0 to 300, more preferably from 50 to 2
00 range. In particular, among polymers having these acid numbers, Dic Angewandte Makromolekulare Chemie 1
28 (1984) pp. 71-91, N- [2- (methacryloyloxy) ethyl]-
A copolymer of 2,3-dimethylmaleimide and methacrylic acid or acrylic acid is useful. By synthesizing the vinyl monomer of the third component at the time of synthesizing the copolymer, a multi-component copolymer suitable for the purpose can be easily synthesized. For example, by using an alkyl methacrylate or an alkyl acrylate having a glass transition point of a homopolymer whose room temperature is equal to or lower than room temperature as a vinyl monomer of the third component, flexibility can be given to the copolymer.

In addition, as the photocrosslinkable polymer having an unsaturated bond capable of photodimerization used in the present invention, a polymer having at least two groups represented by the following general formula (V) or (VI) can be mentioned. Can be

[0027]

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(However, A: aryl group, substituted aryl group, furyl group or thienyl group, B: alkoxy group, aryl group, substituted aryl group or alkyl group, X: H, CN, halogen atom, phenyl group or alkyl group , Y ¹ ; H, CN, a halogen atom, a phenyl group or an alkyl group, and n represents an integer of 0 or 1.) having at least two groups represented by the general formula (V) or (VI) as a side chain Specific examples of the polymer include a homopolymer of an acrylic acid ester, a methacrylic acid ester, or a vinyl ether compound containing a group represented by the general formula (V) or (VI), a copolymer of two or more of these, and There is a copolymer copolymerized with another addition-polymerizable vinyl monomer as needed. An acrylic acid ester, methacrylic acid ester or vinyl ether compound containing a group represented by the general formula (V) or (VI) is disclosed in British Patent No. 94.
9,919, JP-B-45-36755, JP-B-46-4
No. 603, JP-A-47-34794, JP-B-59-1
No. 4352, JP-B-49-28122, JP-A-49-28122
36794, JP-A-49-103975, JP-B-5
No. 0-11283, Japanese Patent Publication No. 50-24621, Japanese Patent Publication No. 51-481, Japanese Patent Publication No. 55-44930, Japanese Patent Publication No. 5
No. 6,37,244, JP-B-56-52923, JP-B-57-28488, and the like. Of these, preferred are polyacrylates, polymethacrylates, and polyvinyl ether compounds having a cinnamate group in the side chain. The preferred molecular weight range of these photosensitive polymer compounds is from 2,000 to 1,000,000. More preferably, it is 10,000 to 200,000.

Other examples of the crosslinkable polymer having a photodimerizable unsaturated double bond in the main chain include phenylenediacrylic acid or a photosensitive polyester produced by condensation of an alkyl ester thereof with glycol. , Which have high photosensitivity. These polymers are
There have been many attempts to solubilize in an alkaline aqueous solution. For example, Japanese Patent Application Laid-Open No. 60-191244 describes a photosensitive composition capable of being developed with an alkaline water, comprising a photosensitive polymer compound having a carboxyl group introduced into a side chain. ing. In addition, U.S. Pat.No. 2,861,058 discloses a method for obtaining a compound obtained by reacting hydroxyl groups of polyvinyl alcohol with cinnamic acid chloride and an acid anhydride to impart photosensitivity and alkali water solubility simultaneously. No. 2,835,656 discloses a method of reacting a copolymer of maleic anhydride and styrene with β-hydroxyethylcinnamic acid ester, U.S. Pat.
No. 7,831, the method of introducing methacrylic acid into cinnamic acid acrylic ester polymer, U.S. Pat.
In the specification of JP-A-63-218945, a method of esterifying p-phenylenediacrylic acid monoethyl ester with a phenoxy resin and then hydrolyzing it is described in JP-A-63-218945. Various methods are described, such as a method of adding active mercaptocarboxylic acid.

The content of these photosensitive polymers is about 20 to 99% by weight, preferably 50 to 99% by weight in the photosensitive layer.
Is appropriate. As the sensitizer used in the photocrosslinkable composition of the present invention, a triplet sensitizer having a maximum absorption that actually allows sufficient light absorption in a range of 300 nm or more is preferable. Such sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, anthraquinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, xanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, naphthofuranone Compounds, benzoin compounds,
Examples include acetophenone compounds, fluorenone compounds, pyrylium salts, and thiapyrylium salts. Specifically, Michler's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-methyl-1,3-
Diaza-1,9-benz) anthrone picramide, 5-
Nitroacenaphthene, 2-nitrofluorene, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,
3-carbonyl-bis (7-diethylaminocoumarin), 2,4,6-triphenylthiapyrylium perchlorate, 2- (p-chlorobenzoyl) naphthothiazole, benzoin, benzoin methyl ether, benzoin ethyl ether, 2,2 -Dimethoxy-2-phenylacetophenone, 9-fluorenone, 2-chloro-9
Fluorenone, 2-methyl-9-fluorenone, 9,
10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, Dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone and the like can be mentioned.

Further, thioxanthone derivatives such as 2-
Chlorthioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone and the like, and German Patent No. 301889
Nos. 1 and 3117568, and EP 33720
It is preferred to use substituted thioxanthones as described in U.S. Pat. No. 2,075,506. Furthermore,
Merocyanine dyes, for example, 2- (heterocyclylcarbonylmethylene) benzo (or naphtho) thiazoline, 2- (diheterocyclecarbonylmethylene) benzo (or naphtho) thiazonin, 2-dibenzoylmethylenebenzo (or naphtho) thiazoline Specifically, 2- [bis (2-furoyl) methylene] -3-methylbenzothiazoline and 2- [bis (2-thenoyl) methylene] -3-methyl disclosed in Japanese Patent Publication No. 52-129791 Benzothiazonin, 2- [bis (2-furoyl) methylene] -3-methylnaphthothiazoline, 2- [bis (2-furoyl) methylene] -3-methylnaphthothiazoline, 2- (2-furoyl) methylene- 3-methylbenzothiazoline, 2-benzoylmethylene-3-methylbenzothiazoline, 2- (Benzoylmethylene) benzothiazoline, 2-bis (benzoylmethylene) naphthothiazoline, and thiazole, benzothiazole, naphthothiazole, and benzoselenazole having a thiobarbituric acid ring disclosed in Japanese Patent Publication No. 45-8832. Useful are sensitizing dyes of the type and sensitizers disclosed in Japanese Patent Application No. 1-190963.

In addition, if necessary, a binder, a plasticizer, and the like can be contained. Specific examples of the binder include:
Chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester, acrylic acid alkyl ester, copolymer with at least one kind of monomer such as acrylonitrile vinyl chloride, styrene, butadiene, polyamide, methyl cellulose, polyvinyl formal, polyvinyl butyral, methacryl There are acid copolymers, acrylic acid copolymers, itaconic acid copolymers and the like.

Examples of the plasticizer include dialkyl phthalates such as dibutyl phthalate and dihexyl phthalate;
Oligoethylene glycol alkyl esters, phosphate plasticizers and the like can be used. In some cases, for the purpose of coloring the photosensitive layer, a dye or pigment, a pH indicator or the like as a printing-out agent, and a surfactant or an alkyl ether for improving coating properties may be added.

Further, it is preferable to incorporate a thermal polymerization inhibitor and an antioxidant in the photosensitive layer. , Benzoquinone, 4,4'-thiobis (3-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-methyl-t-butylphenol), 2-mercaptobenzimidazole, and the like.

The diazo resin used in the present invention is
An oligomer is synthesized by a ring-opening polymerization reaction between a compound having two oxirane rings in one molecule and the compound represented by the general formula (I), and after converting the substituent Y of the obtained oligomer into an amino group, This is a diazo resin obtained by converting this amino group into a diazonium salt. The compound containing two oxirane rings in one molecule can be used as long as it is a compound containing two oxirane rings in one molecule. Preferably, the compound has a molecular weight of 170 to 1,000. For example, epoxy resins represented by the following general formulas (VII) to (XII) are preferably used.

[0036]

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[0037] In the ^{formula, R 9, R 10, R} 11, R 12 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R ^13, R ^14, the phase in each identical May be different, a hydrogen atom, an unsubstituted or carboxyl group, a sulfonyl group, an alkyl group substituted with an oxygen acid group of phosphorus, and R ¹⁵ and R ¹⁶ may be the same or different, A group having one oxirane ring, preferably a group represented by the following formula (XIII) or (XIV).

[0038]

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R ¹⁷ represents an alkylene group, an alkyl group or an alkoxy group-substituted alkylene group, a phenylene group or a cycloalkylene group; n represents a natural number of 1 or more;
R ¹⁸ represents a phenyl group or a naphthyl group which is unsubstituted or substituted with a hydroxyl group, an alkyl group or an alkoxy group, and R ¹⁹ represents a hydrogen atom or a methyl group. However, the compound is not limited to these as long as the compound has two oxirane rings in one molecule.

Specific examples of these epoxy resins include bisphenol A-epihalohydrin resin (for example, bisphenol A diglycidyl ether), bisphenol A-butadiene dioxide resin, and brominated bisphenol A-epihalohydrin resin (for example, brominated bisphenol A diglycidyl ether). Glycidyl ether), 4,4'-diglycidyloxydiphenylmethane, 4,4'-diglycidyloxybiphenyl, 4,4'-diglycidyloxy-3,
5,3 ', 5'-tetramethylbiphenyl, 2,2'-
Bis (4-glycidyloxyphenyl) ethane, hydrogenated bisphenol A diglycidyl ether, 2,2'-dimethyl-1,3-propanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4 -Butanediol diglycidyl ether, 1,2-propanediol diglycidyl ether, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N,
N-Diglycidyl-2,4,6-tribromoaniline diester of phthalic acid with epihalohydrin, diester of hexahydrophthalic acid with epihalohydrin, diester of tetrahydrophthalic acid with epihalohydrin, diester of 4-methyltetrahydrophthalic acid with epihalohydrin Chloride, vinylcyclohexene dioxide 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, spiroglycol diglycidyl ether 2- (3
4-epoxy) cyclohexyl-5,1-spiro (3,
4-epoxy) cyclohexyl-m-dioxane, diglycidylhydantoin and the like.

Specific examples of the compound represented by the general formula (I) include 4-aminoacetanilide, 4-aminoformanilide, 4-nitroaniline, and 4-amino-2-
Methoxyacetanilide, 4-amino-2-ethoxyacetanilide, 4-amino-2,5-dimethoxyacetanilide, 4-amino-2,5-dibutoxyacetanilide, 4-amino-2-methylacetanilide, 4-amino-3- Methyl acetanilide, 4-amino-3-chloroacetanilide, 4-amino-3-bromoacetanilide, 4-amino-2-methoxyformanilide, 4
-Amino-2-fluoropoxyformanilide, 4-amino-2,5-dimethoxyformanilide, 4-amino-3
-Ethylformanilide, 4-amino-3-bromoformanilide, 3-methoxy-4-nitroaniline, 3-
Butoxy-4-nitroaniline, 2-methyl-4-nitroaniline, 2-chloronitroaniline, 2,5-dimethoxy-4-nitroaniline, 4-amino-4'-nitrodiphenylamine, 4-acetylamino-4 ' -Aminodiphenylamine and the like.

Next, to synthesize the diazo resin used in the present invention, (1) a ring-opening polymerization reaction between a compound having two oxirane rings in one molecule and a compound represented by the above general formula (I) (2) Conversion of the substituent Y of the oligomer obtained in (1) to an amino group (3) Synthesis of the oligomer group of the oligomer obtained in (2) into a diazonium salt.

The details will be described below. (1) Synthesis of an oligomer by a ring-opening polymerization reaction of a compound having two oxirane rings in one molecule with a compound represented by the above general formula: a compound having two oxirane rings in one molecule (ie, epoxy Compound) and compound (I) in an appropriate solvent (for example, acetic acid, phenol, water, methanol, ethanol, isopropanol, propanol, butanol, 2-methoxyethanol, 1-methoxy-2)
-Propanol, acetone, ethyl acetate, methyl ethyl ketone, dimethylformamide, dimethylsulfoxide or a mixture thereof) in a short time, that is, for 1 to 20 hours at an arbitrary temperature of 0 ° C to 150 ° C, whereby the objective oligomer is obtained. can get.

In order to shorten the reaction time, it is preferable to carry out the reaction at a higher temperature, that is, while heating and refluxing the solvent. At that time, the epoxy compound and the compound (I)
May be used alone or in combination of two or more. The charging ratio between the epoxy resin and the compound is 0.1: 1 to 1: 0.1, preferably 0.2: 1 to 1: 0.2.
More preferably, it is 1: 1 to 1: 0.5. (2) The substituent Y of the oligomer obtained in (1) is converted to an amino group.

The substituent Y is preferably one which can be easily converted to an amino group, and examples thereof include an amide group and a nitro group. The amide group can be hydrolyzed by a known method, but is preferably performed under acidic conditions in order to prevent a side reaction of the polymer. The conversion of a nitro group to an amino group can be performed by a known reduction reaction. (3) The amino group of the oligomer obtained in (2) is converted to a diazonium salt.

The conversion of the amino group into a diazonium group is carried out according to a known method in an acidic solvent such as hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid with nitrite, sodium nitrite, potassium nitrite or ammonium nitrite. Are synthesized. The counter ion of the diazo resin used in the present invention is preferably an anion which stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent.

Specific examples include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids. Typical examples include hydrohalic acids such as hydrofluoric acid. , Hydrochloric acid, hydrobromic acid; sulfuric acid, nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid,
Inorganic iso- and heteropolyacids, for example phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters, arsonic acids, phosphinic acids, fluorocarboxylic acids such as trifluoroacetic acid, amide sulfonic acids, selenic acids , Hydrofluoric acid, hexafluorophosphoric acid, perchloric acid, and also aliphatic and aromatic sulfonic acids such as methanesulfonic acid, trifluoroalkanesulfonic acid such as trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexyl Sulfosuccinic acid, camphorsulfonic acid, tolyloxy-3
-Propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, diamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid Acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4
-Butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid , 5-nitro-o
-Toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxy Benzenesulfonic acid, dodecyloxybenzenesulfonic acid,
2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid , Dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3, 6-disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide 5-sulfonic acid and 1,2-naphthoquinone-1-diazide-4-sulfonic acid anion or, mixtures of these anions. Particularly preferred among these anions are hexafluorophosphoric acid, dibutylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid or 2-methoxy-4-hydroxy-5.
-Anion of benzoylbenzenesulfonic acid.

The diazo resin of the present invention is used in order to further enhance developability and to enable development with alkaline water, and includes carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, oxygen acid groups of phosphorus, phenolic hydroxyl groups and the like. May be contained. Incidentally, the oxygen acid group of phosphorus means a group represented by the following general formulas (XV) to (XX).

[0049]

Embedded image

In the formula, R ²⁰ is a hydrogen atom, R ²¹ is a hydrogen atom,
R ²² represents a hydrogen atom, an alkyl group or an aryl group; Preferably, R ²¹ represents a hydrogen atom, and R ²² represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. Particularly preferred oxygen acid groups of phosphorus include the groups represented by (XV) and (XVII).

There are the following two methods for introducing an alkali-soluble group. (i) The compound (I) is used in combination with a compound represented by the following general formula (XXI). NH ₂ —R ²³ —Z (XXI) In the formula, R ²³ is an alkylene group, a phenylene group, a naphthylene group, a cycloalkylene group which may have a single bond substituent, or any of those having a single bond, an ether bond, or the like. And Z represents an alkali-soluble group such as a carboxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, and a hydroxyaryl group which may have a substituent.

Specific examples of the compound represented by the general formula (XXI) include glycine, alanine, 2-amino-n-butanoic acid, 3-amino-n-butanoic acid, and 4-amino-n-butanoic acid.
Butanoic acid, 2-amino-iso-butanoic acid, 3-amino-
iso-butanoic acid, norvaline, valine, 6-amino-n
-Caproic acid, isoleucine, leucine, norleucine, 4-aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, 3-amino-2-naphthoic acid, 3-amino-1-naphthoic acid, sulfamic acid, amino Methanesulfonic acid, taurine, 2-aminobenzenesulfonic acid,
3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, O-phosphorylethanolamine, O-phosphoserine, aminomethylphosphonic acid, 1-aminoethylphosphonic acid, 2-aminophenylphosphonic acid, 3-aminophenylphosphonic acid, -Aminophenylphosphonic acid, 2-aminophenol, 3-aminophenol, 4
-Aminophenol and the like.

The compounds of the general formula (XXI) may be used alone or as a mixture of two or more. When synthesizing a diazo resin containing an alkali-soluble group, the compound of the general formula (I) and the compound of the general formula (XXI) are mixed and used at an arbitrary ratio. However, if the purpose of containing an alkali-soluble group is simply to improve developability, the ratio of the compound of the general formula (I) to the compound of the general formula (XXI) is as follows:
1: 0.01 to 0.1: 1, preferably 1: 0.05 to 0.5:
1, more preferably 1: 0.05 to 1: 1. If the purpose of introducing an alkali-soluble group is to develop with substantially alkaline water containing no organic solvent, the ratio between the two is:
0.1: 1 to 1: 0.1, preferably 0.2: 1 to 1: 0.2,
More preferably, it is 0.5: 1 to 1: 0.5. After the ring-opening polymerization reaction, it can be similarly synthesized according to the above-mentioned synthesis (1) to (3) of the diazo resin containing no alkali-soluble group. (ii) As the epoxy compound, an epoxy compound having an alkali-soluble group is used in combination with an epoxy compound containing no alkali-soluble group, or used alone.

Specific examples of such an epoxy compound having an alkali-soluble group include, for example, US Pat.
Nos. 933,471 and 2,933,472, epoxy compounds such as 2,3-diglycidyloxypropionic acid, 2,3-diglycidyloxypropyl-1-phosphate, and 2,3-diglycidyloxy- 1-phosphonic acid,
1,3-diglycidyloxypropyl-2-phosphate,
1,3-diglycidyloxy-2-phosphonic acid, 2,3
-Diglycidyloxypropyl-1-sulfonic acid, etc., but is not limited thereto.

When synthesizing a diazo resin containing an alkali-soluble group, an epoxy compound having an alkali-soluble group may be used alone or in combination with an epoxy compound containing no alkali-soluble group to form a compound of the formula (I). Used for ring-opening polymerization reaction. However, if the purpose of introducing an alkali-soluble group is simply to improve developability, the epoxy compound containing an alkali-soluble group and the epoxy compound not containing an alkali-soluble group are preferably 1: 0.1 to 0.01: 1, preferably. Is 1: 0.5-0.05: 1, more preferably 1: 1-0.0.
5: 1. Further, if the purpose of introducing an alkali-soluble group is to develop with substantially alkaline water that does not contain a diazo solubilizing agent such as an organic solvent or sodium sulfite,
The ratio of the two is 1: 0 to 0.1: 1, preferably 1: 0 to 0.1.
The ratio is 2: 1, more preferably 1: 0 to 0.5: 1. After the ring-opening polymerization reaction, it can be synthesized in exactly the same manner according to the above-mentioned synthesis (1) to (3) of the diazo resin containing no alkali-soluble group.

If necessary, the compound of the formula (I) and the compound having an alkali-soluble group of the formula (XXI) may be further used in combination. When synthesizing the diazo resin of the present invention, a compound having three or more oxirane rings in one molecule is used for the purpose of increasing the molecular weight of the diazo resin in order to further improve printing durability. May be used in combination with a compound containing an oxirane ring.

Specific examples of the compound having three or more oxirane rings in one molecule include 1,3,5-triglycidyl isocyanuric acid, phenol novolak epoxy compound, brominated novolak epoxy compound, and orthogre Sol novolak type epoxy compound, metacresol type epoxy compound, paragresol type epoxy compound, tetrakis (glycidyloxyphenyl) ethane,
N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, mN, N-diglycidylaminophenylglycidyl ether, triglycidyl ether of 2,2-dihydroxymethyl-n-butanol, etc. But not limited to these.

At this time, the charge ratio of the compound containing three or more oxirane rings in one molecule to the compound containing two oxirane rings in one molecule is arbitrary, but is generally from 0 to 5
0 mol%, preferably 0 to 20 mol%. further,
The total number of moles of the oxirane ring is preferably at least twice as much as the compound (I). Further, for the purpose of increasing the molecular weight, a compound having two or more amino groups in one molecule may be used in combination with the compound (I).

Specific examples of the compound having two or more amino groups in one molecule include, for example, diethylenetriamine,
Triethylenetetramine, diethylaminotetramine,
N-aminoethylpiperazine, 1,4-phenylenediamine, 1,3-phenylenediamine, diaminodiphenylmethane, diaminodiphenylamine, diaminodiphenylsulfone, xylylenediamine, hexamethylenediamine, and the like, but are not limited thereto. .

At this time, the charge ratio of the compound having two or more amino groups in one molecule to the compound (I) is arbitrary, but is generally about 0 to 40 mol%, preferably 0 to 20 mol%. Further, the total number of moles of the oxirane ring is preferably at least twice the primary amine and at least one times the secondary amine. The molecular weight of the diazo resin of the present invention can be obtained as an arbitrary value by variously changing the molar ratio of each monomer and the reaction conditions in the crosslinking reaction. However, the diazo resin can be effectively used for the purpose of the present invention. For the purpose of use, those having a weight average molecular weight of about 1,000 to 100,000 can be used, but those having a weight average molecular weight of about 1,500 to 20,000 are suitable.

Next, typical examples of the synthesis of the diazo resin of the present invention will be described. Synthesis Example 1 17.4 g (0.100 mol) of ethylene glycol diglycidyl ether and 14.3 g (0.0950 mol) of 4-aminoacetanilide were dissolved in 50 ml of glacial acetic acid with stirring. This reaction solution was stirred and reacted at 80 ° C. for 8 hours.
Thereafter, the reaction solution was poured into 500 ml of water with vigorous stirring, and the resulting solid was filtered and dried to obtain a diazo resin prepolymer.

Next, the obtained white air was washed with 80 m of ethanol.
and dissolved in 80 ml of water, concentrated hydrochloric acid was added, and the mixture was heated under reflux at 75 ° C. for 6 hours. By sampling a part of the reaction solution, it was confirmed by NMR and IR spectra that the acetylamide group was converted to an amino group. The reaction solution was further cooled on ice and 6.56 g of sodium nitrite (0.09 g) was added.
A solution of 50 mol) in 20 ml of water was slowly added dropwise so that the internal temperature of the reaction solution did not exceed 10 ° C. Thereafter, stirring was further continued for 30 minutes under ice cooling. Thereafter, the reaction solution was diluted with 400 ml of water.
EK 200 ml and di-n with vigorous stirring.
32.7 g of sodium butylnaphthalenesulfonate (0.
(0950 mol) in 100 ml of water and stirring was continued for 30 minutes. After the completion of the reaction, the reaction solution was allowed to stand and separated into two layers. When this upper layer was poured into 1 liter of water with vigorous stirring, a yellow-green solid precipitated. This is filtered,
After washing with water and drying, a diazo resin (diazo resin 1 of the present invention) was obtained.

The obtained diazo resin was treated with 1-phenyl-3
After coupling with -methyl-5-pyrazolone, the molecular weight was measured by gel permeation chromatography (hereinafter abbreviated as GPC).
00. (Synthesis Example 2) Bisphenol A diglycidyl ether (33.2 g, 0.100 mol) in place of ethylene glycol diglycidyl ether in Synthesis Example 1 and 4-amino-2-methoxyformanilide (15.8 g) instead of 4-aminoacetanilide (0.0950 mol), a diazo resin was obtained in exactly the same manner as in Synthesis Example 1, except that 50 ml of methanol was used instead of glacial acetic acid, and the reaction temperature was changed to 60 ° C. (Diazo resin 2 of the present invention). The weight average molecular weight is 42
60.

Synthesis Example 3 Instead of ethylene glycol diglycidyl ether in Synthesis Example 1, 61.8 g of tetrabromobisphenol A diglycidyl ether (0.0
The diazo resin was obtained in the same manner as in Synthesis Example 1 except that 950 mol) was used (diazo resin 3 of the present invention). The weight average molecular weight was 4780. (Synthesis Example 4) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 16.6 g
(Diazo resin 4 of the present invention), except that (0.0500 mol) was used.

The weight average molecular weight was 7,320. (Synthesis Example 5) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
), Bisphenol A diglycidyl ether 16.6 g
(0.0500 mol), and 31.4 g (0.0900 mol) of sodium dodecylbenzenesulfonate was used in place of sodium dibutylnaphthalenesulfonate. Diazo resin 5).

The weight average molecular weight was 7,320. (Synthesis Example 6) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
), Bisphenol A diglycidyl ether 16.6 g
(The diazo resin of the present invention), except that (0.0500 mol) and 18.4 g (0.100 mol) of potassium hexafluorophosphate were used instead of sodium dibutylnaphthalenesulfonate. 6).

The weight average molecular weight was 7,320. (Synthesis Example 7) Instead of 0.0950 mol of 4-aminoacetanilide in Synthesis Example 1, 12.0 g (0.0800 mol) of 4-aminoacetanilide, 2.1 amino 4-aminobenzoic acid
It was synthesized in exactly the same manner as in Synthesis Example 1 except that 9 g (0.0160 mol) was used (diazo resin 7 of the present invention).

The weight average molecular weight was 5,300. (Synthesis Example 8) Instead of 0.0950 mol of 4-aminoacetanilide in Synthesis Example 1, 4-aminoacetanilide was used.
6.01 g (0.0400 mol), 7.9 4-aminobenzoic acid
It was synthesized in exactly the same manner as in Synthesis Example 1 except that 5 g (0.05800 mol) was used (diazo resin 8 of the present invention).

The weight average molecular weight was 5,250. (Synthesis Example 9) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
), Bisphenol A diglycidyl ether 16.6 g
(0.0500 mol) in 4-aminoacetanilide 0.0
4-aminoacetanilide instead of 950 mol 11.3
g (0.0750 mol), 2.74 g of 4-aminobenzoic acid
(Diazo resin 9 of the present invention) except that (0.0200 mol) was used.

The weight average molecular weight was 7110. (Synthesis Example 10) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g of ethylene glycol diglycidyl ether (0.0500 mol
l), bisphenol A diglycidyl ether 16.6 g
(0.0500 mol) in 4-aminoacetanilide 0.0
Instead of 950 mol, 4-aminoacetanilide 5.71
g (0.0380 mol), 8.23 g of 4-aminobenzoic acid
(Diazo resin 10 of the present invention) except that (0.0600 mol) was used.

The weight average molecular weight was 7,280. (Synthesis Example 11) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 10.5 g of ethylene glycol diglycidyl ether (0.0600 mol
l), bisphenol A diglycidyl ether 13.3 g
(0.0400 mol) is replaced by 4-amino-2-methoxyformanilide 6.65 in place of 4-aminoacetanilide.
g (0.0400 mol), 4.13 g of glycine (0.05550)
mol) was used in the same manner as in Synthesis Example 1 (diazo resin 11 of the present invention).

The weight average molecular weight was 6410. (Synthesis Example 12) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 7.00 g (0.0400 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 19.9 g
(0.0600 mol) in 4-aminoacetanilide 0.0
4-aminoacetanilide instead of 950 mol 11.3
g (0.0750 mol), aminomethanesulfonic acid 2.22
g (0.0200 mol) was used in the same manner as in Synthesis Example 1 (diazo resin 12 of the present invention).

The weight average molecular weight was 4,830. (Synthesis Example 13) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 7.00 g (0.0400 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 19.9 g
(0.0600 mol) in 4-aminoacetanilide 0.0
Instead of 950 mol, 4-aminoacetanilide 5.71
g (0.0380 mol), aminomethanesulfonic acid 6.44
g (0.0580 mol) was used in the same manner as in Synthesis Example 1 (diazo resin 13 of the present invention).

The weight average molecular weight was 5020. (Synthesis Example 14) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 12.2 g of ethylene glycol diglycidyl ether (0.0700 mol
l), 19.5 g (0.0300 mol) of tetrabromobisphenol A diglycidyl ether, 10.5 g (0.0700 mol) of 4-aminoacetanilide instead of 0.0950 mol of 4-aminoacetanilide, and 3.70 g of O-phosphorylethanolamine It was synthesized in exactly the same manner as in Synthesis Example 1 except that 53 g (0.025 mol) was used (diazo resin 14 of the present invention).

The weight average molecular weight was 5,470. (Synthesis Example 15) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 12.2 g of ethylene glycol diglycidyl ether (0.0700 mol
l), 9.97 g of bisphenol A diglycidyl ether
(0.0300 mol) in 4-aminoacetanilide 0.0
6.76 mol of 4-aminoacetanilide instead of 950 mol
g (0.045 mol), O-phosphonylethanolamine
It was synthesized in exactly the same manner as in Synthesis Example 1 except that 7.34 g (0.052 mol) was used (diazo resin 15 of the present invention).

The weight average molecular weight was 5530. (Synthesis Example 16) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 13.9 g (0.0800 mol) of ethylene glycol diglycidyl ether was used.
l), 4,4-bis (4-glycidyloxyphenyl)
Except that 7.81 g (0.0200 mol) of pentanoic acid was used,
It was synthesized in exactly the same manner as in Synthesis Example 1 (the diazo resin 1 of the present invention).
6).

The weight average molecular weight was 4,920. (Synthesis Example 17) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 39.0 of 4,4-bis (4-glycidyloxyphenyl) pentanoic acid was used.
Synthetic Example 1 was synthesized in exactly the same manner as in Synthesis Example 1 except that g (0.100 mol) was used (diazo resin 17 of the present invention).

The weight average molecular weight was 5220. (Synthesis Example 18) Instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 21.8 g of 2,3-diglycidyloxypropionic acid (0.100 mol
) Was synthesized in exactly the same manner as in Synthesis Example 1 (diazo resin 18 of the present invention).

The weight average molecular weight was 3,980. The content of the diazo resin used in the present invention in the photosensitive layer is 0.1 to 30% by weight, preferably 1 to 10% by weight.
It is. The diazo resin used in the present invention can be highly sensitized because it can be easily made to have a high molecular weight, and has a low absorption of diazo on the long wavelength side, so that it does not easily cause fog against white fluorescent light and the like.

The photosensitive composition of the present invention is dissolved in a suitable organic solvent, and dried on a support having a hydrophilic surface.
When coated so as to be 0.2 to 10 g / m ² , a photosensitive lithographic printing plate can be obtained. The concentration of the photosensitive composition at the time of application is desirably in the range of 1 to 50% by weight. As the coating solvent used, methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, dimethoxyethane, diethylene glycol monomethyl ether,
Examples thereof include diethylene glycol dimethyl ether, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl lactate, ethyl lactate, ethylene dichloride, cyclohexanone, dioxane, and tetrahydrofuran. A mixed solvent obtained by adding a mixed solvent thereof or a solvent which does not dissolve a small amount of water or a diazo resin such as toluene or a high molecular compound to the mixed solvent or the mixed solvent is also suitable. When a photosensitive solution dissolved in these solvents is applied to a support and dried 5
It is desirable to dry at 0 ° C to 120 ° C. The drying may be carried out at a low temperature at the beginning, followed by preliminary drying, followed by drying at a high temperature. Alternatively, drying may be carried out directly at a high temperature by selecting an appropriate solvent and concentration.

The surface of the photosensitive layer provided as described above is preferably matted in order to shorten the evacuation time in the close contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, JP-A-50-125805 and JP-A-58-18263
No. 6, a method of providing a mat layer as described in JP-B-57-6582, and a method of heat-fusing solid powder as described in JP-B-62-62337. Can be

In the present invention, an intermediate layer may be added, if necessary, for the purpose of enhancing the adhesion between the support and the photosensitive layer, preventing the photosensitive layer from remaining after development, or preventing halation. It may be provided. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin or a phosphoric acid compound adsorbed on aluminum, for example. The intermediate layer made of a substance having high solubility so that the photosensitive layer does not remain after development is generally made of a polymer having good solubility or a water-soluble polymer. Furthermore, for antihalation, the intermediate layer generally contains dyes and UV absorbers. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Usually, the coating ratio of about 1 to 100 mg / m ² on a dry solids well, 5 to 40 mg / m ² is particularly favorable.

The use ratio of the diazo resin of the present invention in the intermediate layer is 30 to 100% by weight, preferably 60 to 10% by weight.
0% by weight. In the intermediate layer, if necessary, a sensitizer,
Diazo stabilizer, polymer binder, antihalation agent,
In addition to the surfactant, various additives may be added. To provide the intermediate layer, the compound is obtained by dissolving the above compound in a desired solvent at a desired concentration, coating or dipping it, and then drying.

As the support having a hydrophilic surface used in the present invention, various substrates such as paper, plastic, and metal are used. When used for a photosensitive lithographic printing plate, particularly, a hydrophilic plate is used. Aluminum plates are preferred. The surface of the aluminum plate is made of a mechanical method such as wire brush graining, brush graining using a nylon brush while pouring a slurry of abrasive particles, and ball graining, or a chemical using HF, AlCl ₃ , or HCl as an etchant. Graining, after graining the surface by electrolytic graining using nitric acid or hydrochloric acid as the electrolytic solution or composite graining performed by combining these surface roughening methods, and then etch-treated with acid or alkali as necessary, Subsequently, it is preferable to perform anodization in a sulfuric acid, a phosphoric acid, an oxalic acid, a boric acid, a chromic acid, a sulfamic acid or a mixed acid thereof with a direct current or an alternating current power supply to provide a strong passivation film on the aluminum surface. Although the aluminum surface is hydrophilized by such a passivation film itself, the silicate treatment (sodium silicate) described in U.S. Pat. No. 2,714,066 and U.S. Pat. ,
Potassium silicate), potassium fluoride zirconate treatment described in U.S. Pat. No. 2,946,638, phosphomolybdate treatment described in U.S. Pat. Alkyl titanate treatment, polyacrylic acid treatment described in German Patent 1,091,433, German Patent No. 1,091,433
No. 134,093 and British Patent No. 1,230,447, polyvinylphosphonic acid treatment, JP-B-44-640.
No. 9, published by U.S. Pat.
Phytic acid treatment described in 3,307,951
JP-A-58-16893 and JP-A-58-18291 each describe a treatment with a salt of a hydrophilic organic polymer compound and a divalent metal, described in JP-A-59-101651. It is particularly preferable that the hydrophilic treatment is performed by undercoating the water-soluble polymer having a sulfonic acid group. Other hydrophilic treatment methods include silicate electrodeposition described in U.S. Pat. No. 3,658,662.

Further, after graining treatment and anodic oxidation, sealing treatment is also preferred. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. The photosensitive composition of the present invention coated on a support is exposed through a transparent original having a line image, a halftone dot image, and the like, and then developed with an aqueous alkaline developer to form a negative relief image on the original. give.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, laser beams and the like. The developer used for the development of the photosensitive printing plate according to the present invention may be any of known ones, but preferably the following are preferred. For example, the developer contains at least one alkaline agent and water as essential components.

The alkaline agent contained as an essential component in the developer includes sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of secondary or tertiary phosphoric acid, Sodium silicate, sodium carbonate, inorganic alkali agents such as ammonia, mono, di, or trimethylamine, mono,
Examples thereof include organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, and ethylenediimine.

The content of these alkali agents in the developer is 0.05 to 10% by weight, preferably 0.5 to 5% by weight. If the amount is less than 0.05% by weight, the development becomes poor, and if it exceeds 10% by weight, the printing performance as a planographic printing plate is adversely affected. The developer for developing the photosensitive printing plate according to the present invention may contain a specific organic solvent, if necessary.

Such an organic solvent is capable of dissolving or swelling the above-mentioned non-exposed portion (non-image portion) of the photosensitive composition layer when incorporated in a developer, and at room temperature (20 ° C.). Refers to an organic solvent having a solubility in water of 10% by weight or less. Any such organic solvent may be used as long as it has such properties.
The following may be mentioned, but are not limited thereto. That is, for example, carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amine acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone; Ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol and methyl amyl alcohol; alkyls such as xylene Substituted aromatic hydrocarbons include halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is generally from 0 to 20% by weight, particularly from 2 to 10% by weight.
A more favorable result is obtained when

The developer for developing the photosensitive printing plate according to the present invention may contain a water-soluble sulfite, if necessary. As such a water-soluble sulfite, an alkali or alkaline earth metal sulfite is preferable, and examples thereof include sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is from 0 to 4% by weight, preferably from 0.1 to 1% by weight.

Further, in place of the water-soluble sulfite, an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or a hydroxy aromatic compound such as methylresorcin may be contained. Of course, water-soluble sulfites of these compounds can be used in combination. In addition, a certain solubilizing agent may be included to assist the dissolution of the above-mentioned organic solvent in water. As such a solubilizing agent, in order to realize the predetermined effect of the present invention, it is preferable to use low molecular alcohols and ketones which are more soluble in water than the organic solvent used.

Further, an anionic activator, a surface active agent and the like can be used. Such alcohols and ketones include, for example, methanol, ethanol, propanol,
It is preferable to use butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxy-4-methylbutanol, N-methylpyrrolidone, and the like. As the surfactant, for example, sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, sodium N-methyl-N-pentadecylaminoacetate, sodium lauryl sulfate, and the like are preferable. Generally, the amount of the solubilizer such as alcohol and ketone used is preferably about 30% by weight or less based on the whole developer.

However, if an organic solvent or the like is contained, problems such as toxicity at work, hygiene problems such as odor, safety problems such as fire and gas explosion, workability problems such as generation of bubbles, pollution by waste liquid, etc. Therefore, those which do not substantially contain an organic solvent are preferred because they cause problems such as the above problem and cost. In addition, "substantially does not contain an organic solvent" means that the organic solvent is not contained to the extent that causes inconvenience in view of the above-mentioned environmental health, safety, workability, etc., and in the present invention, The ratio of the substance in the composition is 2% by weight or less, preferably 1% by weight or less.

As such an aqueous alkaline developer containing substantially no organic solvent, a positive type lithographic printing plate described in, for example, JP-A-59-84241 and JP-A-57-192952 can be used as an image. After exposure, a developer composition used for development can be used. The photosensitive lithographic printing plate using the photosensitive composition of the present invention is described in JP-A-54-8002 and JP-A-55-1.
It goes without saying that the plate-making process may be carried out by the methods described in JP-A-15045 and JP-A-59-58431. That is, after the development processing, washing with water and then desensitization processing, or desensitization processing as it is, or treatment with an aqueous solution containing an acid,
Alternatively, a desensitization treatment may be performed after treatment with an aqueous solution containing an acid. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity decreases, in that case, JP-A-54-62004, 55-227
No. 59, No. 55-115039, No. 56-12645, No. 58-95349,
The replenisher and the replenishment method described in JP-A-64-21451, JP-A-1-180548 and JP-A-2-3065 can restore the processing capacity.

Further, the above plate making process is disclosed in
It is preferably carried out by an automatic developing machine as described in JP-A Nos. 7054 and 2-32357. In addition, as the desensitized gum applied as desired in the final step of the plate making process,
No. 62-16834, No. 62-25118, No. 63-52600, JP-A-62-7
Nos. 595, 62-11693 and 62-83194 are preferred.

[0096]

The photosensitive lithographic printing plate of the present invention maintains excellent sensitivity and performance possessed by the photosensitive layer, has excellent adhesion to a support without generating printing stains, and is suitable for white fluorescent lamps and the like.
Less fogging. Hereinafter, the present invention will be described in more detail with reference to Examples. "%" Indicates% by weight unless otherwise specified. Example 1 An aluminum plate of 1S material having a thickness of 0.24 mm was sand-grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then thoroughly washed with water. This one
0% was dipped for 60 seconds at 70 ° C. in sodium hydroxide solution after etching, after neutralized and washed with 20% nitric acid washed with running _{water, V A = 12.7V, V C} = 9.1V sinusoidal alternating waveform Using current, 170 coulomb / dm ² in 1% nitric acid aqueous solution
The electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. Continue 3
After immersion in a 0% sulfuric acid aqueous solution and desmutting at 55 ° C. for 2 minutes, anodizing treatment was performed in a 7% sulfuric acid aqueous solution such that the coating amount of aluminum oxide was 1.8 g / m ² . Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. The following photosensitive solution was applied to the aluminum plate obtained as described above using a wheeler and dried at 80 ° C. for 2 minutes to a dry weight of 2.0 g / m ² .

The photosensitive lithographic printing plate thus obtained is referred to as [A]. Photosensitive solution (1) o Poly (allyl methacrylate / methacrylic acid) copolymer 5.0 g (molar ratio 70/30) o Pentaerythritol tetraacrylate 1.5 g o The following photopolymerization initiator 0.3 g

[0098]

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O 0.2 g of the diazo resin of Synthesis Example (1) of the present invention 0.15 g of Oil Blue # 603 (manufactured by Orient Chemical Industries) o 0.05 g of Megafac F-177 (0.05 g of Dainippon Ink and Chemicals, Inc.) O phosphite (50%) 0.05 g o Behenamide 0.10 g o Ethylene glycol monomethyl ether 50 g o Methyl ethyl ketone 50 g o Methanol 20 g Comparative Example 1. Substitute for diazo resin of photosensitive solution 1 4-diazodiphenylamine (0.1 mol) and formaldehyde (0.1 mol)
l) A photosensitive lithographic printing plate [B] was obtained in the same manner as in Example 1 except that dibutylnaphthalenesulfonate (weight average molecular weight 2100) as a condensate with l) was used.

These photosensitive lithographic printing plates [A] and [B]
To a white fluorescent light (Mitsubishi Neorumi Super FLR40S)
(W50EDL-MNU) at a brightness distance of 400 Lux for 5 minutes each. After that, a gray scale tablet manufactured by Fuji Photo Film Co., Ltd. and a dot negative film are stacked, and a printer FT26V manufactured by Nuark, USA
50 with 2UPNS (light source: 2kw metal halide lamp)
The plate was exposed to count light, immersed in a developing solution shown below at 25 ° C. for 1 minute, rubbed lightly with absorbent cotton, washed with water, and treated with a desensitizing solution to obtain a lithographic printing plate. (Developer) Sodium sulfite 5 g Benzyl alcohol 30 g Sodium carbonate 5 g Sodium isopropylnaphthalenesulfonate 12 g Water 1000 g (Desensitizing solution) o Arabic gum 5 g o White dextrin 30 g o Ethylene glycol 10 g o Phosphoric acid 3 g o Water 1000 g These printing plates Was printed on high quality paper with a commercially available ink using a SOR printer manufactured by Heidelberg.

The printing performance was as shown in Table 1. Table 1 ─────────────────────────── Printing plate [A] Printing plate [B] ───────────り Thickness of halftone dots ^* No fatty Fatty ────────────────────────汚 れ Dirt on non-image area No dirt Light dirt ─────────────────────────── Printing durability 500000 printing 5 0.00000 prints completed ^* Comparison with a plate that was not fogged under white light Example 2. Photosensitive solution (2) was prepared and coated on the support of Example 1 in the same manner as in Example 1.

Photosensitive solution (2) o Benzyl methacrylate / methyl methacrylate / methacrylic acid = 50/10/40 (molar ratio) copolymer 5 g o Dipentaerythritol hexaacrylate 2.0 g o Lophine dimer / Michler's ketone 0.3 / 0 0.3 g o Copper phthalocyanine pigment (CIPigment Blue 15) 1.0 g o Diazo resin 8 of Synthesis Example 8 of the present invention 8 0.3 g o Malic acid o Megafac F177 (Dainippon Ink Chemical Industry Co., Ltd.) 0.2 g o Ethylene Glycol monomethyl ether 50g o Methyl ethyl ketone 50g o Methanol 50g Then polyvinyl alcohol (saponification degree 86.5-89.0mo)
l% polymerization degree of about 1000) was provided on the surface of the photosensitive layer so as to have a dry weight of 1.0 g / m ² ,
A photosensitive lithographic printing plate [C] was obtained. Comparative Example 2 The procedure of Example 2 was repeated except that the diazo resin of the photosensitive solution (2) was replaced by dodecylbenzenesulfonate, which is a condensate of 4-diazodiphenylamine (0.10 mol) and formaldehyde (0.10 mol). In the same manner as in Example 2, a photosensitive lithographic printing plate [D] was obtained.

These photosensitive lithographic printing plates [C] and [D] were
After exposure under a white fluorescent lamp as in Example 1, exposure was performed.
It was developed with the following developer and desensitized. (Developer) 20 g of potassium silicate having a molar ratio of SiO ₂ / K ₂ O of about 1.1 20 g of water 1000 g of the obtained printing plate was printed in the same manner as in Example 1. Table 2 shows the results.

Table 2 {Printing plate [C] Printing plate [D]}網 Thickness of halftone dot No fat Thickening ──────────────────────汚 れ Stain on non-image area No stain Stain on the entire surface 刷 Printing durability 40,000 Finishing 40,000 printings ─────────────────────────── Example 3. Using the same AL support as in Example 1. Then, the following photocrosslinkable photosensitive solution (3) was prepared.

Photosensitive solution (3) o Methyl methacrylate / N- [6- (methacryloyloxy) hexyl] -2,3-dimethylmaleimide / methacrylic acid = 10/60/30 (molar ratio) copolymer 5 g o The following structure 0.3 g of a sensitizer represented by the formula

[0106]

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O 0.15 g of diazo resin 11 of Synthesis Example 11 of the present invention o 0.10 g of Victoria Pure Blue BOH (Hodogaya Chemical) 0.10 g of 2,4 trichloromethyl (4'-methoxynaphthyl) 6-triazine FAC F177 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.10 g o Propylene glycol monomethyl ether 50 g o Methyl ethyl ketone 50 g o Methyl alcohol 20 g The dry weight of this photosensitive solution was adjusted to 1.0 g / m ² using a wheeler. Dried at 80 ° C. for 2 minutes. The photosensitive lithographic printing plate thus obtained is referred to as [E]. Comparative Example 3 Instead of the photosensitive solution (3) diazo resin of Example 3, 4-diazodiphenylamine (0.100 mol) and 4,4'-bishydroxymethyldiphenyl ether (0.100 mol) were used.
A photosensitive lithographic printing plate [F] was obtained in the same manner as in Example 3 except that the condensate of the above was replaced with dodecylbenzenesulfonate (weight average molecular weight 3950).

A lithographic printing plate was obtained from these photosensitive lithographic printing plates and printed in the same manner as in Example 2. Table 3 shows the results. Table 3 ─────────────────────────── Printing plate [E] Printing plate [F] ───────────網 Thickness of halftone dot No fat Thickening あ り汚 れ Stain on non-image area No stain Stain on entire surface ─────────────────────────── Printing durability 40,000 printings 4. 100,000 prints completed Example 4 The following photocrosslinkable photosensitive solution (4) was prepared.

Photosensitive solution (4) o 5.0 g of a polymer having the following structure produced by condensation of p-phenylenediethoxy acrylate and 1,4-di-β-hydroxyethoxycyclohexane

[0110]

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O 0.3 g of the following sensitizer

[0112]

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O 0.15 g of diazo resin 14 of Synthesis Example 14 of the present invention o Plasticizer of copper phthalocyanine pigment (CI Pigment Blue 15) 10% dispersion 1.0 g o Methyl ethyl ketone 20 g o Propylene glycol monomethyl ether 30 g This photosensitive composition The product was dried on the same aluminum support as in Example 1 using a spin coater to obtain a weight after drying, which was 1.
The composition was applied so as to be 0 g / m ² and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate [G].

Further, as a comparative example, a photosensitive lithographic printing plate [H] was obtained in the same manner except that the diazo resin was replaced with a formaldehyde condensate of 4'-methoxy-4-diazodiphenylamine. These photosensitive lithographic printing plates were left under a white fluorescent lamp, exposed, developed and printed in the same manner as in Example 1.
Table 4 shows the results.

Table 4 {lithographic printing plate [G] lithographic printing plate [H]}網 Thickness of halftone dot No fat Thickening ────────────────── ────────── Non-image area dirt No dirt Dirt 刷 Printing durability 4 0.00000 prints 40,000 prints ──────────────────────────── Example 5 The following undercoat liquid was prepared. To (undercoat liquid) o the present invention Synthesis Example 18 of the diazo resin 18 0.10 g o methanol 50g o methylethylketone 50g the undercoating liquid on the support of Example 1, and the dry weight, coated to a 10 mg / m ² And dried at 80 ° C. for 1 minute.

Next, the following photosensitive solutions were prepared. Photosensitive solution 5. o N- [2- (methacryloyloxy) ethyl] -2,3-dimethylmaleimide / methacrylic acid = 65/35 (molar ratio) copolymer 5 g o The following sensitizer 0.4 g

[0117]

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O Ethyl violet 0.15 g o 4-diazodiphenylamine hexafluorophosphate 0.10 g o Megafac F177 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.10 g o Propylene glycol monomethyl ether 50 g o Methyl ethyl ketone 50 g This photosensitive solution 5 was dried on the support of Example 1 in a dry weight of 1.
Coating and drying to ² g / m ² , photosensitive lithographic printing plate [I]
I got Comparative Example 5. Example 5 was replaced with diazo resin in the undercoat liquid,
-A photosensitive lithographic printing plate [J] was obtained in the same manner as in Example 5, except that a hexafluorophosphate salt of a condensate of diazodiphenylamine (0.100 mol) and formaldehyde (0.100 mol) was used.

After exposing these photosensitive lithographic printing plates to a white fluorescent lamp in the same manner as in Example 2, exposure, development, desensitization treatment and printing were performed. Table 5 shows the results. Table 5 ──────────────────────────── Lithographic printing plate [I] Lithographic printing plate [J] ────────網 Thickness of halftone dot No fat Thickening ─────────────────────汚 れ Stain on non-image area No stain Stain on the entire surface 刷 Press life 4 0.0000 printings 40,000 printings ──────────────────────────── Thus, the photosensitive lithographic printing plate of the present invention Has excellent adhesion to a support, high work safety under a white fluorescent lamp, and has excellent alkali developability and is hardly stained.

Claims (1)

(57) [Claims] 1. A photosensitive lithographic printing plate comprising a support having a hydrophilic surface and a photopolymerizable or photocrosslinkable photosensitive layer provided thereon, wherein an intermediate layer in the photosensitive layer or between the support and the photosensitive layer is provided. A photosensitive lithographic printing plate comprising a diazo resin obtained by the following method. An oligomer is synthesized by a ring-opening polymerization reaction between a compound containing two oxirane rings in one molecule and a compound represented by the following general formula (I), and the substituent Y of the obtained oligomer is converted into an amino group. A diazo resin obtained by converting this amino group into a diazonium salt. Embedded image In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, W represents a single bond or any divalent organic group, and Y represents any convertible amino group. Shows a substituent.