JPH0425845A - Photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To enhance the sensitivity of the planographic printing plate, developability with an alkaline developer and printing performance by incorporating a specific diazo resin. CONSTITUTION:This printing plate is constituted by providing a photosensitive layer contg. a photocrosslinking type polymer compd. which is soluble alkaline water or swellable and is photodimerizable via an intermediate layer at need on a base having a hydrophilic surface. The diazo resin (e.g. the compd. expressed by formula) having >=1 oxygen acid groups of phosphorus is incorporated into this photosensitive layer and/or intermediate layer. In the formula, R<7> denotes the oxygen acid group of phosphorus or the group having the oxygen acid group; (n) denotes 1 or 2; R<8> denotes H, alkyl, hydroxy, etc.; R<9>, R<10> denote H, alkyl or alkoxy; X<-> denotes anion; Y denotes >NH, -O- or -S-.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate having improved adhesion to a support having a hydrophilic surface. The present invention relates to a photosensitive lithographic printing plate provided with a photosensitive layer containing a photocrosslinkable polymer.

[Prior Art] Photocrosslinkable materials that are crosslinked by cycloaddition reaction are well known, and many of these are used as main components of photosensitive compositions used in the production of photosensitive lithographic printing plates and the like. Examples of such photocrosslinkable polymers include polymers having maleimide groups in their side chains, cinnamyl groups, cinnamoyl groups, cinnamylidene groups, cinnamylidene acetyl groups, and others having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus. Polymers having chalcone groups etc. in the side chain or main chain are useful,
Some have even been put into practical use. In particular, polymers with maleimide groups in their side chains and polyester resins with a cinnamic acid skeleton in the molecular chain produced by condensation of phenylene diacrylic acid or its alkyl ester with glycol have relatively high sensitivity. . From the viewpoint of safety in the working environment, it is preferable not to use an organic solvent in the developing solution, and attempts have also been made to solubilize these polymers in alkaline water. Such polymers include De-Angebandute, Macromolecule,
Chemie (Die Angewandte Makr.

molecular chemistry) 128 (1
Copolymers of N-C2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide and methacrylic acid or acrylic acid as described in JP-A-62-175729, JP-A-62- No. 175730,
JP-A-63-254.43, JP-A-63-21894
Examples include polymers having a photodimerizable functional group in a side chain and a carboxyl group in a side chain, which are described in Japanese Patent Application Laid-Open No. 63-218945.

However, when these photosensitive polymers are used as a photosensitive layer, they do not have sufficient adhesion to the aluminum support, so they cannot be used as a photosensitive layer for printing plates.
Used only for some purposes. If the adhesion to the support is poor, the image may peel off when rubbed with a brush during development, or the image area may easily peel off during printing, resulting in problems such as insufficient stiffness. was.

This tendency is particularly noticeable at low exposure times, resulting in lower sensitivity and other problems.

Several attempts have been made to improve such poor adhesion; for example, as described in Japanese Patent Publication No. 46-26521, an anodized film formed on an aluminum support was electrolyzed with phosphoric acid. Support material, JP-A-49
-8428, JP-A-49-12903 and JP-A-5
As stated in each publication of No. 0-138903,
Aluminum support subjected to sulfuric acid electrolysis and then etched using phosphoric acid or polyphosphoric acid; Aluminum support subjected to sulfuric acid electrolysis and then etched using alkaline solution as described in JP-A-49-93101 There is a technique using etc. Also, Special Publication No. 50-7481,
JP-A No. 62-78544 describes techniques such as applying a negative-acting diazo resin as an undercoat or adding it to a photosensitive layer.

However, with techniques that increase the adhesion with the oxide film on the support using various processing methods, while the adhesion with the photosensitive layer increases due to the anchor effect, non-image areas tend to receive ink during printing, resulting in printing stains. This has caused problems such as the tendency to cause In addition, in the technique of adding a negative-acting diazo resin to the photosensitive layer or using it as an undercoat, the diazo resin is substantially difficult to dissolve in a developer consisting of alkaline water, so the diazo resin is left in the non-image area after development. There were drawbacks such as remaining residue and causing stains during printing.

[Intelligence B to be Solved by the Invention] Therefore, the present invention provides excellent adhesion between the support and the photosensitive layer while maintaining the excellent sensitivity and performance of the photosensitive layer, and is also developable with alkaline water, allowing for printing. The purpose is to provide a photosensitive lithographic printing plate with excellent performance.

A further object of the present invention is to provide a negative-working photosensitive lithographic printing plate that can be developed with a developer for positive-working photosensitive lithographic printing plates.

[Means for Solving the Problems] The present inventor has provided a photosensitive layer containing an alkaline water-soluble or swellable photodimerizable photocrosslinkable polymer on a support having a hydrophilic surface, and optionally the support. In a photosensitive lithographic printing plate having an intermediate layer between the body and the photosensitive layer, the above object can be solved by incorporating a diazo resin having a specific functional group into the photosensitive layer and/or the intermediate layer. This is the heading that led to the present invention.

That is, the present invention provides a photosensitive layer having an alkaline water-soluble or swellable photodimerizable photocrosslinkable polymer on a support having a hydrophilic surface, and optionally a photosensitive layer between the support and the photosensitive layer. In the photosensitive lithographic printing plate having an intermediate layer, the photosensitive layer and/or the intermediate layer may contain a diazo resin having at least one phosphorus oxygen acid group. It is a photosensitive lithographic printing plate characterized by:

The present invention will be explained in detail below.

Examples of the photocrosslinkable polymer used in the present invention include polymers having a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, a chalcone group, or the like in a side chain or main chain.

As a polymer having a maleimide group in the side chain,
No. 2-988 (corresponding U.S. Pat. No. 4,079,041)
Publications, German Patent No. 2,626,769, European Patent No. 21,019, European Patent 3.5
No. 52 specification and Die Angehandte Macromolecule Clarei Chemie (Die Angehandte M
115
(1983), pages 163 to 181, of the following form (A): (wherein R and R1 each independently represent an alkyl group having up to 4 carbon atoms, or (R1 may be taken together to form a 5- or 6-membered carbon ring.) A polymer having a maleimide group in the side chain represented by
JP 49-128991, JP 49-128992, JP 49-128993, JP 50-5376, JP 5
No. 0-5377, No. 505379, No. 50-5378
No. 50-5380, No. 53-5298, No. 53
-5299, 53-5300, 5 (1-501)
No. 07, No. 51-47940, No. 52-13907, No. 50-45076, No. 52-121700, No. 50-10884, No. 50-45087,
German Patent No. 2,349,948, German Patent No. 2,616,2
The following format (B) (
In the formula, R2 represents an aromatic group, and R3 represents a hydrogen atom, a halogen atom, an alkyl group or a cyano group. ) Polymers having a maleimide group in a side chain, etc., can be mentioned. The average molecular weight of these polymers is 1000 or more, preferably 30,000 to 40,000. Furthermore, these polymers have an average of two or more maleimide groups per molecule in their side chains.

Polymers having these maleimide groups in their side chains can be made soluble or swellable in alkaline water by including acid groups in the polymer.

Specific examples of acid groups include carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, alkali metal salts and ammonium salts thereof, and those with a pKa dissociated from alkaline water of 6 to 1.
2 acid group, specifically, SO□NHCO--CONH
A monomer having a CO--SO□NllCOO- group,
A monomer having a maleimide group, for example, 10/90
~50150, preferably 20/80~40/60 (
The photocrosslinkable polymer of the present invention can be easily obtained by copolymerizing at a ratio of (molar ratio).

The acid value of maleimide polymer containing acid groups is 30 to 300.
The range is preferably 50 to 250, more preferably 50 to 250. Preferable examples of the monomer having a copolymerizable acid group include vinyl monomers having a carboxyl group such as alluric acid and methacrylic acid, maleic anhydride, and itaconic anhydride.

Among polymers with these acid values, Die
Angeimandte Makromolekula
re Chemie) 128 (1984), 71-9
Copolymers of N-[2-methacryloyloxylaethyl>2,3-dimethylmaleimide and methacrylic acid or acrylic acid, as described on page 1, are useful. Furthermore, by copolymerizing a vinyl monomer as a third component during the synthesis of this copolymer, a multicomponent copolymer suitable for the purpose can be easily synthesized. For example, flexibility can be imparted to the copolymer by using, as the third component vinyl monomer, an alkyl methacrylate or alkyl acrylate whose homopolymer has a glass transition point below room temperature.

Among other photocrosslinkable polymers used in the present invention having a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, a chalcone group, etc. in the side chain or main chain, examples of photosensitive main chains include: There are photosensitive polyesters described in U.S. Pat. No. 3,030,208, U.S. Pat. The above polyesters are prepared by condensing a suitable polycarboxylic acid, or a lower alkyl ester of a suitable polycarboxylic acid, or a chloride with a suitable polyhydric alcohol in the presence of an esterification catalyst.

Examples of these photocrosslinkable polymers made solubilized in alkaline water include the following.

That is, as described in JP-A-60-191244, the main chain has a photodimerizable unsaturated double bond adjacent to the aromatic nucleus, the side chain has a carboxyl group, and the terminal has a hydroxyl group. A chain extender having two or more functional groups in the molecule that can react with hydroxyl groups in the polyester prepolymer,
For example, photosensitive polymers obtained by reacting diisocyanate compounds, diphenyl terephthalate-1, diphenyl carbonate, terephthaloyl bis(N-caprolactam), etc., and photo-dimerizable molecules adjacent to the aromatic nucleus in the main chain. A polyester prepolymer or a polyurethane prepolymer having a saturated double bond and a hydroxyl group at the end is reacted with vilomelin l-acid dianhydride or cyclopenkune tetracarboxylic dianhydride as a chain extender to form a side chain. Examples include photosensitive polymers into which carboxyl groups have been introduced.

Furthermore, photosensitive polymers having an acid value of 20 to 200 and soluble or swellable in alkaline water, which have a photodimerizable functional group in the side chain and a carboxyl group in the side chain, can be mentioned. These photosensitive polymers are disclosed in Japanese Patent Application Laid-Open No. 62-175729.
No., JP-A-62-175730, JP-A-63-254
No. 43, JP-A-63-218944, JP-A-63-2
It is described in each publication of No. 18945.

The photocrosslinkable polymer used in the present invention preferably has a molecular weight of 1,000 or more, preferably 10,000 to 500,000, particularly preferably 20,000 to 300,000.

The amount of the photocrosslinkable polymer added to the photosensitive layer is 10 to
99% by weight, preferably 50-99% by weight.

The diazo resin used in the present invention has at least one phosphorus oxygen acid group.

The oxygen acid group of phosphorus in the present invention has the following formats (1) to
(Vl) is a group represented by any of the following.

=P~OR' (V) P-OR' (Vl) Indicates an alkyl group or an alkyl group.

Preferably, R5 represents a hydrogen atom, and R6 is a hydrogen atom or has 12 carbon atoms.
The following alkyl groups are shown. Particularly preferable phosphorus oxygen acid groups include groups represented by (1) or (III). Note that the phosphorus oxygen acid group may form an inner salt in the diazo resin.

As a method for introducing a phosphorus oxygen acid group into the diazo resin used in the present invention, any method possible in terms of organic synthesis can be used, but the following methods can be mentioned as main methods, for example.

(i) Condensation reaction of an aromatic diazonium compound having a phosphorus oxygen acid group with an aldehyde or ketone or an active carbonyl compound thereof.

(11) Condensation reaction between an aromatic diazonium compound and an aldehyde or ketone having a phosphorus oxygen acid group or an active carbonyl compound thereof.

(ji) A cocondensation reaction between an aromatic diazonium compound, an aromatic compound having a phosphorus oxygen acid group, and an aldehyde or ketone or an equivalent individual of an active carbonyl compound thereof.

The methods (i) to (iii) above will be described in detail below.

The method (a) is based on a condensation reaction between a diazonium compound having a phosphorus oxygen acid group and an equivalent individual of an aldehyde or ketone or an active carbonyl compound thereof,
As a specific example of a diazonium compound having a phosphorus oxygen acid group, the following format (■), (■) or (
Examples include compounds represented by IX).

In the formula, Ra represents a valine oxygen acid group or a group having at least one phosphorus oxygen acid group, and Ra is a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a hydroxy group, or a carboxy ester. Indicates a group, Rq
represents a hydrogen atom, an alkyl group, or an alkoxy group, and R1
0 represents a hydrogen atom, an alkyl group, or an alkoxy group;
- represents an anion, and Y is -NH--〇--8-
, and n represents 1 or 2. Note that X- may be an anion of a phosphorus oxyacid bonded to a diazonium compound.

More preferably, R7 has a phosphorus oxygen acid group, a C1-C16 alkyl group having a phosphorus oxygen acid group, a C1-16 alkoxy group having a phosphorus oxygen acid group, or a phosphorus oxygen acid group. represents an alkylamide group having 1 to 16 carbon atoms or an alkyl ester group having 1 to 16 carbon atoms having a phosphorus oxygen acid group, R8 represents a hydrogen atom, R9 represents a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, RIO represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Y is -N
H- is shown, and n is 1.

Specifically, the compounds represented by the above formula (■), (■) or (IX) include, for example, 4-diazo-4'-
Dihydroxyphosphinyldiphenylamine, 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine, 4-diazo-2-dihydroxyphosphinyldiphenylamine, 4-diazo-2-dihydroxyphosphinyloxydiphenylamine, 4 -thiaso3-dihydroxyphosphinyldiphenylamine, 4-diazo3
-dihydroxyphosphinyloxydiphenylamine,
4-diazo-2'-dihydroxyphosphinyldiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxydiphunylamine, 4-diazo-2'-dihydroxyphosphinyl-4'-methoxydiphenylamine,
4-Diazo-2'-dihydroxyphosphinyloxy-
4'-methoxydiphenylamine, 4-diazo-3-dihydroxyphosphinyl-4'-methoxydiphenylamine, 4-diazo-3-dihydroxyphosphinyloxy-4'-methoxydiphenylamine, 4-diazo-2
-dihydroxyphosphinyl-4'-ethoxydiphenylamine, 4-diazo-2-dihydroxyphosphinyloxy-4'ethoxydiphenylamine, 4-diazo-
2'dihydroxyphosphinyl-4'-ethoxydiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxy-4'-ethoxydiphenylamine, 4-
Thiaso 3-dihydroxyphosphinyl-4'-ethoxydiphenylamine, 4-diazo-3-dihydroxyphosphinyloxy4'-ethoxydiphenylamine, 4
-Diazo-2'-dihydroxyphosphinyl-4'-methyldiphenylamine, 4-diazo-2'-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-diazo-2-dihydroxyphosphinyl-4'-
Methyldiphenylamine, 4-dian-2-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-diazo-3-dihydroxyphosphinyl-4'-
Methyldiphenylamine, 4-diazo-3-dihydroxyphosphinyloxy-4'-methyldiphenylamine, 4-diazo-2-dihydroxyphosphinyl-4'-
Ethyldiphenylamine, 4-diazo-2-dihydroxyphosphinyloxy-4'-ethyldiphenylamine, 4-diazo-2'-dihydroxyphosphinyl-4'
-ethyldiphenylamine, 4-diazo-21-dihydroxyphosphinyloxy-4'-ethyldiphenylamine, 4-diazo-3'-dihydroxyphosphinyl-4'-ethyldiphenylamine, 4-thiaso3'-
Dihydroxyphosphinyloxy-4'-ethyldiphenylamine, 4-diazo-4'-(2-dihydroxyphosphinylethyl)diphenylamine, 4-diazo-4
' -(2-dihydroxyphosphinyloxyethyl)
Diphenylamine, 4-diazo-4'-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-4'
-dihydroxyphosphinyloxymethyldiphenylamine, 4diazo-4' -(2-dihydroxyphosphonyloxyethoxy)diphenylamine, 4-diazo4'
-(2-dihydroxyphosphonyloxyethoxy)diphenylamine, 4-diazo-4'(3-dihydroxyphosphonylpropoxy)diphenylamine, 4-diazo-4'-(3-dihi)'roxyphosphinyloxybroboxy)diphenylamine , 4-diazo-4'-(
3-dihydroxyphosphinylpropyl)diphenylamine, 4-diazo-4'-(3-dihydroxyphosphinyloxypropyl)diphenylamine, 4-diazo-
2,5-bis-(dihydroxyphosphinylmethyl)diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinyloxymethyl)diphenylamine,
4-Diazo-2,5-bis-(2-dihydroxyphosphinylethyl)diphenylamine, 4-thiaso25-
Bis-(2-dihydroxyphosphinyloxyethyl)
diphenylamine, 4-diazo-25-bis-(3-dihydroxyphosphinylpropyl)diphenylamine,
4-Diazo-2,5-bis-(3-dihydroxyphosphinyloxypropyl)diphenylamine, 4-diazo-2-(3-dihydroxyphosphinylpropyl)diphenylamine, 4-diazo-2-(3-dihydroxyphosphinylpropyl)diphenylamine finyloxypropyl)diphenylamine, 4-diazo-3-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-3-dihydroxyphosphinylmethyldiphenylamine, 4-diazo-3-(2-
dihydroxyphosphinylethyl) diphenylamine,
4-Diazo-3-(2-dihydroxyphosphinyloxyethyl)diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinylmethoxy)diphenylamine, 4-diazo-2,5-bis-(dihydroxyphosphinyl) finyloxymethoxy)diphenylamine, 4-diazo-2,5-bis-(3-dihydroxyphosphinylpropoxy)diphenylamine, 4-diazo-2,5-
Bis-(3-dihydroxyphosphinyloxypropoxy)diphenylamine, 4-diazo-4'-dihydroxyphosphinyl diphenyl ether, 4-diazo-4'
-dihydroxyphosphinyloxydiphenyl ether, 4-diazo-4'-dihydroxyphosphinyldiphenyl sulfide, 4-diazo-4'-dihydroxyphosphinyloxydiphenyl sulfide, 4-diazo-2
-dihydroxyphosphinyl diphenyl ether, 4-
Diazo-2-dihydroxyphosphinyloxydiphenyl ether, 4-diazo-3-dihydroxyphosphinyldiphenyl ether, 4-diazo-3-dihydroxyoxydiphenyl ether, 4-diazo-3-dihydroxyphosphinyldiphenyl sulfide, 4-diazo-
3-dihydroxyphosphinyloxydiphenyl sulfide, 4-diazo-4'-dihydroxyphosphinylmethyldiphenyl ether, 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenyl ether, 4
-Diazo-4'-(2-dihydroxyphosphinylethyl)diphenyl ether, 4-diazo-4'-(2-dihydroxyphosphinyloxyethyl)diphenyl ether, 4-diazo-4'-dihydroxyphosphinylmethyldiphenyl sulfide , 4-diazo-4'-dihydroxyphosphinyloxymethyldiphenyl sulfide, 4-diazo-4'(2-dihydroxyphosphinylethyl) diphenyl sulfide, 4-diazo-4'-(
2-dihydroxyphosphinyloxyethyl) diphenyl sulfide, 4-diazo-4'-dihydroxyphosphinylmethoxydiphenyl ether, 4-diazo-4'
-dihydroxyphosphinyloxymethoxydiphenyl ether, 4-diazo-4' (2-dihydroxyphosphinyl ethoxy) diphenyl sulfide, 4-thiazo 4' -(2-dihydroxyphosphinyloxyethoxy) diphenyl sulfide, 4- diazo-2-(2-dihydroxyphosphinylethyl)diphenyl ether,
4-Diazo-2-(2-dihydroxyphosphinyloxyethyl)diphenyl sulfide, 4-diazo-3-dihydroxyphosphinylmethyldiphenyl ether, 4
-Diazo-3-dihydroxyphosphinyloxymethyldiphenyl sulfide, 4-diazo-4'-dihydroxyphosphinooxydiphenylamine, 4-diazo-4
'-dihydroxyphosphinodiphenylamine, 4-diazo4'-hydroxyphosphinodiphenylamine, 4
-Diazo-4'-hydroxyphosphinyldiphenylamine, 4-diazo-3-dihydroxyphosphinooxydiphenylamine, 4-diazo-3-dihydroxyphosphinodiphenylamine, 4-thiaso-2-dihydroxyphosphinooxydiphenylamine, 4-diazo- 2
-dihydroxyphosphinodiphenylamine, 4-diazo-2'-hydroxyphosphinodiphenylamine, 4
-Diazo-2'-hydroxyphosphinyldiphenylamine, 4-diazo-4'-dihydroxyphosphinooxymethyldiphenylamine, 4-diazo-4'-dihydroxyphosphinomethyldiphenylamine, 4-diazo-4'-dihydroxyphosphinooxy Methoxydiphenylamine, 4-diazo-4'-dihydroxydiphosphinomethoxydiphenylamine, 4-diazo-4'-(
2-dihydroxyphosphinooxyethoxy)diphenylamine, 4-diazo-4'-(2-dihydroxyphosphinoethoxy)diphenylamine, 4-diazo-3
-dihydroxyphosphinooxymethyldiphenylamine, 4-diazo-2-dihydroxyphosphinomethoxydiphenylamine, 4-diazo-2'-(2-hydroxyphosphinoethyl)diphenylamine, 4-diazo-3'-(2-hydroxyphosphinoethyl) (ethoxy)diphenylamine and the like.

Examples of the method for synthesizing the diazo resin in method (i) used in the present invention include, for example, using a diazonium compound having a phosphorus oxygen acid group and formaldehyde, acetaldehyde, propionaldehyde, phthylaldehyde, 1SO-butyraldehyde, benzaldehyde, acetone. , methyl ethyl-ketone or active carbonyl compounds having a phosphorus oxygen acid group such as acetophenone or their acetanoyl, each preferably in a molar ratio of 1:
1. OO~1:0.2, more preferably 1:10
A method of condensation in an acidic medium at a ratio of ~1:0.5 may be mentioned. When carrying out the condensation reaction, in order to adjust the phosphorus oxygen acid group content of the diazo resin to be produced, a diazonium compound that does not have a phosphorus oxygen acid group and/or a phosphorus oxygen acid group, a diazonium group is used. Aromatic compounds that do not have either can be used in combination. Examples of the diazonium compound that does not have a phosphorus oxygen acid group include aromatic diazonium compounds that preferably have a 4-diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl sulfide skeleton.

More specifically, for example, 4-diazodiphenylamine, 4
'-Hydroxy-4-diazodiphenylamine, 4'-
Methoxy-4-diazodiphenylamine, 4'-ethoxy-4-diazodiphenylamine, 4'-n-propoxy-4-diazodiphenylamine, 4'-1-propoxy-4-diazodiphenylamine, 4'-methyl-4-
Cyandiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-proyl-4-diazodiphenylamine, 4'-1-propyl-4-diazodiphenylamine, 4'-n-ph'thyl-4-diazodiphenylamine , 4'-hydroxymethyl-4-diazodiphenylamine, 4'-β-hydroxyethyl-4-diazodiphenylamine, 4'-γ-hydroxypropyl-4
-cyano'diphenylamine, 4'-methoxymethyl-4-diazodiphenylamine, 4'-ethoxymethyl-4-diazodiphenylamine, 4'-β-methoxyethyl-4-diazodiphenylamine, 4'-β-ethoxyethyl- 4-Diazodiphenylamine, 4'-carbomethoxy-4-diazodiphenylamine, 4'-carboethoxy-4-diazodiphenylamine, 4'-carboethoxy-4-diazodiphenylamine, 4-diazo-3-
Methoxydiphenylamine, 4-diazo-2-methoxydiphenylamine, 2'-methoxy-4-diazodiphenylamine, 3-methyl-4-diazodiphenylamine, 3-ethyl-4-diazodiphenylamine, 3'-methyl-4-diazodiphenylamine, 3-ethoxy-4-
Diazodiphenylamine, 3-hexyloxy-4-diazodiphenylamine, 3β-hydroxyethoxy-4-
Diazodiphenylamine, 2-methoxy-5'-methyl-4-diazodiphenylamine, 4-diazo-3-methoxy-6-methyldiphenylamine, 3,3'-dimethyl-4-diazodiphenylamine, 3'-n-butoxy-4- Diazodiphenylamine, 34'-dimethoxy-
4-diazodiphenylamine, 2'-carboxy-4-
Diazodiphenylamine, 4-diazodiphenyl ether, 4'-methoxy-4-diazodiphenyl ether,
4'-Methyl-4-diazodiphenyl ether, 3.4
-dimethoxy-4-diazodiphenyl ether, 4'carboxy-4-diazodiphenyl ether, 33'-dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl 4-diazodiphenyl sulfide, 4'-methyl-25- Dimethoxy-4-
Examples include diazodiphenyl sulfide.

Examples of the aromatic compound having neither a phosphorus oxygen acid group nor a diazonium group include the compounds described in Japanese Patent Publication No. 49-48001.

Further, the active carbonyl compounds or their acetals may be used in combination of two or more, and instead of the active carbonyl compounds or their acetals,
Methylol derivatives such as those described in Japanese Patent Publication Nos. 49-45322 and 49-45323, or olefinically unsaturated compounds such as those described in JP-A-58-187925 may also be used. can.

Specific examples of the acidic medium used when synthesizing the diazo resin used in the present invention by method (i) include strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, or sulfuric acid.

These media contain at least 30% by weight, advantageously from 70% to
Used at a concentration of 100% by weight. Generally the balance is water, but may also consist partially or completely of organic solvents such as methanol, acetic acid, N-methylpyrrolidone, and the like. Good results are for example 85-93% phosphoric acid, 80-9
This is achieved with 8% sulfuric acid or 90% methanesulfonic acid or mixtures of these acids.

The temperature during condensation is about 0 to 70°C, preferably about 0 to 70°C.
It is 50°C.

The method (11) is based on a condensation reaction between an aromatic diazonium compound and an aldehyde having a phosphorus oxygen acid group or its equivalent, and examples of the synthesis method include, for example, 4-diazodiphenylamine skeleton, 4-diazodiphenyl ether A diazo monomer having a skeleton or a 4-diazodiphenyl sulfide skeleton and an aldehyde having a phosphorus oxygen acid group or an acetal thereof in a molar ratio of preferably 1:1, respectively.
0 to 1:0.05, more preferably 1:2 to 1:0,
A method may be mentioned in which condensation is carried out in an acidic medium at a ratio of 2:2. When carrying out the condensation reaction, in order to adjust the phosphorus oxygen acid group content and molecular weight of the diazo resin produced,
Active carbonyl compounds that do not have a phosphorus oxygen acid group, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 1so-butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone or acetophenone, or their acetals are used together as a condensing agent, Aromatic compounds that do not have a diazonium group can be co-condensed. Formaldehyde is most preferable as the active carbonyl compound having no phosphorus oxygen acid group, and the molar ratio thereof to the diazo monomer is preferably 0 to 5, more preferably 0. 1-1. In addition, when using together an aldehyde having a phosphorus oxygen acid group and an active carbonyl compound not having a phosphorus oxygen acid group, first, a diazo monomer and an aldehyde having a phosphorus oxygen acid group are mixed in an acidic medium. Condensation followed by post-condensation with more reactive active carbonyl compounds or their acetals which do not have a phosphorus oxygen acid group, such as formaldehyde, yields higher molecular weight diazo resins. be able to.

Further, examples of the aromatic compound having no diazonium group include the compounds described in Japanese Patent Publication No. 49-48001.

In addition, instead of the active carbonyl compound having no phosphorus oxygen acid group or its acecur, methylol derivatives such as those described in Japanese Patent Publications No. 49-45322 and No. 49-45323, Alternatively, olefinically unsaturated compounds such as those described in JP-A-58-187925 may also be used.

The diazo monomer used in the present invention is a compound having an aromatic ring substituted with at least one diazonium group, and preferably an aromatic diazo compound represented by the following formula (χ).

In the formula, R11 represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a hydroxyl group, a carboxyester group, or a carboxyl group, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom. It represents a number 1 to 3 alkoxy group or hydroxyl group.

R" represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably, it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms.

R" represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably, it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms.

X- represents an anion, preferably an anion of an inorganic or organic acid having a pKa of 4 or less.

Specifically, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrochloric acid-zinc chloride complex, hydrobromic acid; sulfuric acid; nitric acid; phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid, Inorganic iso- and polyacids, such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters, arsonic acid, phosphinic acid, fluorocarboxylic acids such as trifluoroacetic acid, amidosulfonic acid, selenic acid , hydrofluoroboric acid, hexafluorophosphoric acid, perchloric acid, as well as aliphatic and aromatic sulfonic acids.

Y represents -NH--0-1 or -S-, preferably -
Indicates NH-.

Specific examples of the aromatic diazo compound represented by the above-format (X) include 4-diazodiphenylamine, 4'
-Hydroxy-4-diazodiphenylamine, 4'-methoxy-4-diazodiphenylamine, 4'-ethoxyl 4-diazodiphenylamine, 4'-n-propoxy-4-diazodiphenylamine, 4'-1-propoxy-4- Diazodiphenylamine, 4'-methyl-4-diazodiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-propyl-4-diazodiphenylamine, 4'-i-propyl-4-diazodiphenylamine, 4'- n-Butyl-4-diazodiphenylamine, 4'-hydroxymethyl-4-diazodiphenylamine, 4'β-hydroxyethyl-4-diazodiphenylamine, 4'-T-hydroxypropyl-4-
Diazodiphenylamine, 4'-methoxymethyl-4-
Diazodiphenylamine, 4'-ethoxymethyl-4-
Diazodiphenylamine, 4'-β-methoxyethyl-
4-diazodiphenylamine, 4'β-ethoxyethyl-4-diazodiphenylamine, 4'-carbomethoxy-4-diazodiphenylamine, 4'-carboethoxy-4-diazodiphenylamine, 4'-carboxy-4
-diazodiphenylamine, 4-diazo-3-methoxydiphenylamine, 4-diazo-2-methoxydiphenylamine, 2'-methoxy-4-diazodiphenylamine, 3-methyl-4-diazodiphenylamine, 3-ethyl-4-diazodiphenylamine, 3'-methyl-4
-Diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3-hexyloxy-4-diazodiphenylamine, 3-β-hydroxyethoxy-4-diazodiphenylamine, 2-methoxy-5'-methyl 4-
Diazodiphenylamine, 4-thiaso-3methoxy-6
-Methyldiphenylamine, 33'-dimethyl-4-diazodiphenylamine, 3'-〇-butoxy-4-diazodiphenylamine, 3,4'-dimethoxy-4-diazodiphenylamine, 2'-dimethyl-4-diazodiphenylamine, 4- Diazodiphenyl ether, 4'
-methoxy-4-diazodiphenyl ether, 4'-methyl-4-diazodiphenyl ether, 3°4'-dimethoxy-4-diazodiphenyl ether, 4'-carboxy-4-diazodiphenyl ether, 33'-dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl-4-diazodiphenyl sulfide, 4'-methyl-2,5-dimethoxy-4-
Examples include diazodiphenyl sulfide.

Among these, particularly preferred aromatic diazo compounds include:
Examples include 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-4'-ethoxydiphenylamine, and 4-diazo-3-methoxydiphenylamine.

The aldehyde or acetal thereof having a phosphorus oxygen acid group preferably includes an aldehyde having a structure represented by the following formula (XI) or an acetal thereof.

R4(XI) HO In the formula, Rl4 is a single bond or a divalent organic group having 1 to 14 carbon atoms that may have a substituent (for example, an aliphatic hydrocarbon group,
aromatic hydrocarbon group or heterocyclic group). R.I.
Examples of groups that can be substituted for 4 include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms,
It includes a hydroxy group, a substituted or unsubstituted amino group, a carboxy ester group, an amide group, a carboxyl group, and the like. Further, R14 may contain an ether group, amide group, ester group, urethane group, urea group, carbonate group, amino group, etc. as a linking group in the chain. Z represents a phosphorus oxygen acid group represented by the above formulas (1) to (VI).

Specific examples of the aldehyde having a phosphorus oxygen acid group or its acecure represented by the above-format (XI) include, for example, 2-oxo-1-ethyl phosphoric acid, 2-oxo-1-ethyl phosphoric acid,
Ethyl phosphorous acid, 2-oxo-1-ethylphosphonic acid,
2-oxo-1-ethylphosphonic acid, 2-oxo-1
-Ethylphosphinic acid, 2-oxo-1-ethylphosphinic acid, 3-oxo-1-propyl phosphoric acid, 3-oxo-1-propyl phosphorous acid, 3-oxo-1-propylphosphonic acid, 3-oxo -1-propylphosphonic acid,
3-oxo-1-propylphosphinic acid, 3-oxo-
1-Propylphosphinic acid, 4-oxo-1-butylphosphonic acid, 4-oxo-1-butylphosphonic acid, 4-oxo-1-butylphosphonic acid, 4-oxo-1-butylphosphonic acid, 4- Oxo-1-butylphosphinic acid, 4-
Oxo-1-butylphosphinic acid, 5-oxo-1-pentyl phosphorous acid, 5-oxo-1-pentyl phosphorous acid, 5
-oxo-1-pentylphosphonic acid, 5-oxo-1-
Pentylphosphonic acid, 5-oxo-1-pentylphosphinic acid, 5-oxo-1-pentylphosphinic acid, 5
-oxo-1-pentylphosphinic acid, 6-oxo-
1-hexyl phosphoric acid, 6-oxo-1-hexyl phosphorous acid, 6-oxo-1-hexylphosphonic acid, 6-oxo-
1-hexylphosphonic acid, 6-oxo-1-hexylphosphinic acid, 6-oxo-1-hexylphosphinic acid, 2-formylphenylphosphonic acid, 2-formylphenylphosphorous acid, 2-formylphenylphosphonic acid, 2-formylphenyl phosphonic acid, 2-formylphenyl phosphinic acid, 2-formylphenyl phosphinic acid, 3
-Formylphenylphosphoric acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphonic acid, 3-formylphenylphosphinic acid, 3-formylphenylphosphinic acid, 4-formylphenylphosphonic acid , 4-formylphenyl phosphorous acid,
4-formylphenylphosphonic acid, 4-formylphenylphosphonic acid, 4-formylphenylphosphinic acid,
4-Formylphenylphosphinic acid, 2,2-dimethyl-3-oxo-1-propyl phosphorous acid, 2,2-dimethyl-3-oxo-1-propyl phosphorous acid, 2゜2-dimethyl-3-oxo -1-propylphosphonic acid, 2.2-
Dimethyl-3-oxo-1-propylphosphonic acid, 2
．． 2-Dimethyl-3-oxo-1-propylphosphinic acid, 2,2-dimethyl-3-oxo-1-propylphosphinic acid, 2,3-dimethyl-4-oxo-1-butyl phosphoric acid, 2,3- Dimethyl-4-oxo-1-butylphosphonic acid, 2-methyl-6-oxo-1-hexylphosphonic acid, 2-methyl-6-oxo-1-hexylphosphonic acid, 2-formyl-4-methoxyphenylphosphonic acid , 2-
Formyl-4-methoxyphenylphosphonic acid, 4-amino-3-formylphenylphosphonic acid, 4-amino-3-formylphenylphosphonic acid, 4-(2-oxoethyl)
Phenylphosphonic acid, 4-(2-oxoethyl)phenylphosphonic acid, 3-(3-oxopropyl)phenylphosphonic acid, 3-(3-oxopropyl)phenylphosphonic acid,
2,4-bis(dihydroxyphosphinyloxy)benzaldehyde, 2,4-bis(dihydroxyphosphinyl)benzaldehyde, 2,6-bis(dihydroxyphosphinyloxy)benzaldehyde, 2,6-bis(dihydroxyphosphinyloxy)benzaldehyde finyl)benzaldehyde, 2-
Formyl-1-naphthylphosphonic acid, 2-formyl-1-naphthylphosphonic acid, 4-formyl-1-naphthylphosphonic acid, 4-formyl-1-naphthylphosphonic acid, 5-formyl-2-naphthylphosphonic acid, 5-formyl-2 -naphthylphosphonic acid, 1,4-bis(dihydroxyphosphinyloxy)-7-naphthylaldehyde, 1,4-bis(dihydroxyphosphinyl)-7-naphthylaldehyde,
5-amino-7-formyl-2-naphthyl phosphate, 5-
Amino-7-formyl-2-naphthylphosphonic acid, 5-formyl-2-furylphosphonic acid, 5-formyl-2-furylphosphonic acid, 3-formyl-2-furylphosphonic acid, 3-formyl-2-furylphosphonic acid, 5 -Formyl-3-furylphosphonic acid, 5-formyl-3-furylphosphonic acid, 1-
Oxo-1-methylphosphonic acid, 1-oxo-1-methylphosphonic acid, 3-(4-formylphenoxy)-1-propylphosphonic acid, 3-(4-formylphenoxy)-1-propylphosphonic acid, 4-(4-formylphenoxy)-1-propylphosphonic acid, -Formylphenoxy)-
1-Butyl phosphate, 4-(4-formylphenoxy)-
1-Butylphosphonic acid, 3-(3-formylphenoxy)-1-butylphosphonic acid, 3-(3-formylphenoxy)-1-butylphosphonic acid, 4-formyl-2-(2-
dihydroxyphosphinyloxyethyl)benzoic acid, 4
-Formyl-3-(2-dihydroxyphosphinylethyl)benzoic acid, 4-formyl-3-(3-dihydroxyphosphinyloxyprobyl)benzoic acid, 4-formyl-2-(3-dihydroxyphosphinyl) Examples include propyl)benzoic acid, 4-formyl-4-(4-dihydroxyphosphinyloxybutyl)benzoic acid, and acetals thereof.

Specific examples of the acidic medium used when synthesizing the diazo resin used in the present invention by method (11) include, for example,
Strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid or sulfuric acid may be mentioned.

These media contain at least 30% by weight, preferably 70-1
Used at a concentration of 0.00% by weight. Generally the remainder is water, but partially or completely organic solvents, such as methanol,
It may also consist of acetic acid, N-methylpyrrolidone, etc.

Good results are e.g. 85-93%-phosphoric acid, 80-98%
% sulfuric acid or 90% methanesulfonic acid or mixtures of these acids.

The temperature during condensation is about 0 to 70°C, preferably about 0 to 70°C.
It is 50°C.

The method (ij) is based on a co-condensation reaction between an aromatic diazonium compound, an aromatic compound having a phosphorus oxygen acid group, and an aldehyde or ketone, or an equivalent individual of an active carbonyl compound thereof.

Preferable examples of the aromatic ring include aryl groups, such as phenyl and naphthyl groups.

Further, the oxygen acid group of phosphorus may be bonded directly to the aromatic ring or may be bonded via a linking group.

In the present invention, the number of phosphorus oxygen acid groups bonded to one aromatic ring is preferably 1 to 3, and examples of the linking group include alkylene groups having 1 to 4 carbon atoms.

In order for the above-mentioned aromatic compound to be condensed with aldehydes or ketones, it is necessary to have at least two unsubstituted sites on the aromatic ring of one or more aryl groups.

Specific examples of aromatic compounds having a phosphorus oxygen acid group in the molecule used in the present invention include phenylphosphoric acid, phenylphosphorous acid, phenylphosphonic acid, phenylphosphonic acid, phenylphosphinic acid, and phenylphosphinic acid. ,
4-hydroxyphenyl phosphoric acid, 4-hydroxyphenyl phosphorous acid, 4-hydroxyphenylphosphonic acid, 4-
Hydroxyphenylphosphonic acid, 4-hydroxyphenylphosphinic acid, 4-hydroxyphenylphosphinic acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphonic acid, 4-methylphenylphosphonic acid , 4-methylphenylphosphinic acid, 4-methylphenylphosphinic acid, 4-t-butylphenyl phosphoric acid, 4-t-butylphenyl phosphorous acid,
4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphonic acid, 4-t-butylphenylphosphinic acid, 4-t-butylphenylphosphinic acid, 4-aminophenylphosphoric acid, 4-aminophenylphosphonic acid Phosphoric acid, 4
-aminophenylphosponic acid, 4-aminophenylphosphonic acid, 4-aminophenylphosphinic acid, 4-aminophenylphosphinic acid, 4-methoxyphenylphosphoric acid, 4-methoxyphenylphosphorous acid, 4-methoxyphenylvos fonic acid, 4-methoxyphenylbosuvonic acid,
4-methoxyphenylphosphinic acid, 4-methoxyphenylphosphinic acid, 4-ethoxyphenylphosphoric acid, 4
-Ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylphosphonic acid, 4-ethoxyphenylbosphinic acid, 4-ethoxyphenylbosphinic acid, 4-ethylphenyl phosphoric acid, 4-ethylphenylphinous acid Phosphoric acid, 4-ethylphenylphosphonic acid, 4-
Ethylphenylphosphonic acid, 4-ethylphenylphosphinic acid, 4-ethylphenylbosphinic acid, 2-aminophenylphosphonic acid, 2-aminophenylphosphorous acid, 2
-aminophenylbosonic acid, 2-aminophenylphosphonic acid, 2-aminophenylphosphinic acid, 2-aminophenylphosphinic acid, 2,4-dimethylphenylphosphoric acid, 2゜4-dimethylphenylphosphorous acid, 2 ,4-
Dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphonic acid, 2,4-dimethylphenylphosphinic acid, 2,4-dimethylphenylphosphinic acid, 2,6
-Diamituphenyl phosphoric acid, 2,6-dimethylphenyl phosphoric acid, 2,6-diamitphenylphosphonic acid, 2.6
-dimethylphenylphosphonic acid, 2,6-diamitsphenylphosphine L 2,6-diamitsphenylphosphinic acid, 2,5-dihydroxyphenylphosphonic acid, 2゜5
-dihydroxyphenylphosphonic acid, 2.5-dihydroxyphenylphosphonic acid, 2.5-dihydroxyphenylphosphonic acid, 2.5-dihydroxyphenylphosphonic acid, 2.5-dihydroxyphenylphosphinic acid, 2
-amino-4-hydroxyphenyl phosphoric acid, 2-amino-4-hydroxyphenyl phosphorous acid, 2-amino-4-
Hydroxyphenylphosphonic acid, 2-amino-4-hydroxyphenylphosphonic acid, 2-amino-4-hydroxyphenylphosphinic acid, 2-amino-4-hydroxyphenylphosphinic acid, mesityl phosphoric acid, mesityl phosphorous acid, mesityl phosphonic acid tylphosphonic acid, mesitylphosphonic acid,
Mesitylphosphinic acid, mesitylphosphinic acid, 2.
4-dihydroxy-6-methylphenyl phosphoric acid, 2,4
-dihydroxy-6-methylphenylphosphorous acid, 2゜4
-dihydroxy-6-methylphenylbosphonic acid, 2.
4-dihydroxy-6-methylphenylphosphonic acid,
2.4-dihydroxy-6-methylphenylphosphinic acid, 2,4-dihydroxy-6-methylphenylphosphinic acid, benzyl phosphoric acid, benzyl phosphorous acid, benzyl phosphonic acid, benzyl phosphonic acid, benzyl phosphinic acid, benzyl Phosphinic acid, 4-methoxybenzyl phosphorous acid, 4-methoxybenzyl phosphorous acid, 4-methoxybenzyl phosphonic acid, 4-methoxyhensyl phosphonite, 4-methoxybenzylbosphinic acid, 4-methoxybenzyl phosphine acid, 4-hydroxybenzyl phosphoric acid, 4-hydroxybenzyl phosphorous acid, 4-hydroxybenzyl phosphonic acid, 4-hydroxybenzyl phosphonic acid, 4-hydroxybenzyl phosphinic acid, 4-hydroxybenzyl phosphinic acid, 4-( 2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-(2-hydroxyethyl)phenylphosphonic acid, 4-( 2-Hydroxyethyl)phenylphosphinic acid, 4-(2-hydroxyethyl)phenylphosphinic acid, 2-phenylethylphosphoric acid, 2-phenylethylphosphorous acid, 2-phenylethylphosphonic acid, 2-phenylethylphosphonite acid, 2-phenylethylphosphinic acid, 2-phenylethylphosphinic acid, 1-naphthylphosphoric acid, 1-naphthylphosphorous acid,
1-naphthylphosphonic acid, 1-naphthylphosphonic acid,
1-naphthylphosphinic acid, 1-naphthylphosphinic acid, 2-naphthylphosphoric acid, 2-naphthylphosphorous acid, 2-
naphthylphosphonic acid, 2-naphthylphosphonic acid, 2-
Naphthylphosphinic acid, 2-naphthylphosphinic acid,
2-amino-1-naphthylphosphonic acid, 2-amino-1-naphthylphosphorous acid, 2-amino-1-naphthylphosphonic acid, 2-amino-1-naphthylphosphonic acid, 2-amino-1-naphthylphosphinic acid , 2-amino-1-naphthylphosphinic acid, 4-amino-1-naphthyl phosphoric acid, 4
-Amino-1-naphthylphosphonic acid, 4-amino-1-naphthylphosphonic acid, 4-amino-1-naphthylphosphonic acid, 4-amino-1-naphthylphosphinic acid, 4-amino-1-naphthylphosphine acid, 5-amino-2-
naphthyl phosphoric acid, 5-amino-2-naphthyl phosphorous acid,
5-amino-2-naphthylphosphonic acid, 5-amino-2
-Naphthylphosphonic acid, 5-amino-2-naphthylphosphinic acid, 5-amino-2-naphthylphosphinic acid, 4-amino 3-hydroxy-1-naphthylphosphonic acid, 4
-amino-3-hydroxy-1-naphthylphosphonic acid,
4-amino-5-hydroxy-1-naphthyl phosphate, 4
-amino-5-hydroxy-1-naphthylphosphonic acid,
7-amino-3-hydroxy-2-naphthyl phosphate, 7
-amino-3-hydroxy-2-naphthylphosphonic acid,
5-dimethylamino-2-naphthylphosphonic acid, 5-dimethylamino-2-naphthylphosphonic acid, 5-hydroxy-
1-Naphthylphosphonic acid, 5-hydroxy-1-naphthylphosphonic acid, 5-methoxy-2-naphthylphosphonic acid, 5-methoxy-2-naphthylphosphonic acid, 4-phenoxyphenylphosphonic acid, 4-phenoxyphenylphosphonic acid, 4-
(4-methoxyphenoxy)phenyl phosphoric acid, 4-(4
-methoxyphenoxy)phenylphosphonic acid, 4-diphenylaminophosphoric acid, 4-diphenylaminophosphorous acid,
4-diphenylaminophosphonic acid, 4-diphenylaminophosphonic acid, 4-diphenylaminophosphinic acid,
4-diphenylaminophosphinic acid, 4'-methoxy-4-diphenylaminophosphoric acid, 4'-methoxy-4-
Diphenylaminophosphorous acid, 4'methoxy-4-diphenylaminophosphonic acid, 2-phenoxyethyl phosphoric acid,
2-phenoxyethylphosphonic acid, 2-phenoxyethylphosphonic acid, 2-phenoxyethylphosphonic acid, 2-
Phenoxyethylphosphinic acid, 2-phenoxyethylphosphinic acid, benzyl (2-dihydroxyphosphinyloxy) acetate, benzyl (2-dihydroxyphosphinyl) acetate, 4-methoxybenzyl, 2
-dihydroxyphosphinyloxyacetate 4-methoxybenzyl 2-dihydroxyphosphinyl acetate, phenyl 3-dihydroxyphosphinyloxypropionate, phenyl 3-dihydroxyphosphinylpropionate, 3-dihydroxyphosphinyloxypropionic acid (3-methoxyphenyl), 4-dihydroxyphosphinylbutyric acid (3-methoxyphenyl), 4-dihydroxyphosphinyloxybutyric acid (4-hydroxyphenyl), 3-dihydroxyphosphinylpropionic acid (
4-hydroxyphenyl), 2,4.6-)limethyl-
1,3-Hensen-bisphosphoric acid, 2.4.6-toIJ
Methyl-1,3-benzene-bis-phosphonic acid, 2.5
-dihydroxy-14-benzene-bis-phosphoric acid, 2.
5-dihydroxy-1,4-benzene-bis-phosphonic acid, 2,5-dihydroxy-1゜3-benzene-bis-
Phosphoric acid, 2,5-dihydroxy-1,3-benzene-bis-phosphonic acid, l.

5-naphthalene-bis-phosphoric acid, 1,5-naphthalene-
Bis-phosphonic acid, 2,6-naphthalene-bis-phosphonic acid, 2,6-naphthalene-bis-phosphonic acid, 7-amino-1,3-naphthalene-bis-phosphoric acid, 7-amino-1
, 3-naphcrene-bisphosphonic acid, 3-methoxy-
2, Hunaphthalene-pisuphosphoric acid, 3-methoxy-2
, 7-naphthalene-bis-phosphonic acid and the like.

On the other hand, the aromatic diazo compound used in the method (ij) is a compound having an aromatic ring substituted with at least one diazonium group, and preferably has the above-mentioned -format (
Examples include aromatic diazo compounds represented by X).

In the present invention, the condensation type resin with an active carbonyl compound (hereinafter referred to as diazo cocondensation resin) containing an aromatic compound having a phosphorus oxygen acid group and an aromatic diazo compound as structural units can be prepared by a known method, for example, photophotography. graphic·
Science and Engineering (Photo,
Sci., Eng.) Volume 17, Page 33 (1973)
, U.S. Patent No. 2,063,631, U.S. Patent No. 2.679
, No. 498 and Japanese Patent Publication No. 49-48001, diazonium salts, aromatic compounds having a phosphorus oxygen acid group, and aldehydes such as formaldehyde, acetaldehyde,
Propionaldehyde, butyraldehyde, 130-butyraldehyde, benzaldehyde or ketones,
For example, it can be obtained by polycondensing active carbonyl compounds such as acetone, methyl ethyl ketone, acetophenone, or their acetals.

In addition, these aromatic compounds, aromatic diazo compounds, and active carbonyl compounds or their acetals having a phosphorus oxygen acid group in their molecules can be freely combined with each other, and two or more of each can be mixed and co-condensed. is also possible. Furthermore, co-condensation can be carried out by adding a co-condensable aromatic compound which does not have a phosphorus oxygen acid group. Here, examples of aromatic compounds that can be cocondensed include aromatic compounds described in Japanese Patent Publication No. 49-48001.

In addition, instead of the active carbonyl compound or their acetal, Japanese Patent Publication Nos. 49-45322 and 49-49-
It is also possible to use methylol derivatives as described in JP-A-45323 or olefinically unsaturated compounds as described in JP-A-58-187925.

Note that by changing the molar ratio of these cocondensation components, the content of phosphorus oxygen acid groups in the produced diazo resin can be adjusted.

At that time, the charging molar ratio of the aromatic compound having a phosphorus oxygen acid group and the aromatic diazo compound was 1:0.1-0.1:
1; preferably 1:0.2 to 0.2:1, more preferably 1:0.5 to 0.2:1. In this case, the molar ratio of the total of the aromatic compound having a phosphorus oxygen acid group and the aromatic diazo compound to the active carbonyl compound is usually 1:
A diazo cocondensation resin can be obtained by charging the mixture at a ratio of 0.6 to 1.5, preferably 1:0.7 to 1.2, and reacting at a low temperature for a short time, for example, about 1 to 20 hours.

Specific examples of the acidic medium used when synthesizing the diazo resin used in the present invention by method (iii) include strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, or sulfuric acid.

These media have a weight of at least 30% by weight, advantageously from 70%
Used at a concentration of 100% by weight. Generally the balance is water, but may also consist partially or completely of organic solvents such as methanol, acetic acid, N-methylpyrrolidone, and the like. Good results are for example 85-93% phosphoric acid, 80-9
This is achieved with 8% sulfuric acid or 90% methanesulfonic acid or mixtures of these acids.

The temperature during condensation is about 0 to 70°C, preferably about 0 to 70°C.
It is 50°C.

Above, the synthesis methods (i) to (ij) have been explained in detail in order, but the method for synthesizing the diazo resin having a phosphorus oxygen acid group of the present invention is limited to the above (i) to (ji). isn't it.

The weight average molecular weight of the diazo resin used in the present invention is approximately 5
A range of 0.00 to 100,000 is suitable, preferably a range of about 1,000 to 10,000.

The content of phosphorus oxygen acid groups in the diazo resin used in the present invention is preferably 0.1 to 5 mm/I/g,
More preferably, it is 0.5 to 3 milliequivalents/gram.

At this time, if the oxygen acid group content of phosphorus is too high, the solubility of the diazo resin in the organic solvent will be low, and if the oxygen acid group content of phosphorus is too low, printing stains will easily occur.

Note that when the content of phosphorus oxygen acid groups in the diazo resin used in the present invention is less than 1 equivalent relative to the diazonium cation, it is necessary to contain an appropriate amount of counter anion.

The counter anion of the diazo resin used in the present invention is
It preferably contains an anion of an inorganic or organic acid having a pKa of 4 or less, which stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid and sulfonic acids, and 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 such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters , arsonic acid, phosphinic acid, fluorocarboxylic acids such as trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoroboric acid, hexafluorophosphoric acid, perchloric acid, as well as aliphatic and aromatic sulfonic acids such as methanesulfone. acids, fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, trioxy-
3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid,
Cyamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid
4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, P-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid,
Sulfosalicyl 1.2.5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-〇-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid , 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, butquinbenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexyl Naphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic 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'-diazide-stilbene-
33'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-
Diazide-5-sulfonic acid, 1□ 2-naphthoquinone-
1-diazide-4-sulfonic acid, octylbenzenesulfonic acid, dioctylbenzenesulfonic acid, nonylbenzenesulfonic acid, dinonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, bis-dodecylbenzene Sulfonic acid, tridecylbenzenesulfonic acid, undecyloxybenzenesulfonic acid, bis-undecyloxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, bis-dobucyloxybenzenesulfonic acid, dodecyltoluenesulfonic acid, tetradecylbenzenesulfonic acid, penta Decylbenzenesulfonic acid, hexatecylbenzenesulfonic acid, heptadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid, eicosadecylbenzenesulfonic acid, octylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid , dinonylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, bis-decylnaphthalenesulfonic acid, undecylnaphthalenesulfonic acid,
Anions such as dodecylnaphthalenesulfonic acid and tridecylnaphthalenesulfonic acid, or mixtures of these anions are included.

Among these anions, particularly preferred are hexafluorophosphoric acid, methanesulfonic acid, dibutylnaphthalenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and dioctylnaphthalenesulfonic acid. It is an anion.

When the diazo resin used in the present invention is contained in the photosensitive layer, the content is 0.1 to 30% by weight, preferably 1 to 30% by weight.
It is 10% by weight.

In addition to the diazo resin having a specific functional group used in the present invention, Japanese Patent Publication No. 47-1167, JP-A No. 50-1
No. 18802, Japanese Patent Publication No. 52-7364, and Japanese Patent Publication No. 1983
50% by weight of diazo resin as described in various publications such as No.-222834, based on the diazo resin of the present invention.
It may be used in combination in the following amounts.

A sensitizer can be used in the photosensitive layer used in the present invention. Such sensitizers are preferably triplet sensitizers having a maximum absorption that allows practically sufficient light absorption in the range of 300 nm or more.

Such sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds,
Examples include naphthothiapurine derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole i-form, naphthofuranone compounds, biryllium salts, thiapyrylium salts, and the like. Specifically, Michler's ketone, N,N'-diethylaminobenzophenone, benzanthrone, (3
-Methyl-1,3-diaza-1,9-benz)anthrone biclamide, 5-nitroacenaphthene, 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitro Fluorene, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3.
3-carbonyl-bis(7-dinithylaminocoumarin)
, 2.4.6-dryphenylthiavirylium verchlorate, 2-(p-chlorobenzoyl)naphthothiazole, and the like. The amount of these sensitizers added is about 1 to about 20% by weight of the photosensitive layer, more preferably 3 to 1% by weight.
0% by weight is suitable.

The photosensitive layer of the present invention may further contain a binder, if necessary, and is usually appropriately selected from linear organic polymers. Specific examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester,
Acrylic acid alkyl ester, acrylonitrile copolymer with at least one monomer such as vinyl chloride, styrene, butadiene, polyamide, methyl cellulose, polyvinyl formal, polyvinyl butyral, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer There are polymers, etc. In some cases, for the purpose of coloring the photosensitive layer, a dye or a pigment, a pH indicator as a print-out agent, etc. may be added.

Further, the photosensitive layer of the present invention may contain a plasticizer and the like. As the plasticizer, phthalic acid dialkyl esters such as dibutyl phthalate and dibutyl phthalate, oligoethylene glycol alkyl esters, phosphate ester plasticizers, etc. can be used.

Furthermore, it is preferable to incorporate a thermal polymerization inhibitor and an antioxidant into the photosensitive layer, such as hydroquinone, P-methoxyphenol, di-t-butyl-p-4 resol, 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 examples.

The above-mentioned photosensitive layer contains a photosensitive composition consisting of the above-mentioned components,
For example, 2-methoxyethanol, 2-methoxyethyl acetate, methyl cellosolve, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, acetone, methyl ethyl ketone, ethylene dichloride, methyl lactate, ethyl lactate,
It is formed by dissolving the solution in a suitable solvent such as methanol, dimethylformamide, ethanol, methyl cellosolve acetate, etc. alone or in a mixed solvent of an appropriate combination thereof, and coating the solution on a support.

The coating amount is about 0.1g/bo to about 10g after drying.
/n (range is appropriate, preferably 0.5 to 5 g/n)
It's Bo.

In the present invention, an intermediate layer may be provided as necessary for the purpose of increasing the adhesion between the support and the photosensitive layer, preventing the photosensitive layer from remaining after development, or preventing halation. good.

In order to improve adhesion, the intermediate layer is generally made of a diazo resin or a phosphoric acid compound that adsorbs to aluminum, for example. Further, the intermediate layer made of a highly soluble substance so that the photosensitive layer does not remain after development is generally made of a polymer with good solubility or a water-soluble polymer. Additionally, for antihalation purposes, the interlayer typically contains a dye or a U2 absorber. The thickness of the intermediate layer is arbitrary, and it must be thick enough to perform a uniform bond-forming reaction with the upper photosensitive layer when exposed to light. Usually about 1 to 10 on dry solids
A coating amount of 0 .mu./rrf is good, and a coating amount of 5 to 40 .mu./rr is particularly good. The intermediate layer may contain various additives in addition to a sensitizer, a diazo stabilizer, a polymeric binder, an antihalation agent, and a surfactant, if necessary.

Further, the intermediate layer can contain a diazo resin having a specific functional group used in the present invention.

In this way, by including a diazo resin having a specific functional group in the intermediate layer, there is an advantage that adhesion with the support can be obtained with a smaller amount than adding the diazo resin in the photosensitive layer. If it is likely to react with other components in the composition, it has the advantage of being able to be coated separately in multiple layers.

The usage ratio of the diazo resin having a specific functional group of the present invention in the intermediate layer is 30 to 100% by weight, preferably 60% by weight.
~100% by weight.

The intermediate layer can be obtained by dissolving a desired compound in any solvent at a desired concentration, coating or dipping it, and then drying it.

The support having a hydrophilic surface used in the present invention is
A dimensionally stable plate-like material is desirable. Such dimensionally stable plate-like materials include those conventionally used as supports for printed matter, and they can be suitably used in the present invention.

Such supports include paper, paper laminated with plastics (such as polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, triacetic acid, etc. Cellulose, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate,
Plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and plastic films laminated or vapor-deposited with the above metals are included. Among these supports, aluminum plates are preferred because they are extremely dimensionally stable, inexpensive, and have particularly good adhesion to the photosensitive layer of the present invention. In addition, Special Publick No. 48-18327
Also preferred is a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in the publication.

In the case of a metal support, particularly an aluminum support, it is preferable that the support be subjected to a surface treatment such as grain treatment or anodization treatment.

In order to increase the hydrophilicity of the surface, it is preferable to perform immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like. U.S. Patent No. 2,714,0
As described in the specification of No. 66, an aluminum plate was immersed in a sodium silicate aqueous solution after graining, and an aluminum plate was anodized as described in Japanese Patent Publication No. 47-5125. Those which are subsequently immersed in an aqueous solution of an alkali metal silicate are also preferably used.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

Also, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-5
Also useful is a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A-8602 and JP-A-52-30503.

Further, it is also suitable that the material is sequentially subjected to brassidalein treatment, electrolytic grain treatment, anodization treatment, and sodium silicate treatment, as disclosed in JP-A-56-28893.

Further, after these treatments, it is also suitable to apply an undercoat with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, or the like.

These hydrophilic treatments are performed 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 layer. This is done for the purpose of improvement, etc.

The photosensitive lithographic printing plate of the present invention is imagewise exposed using a light source rich in ultraviolet light such as a metal halide lamp or a high-pressure mercury lamp, and treated with a developer to remove unexposed areas of the photosensitive layer,
Finally, a lithographic printing plate is prepared by applying a gum liquid.

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic diphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic amine compounds such as monoethanolamine, jetanolamine, triethanolamine, etc. are suitable, and their concentrations are It is added in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required. Preferred organic solvents include benzyl alcohol, 2-phenoxyethanol, 2-butoxyethanol, and n-propyl alcohol. In addition,
It is also preferable to add a reducing substance such as a dissolution promoter for the diazo resin, such as a sulfite, methylresorcinol, or a pyrazolone compound. Also, U.S. Patent No. 3,475,171
The developer described in the specifications of No. 1 and No. 3,615,480; The developer described above is also excellent as a developer for the photosensitive lithographic printing plate of the present invention.

[Effects of the Invention] The photosensitive lithographic printing plate of the present invention maintains the excellent sensitivity and performance of the photosensitive layer, has excellent adhesion between the support and the photosensitive layer, and can be developed with alkaline water. The lithographic printing plates have excellent printing performance.

Further, the negative-working photosensitive lithographic printing plate of the present invention can be developed with a developer for positive-working photosensitive lithographic printing plates.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples. Note that "%" indicates weight % unless otherwise specified.

Synthesis Example 1 7.79 g (0,0200
mol ) and 23.5 g (0,0800 mol) of 4-diazodiphenylamine hydrogen sulfate in 96% sulfuric acid 8
Dissolved in 0d. To this, paraformaldehyde (95
%) 3.16g (0,100mol) was added and heated at 5°C.
The mixture was stirred for 2 hours. After that, pour the reaction solution into 1.5 f of ice water.
and then add 50% zinc chloride aqueous solution 26
0 g was added to deposit a yellow precipitate. This yellow precipitate was filtered off to obtain a zinc chloride double salt of a condensate of 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine/4-diazodiphenylamine and formaldehyde.

The above condensate was dissolved in 800 d of water, and 39.6 g (0,120 mol) of sodium 2-methoxy-4-hydroxy-5-penzoylhenzenesulfonate was dissolved in 600 d of water.
The 0M solution was added with stirring. The produced yellow precipitate was collected by filtration and dried to give 2-methoxy-4-hydroxy-5-penzoylhenzensulfone, a condensate of 4-diazo-4'-dihydroxyphosphinyloxydiphenylamine/4-diazodiphenylamine and formaldehyde. 33 g of the acid salt were obtained (diazo resin 1 of the invention).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight (polystyrene standard) was measured using gel permeation chromatography (hereinafter abbreviated as GPC) and found to be 2,300.

Synthesis Example 2 4-diazo-4'-(2-dihydroxyphosphinyl)ethoxydiphenylamine hydrogen sulfate 10.4 g
(0,0250 mol) and 24.2 g (0,07
50 mol) was dissolved in 85% phosphoric acid. Add rose formaldehyde (95%) to this 2.84g (0
, 0900 mol) and stirred at 40"C for 20 hours. Then, the reaction solution was diluted with isopropyl alcohol 1
1 with stirring to precipitate a yellow precipitate.

This yellow precipitate was filtered and washed with isopropyl alcohol to form a condensate of 4-diazo-4'-(2-dihydroxyphosphinyl)ethoxydiphenylamine/4-diazo-4'methoxydiphenylamine and formaldehyde. The dihydrogen phosphate salt of was obtained.

The above condensate was mixed with 200 d of water and methyl ethyl ketone (MEK).
) and 31.3 g of sodium dodecylbenzenesulfonate (0,090 On+
A 600 d solution of ol) in water was added with vigorous stirring. After stirring for a while, the mixture was allowed to stand and was separated into two layers. This upper layer was poured into water 21 with stirring, and the produced yellow precipitate was collected by filtration and dried to obtain 4-diazo-4'
36 g of dodecylhenzenesulfonate of a condensate of -(2-dihydroxyphosphinyl)ethoxydiphenylamine/4-diazo-4'-methoxydiphenylamine and formaldehyde was obtained (diazo resin 2 of the present invention).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight was measured using GPC and found to be 2,400.

Planned amount: 32.3 g (0,100 mol) of 4-diazo-4'-methoxydiphenylamine hydrogen sulfate was dissolved in 96% sulfuric acid 7
5 dissolved in paper. To this, 4.14 g (0,0300 mol) of 3-dihydroxyphosphinylpropanal
was added and stirred at 5°C for 2 hours. Next, 2.21 g of paraformaldehyde (95%) (
0,0700 mol) was added thereto, and the mixture was further stirred at 5°C for 2 hours. Thereafter, the reaction solution was poured into 1.54 g of ice water with stirring, and 180 g of a 50% zinc oxide aqueous solution was added to precipitate a yellow precipitate. This yellow precipitate was filtered, and 4-diazo-4'-methoxydiphenylamine and 3-
A zinc chloride double salt of a condensate of dihydroxyphosphinylpropanal and formaldehyde was obtained.

The above condensate was suspended in a mixed solution of 200 rn1 of water and 500 d of MEK, and 29.2 g (0,0840 mol) of sodium dodecylbenzenesulfonate was added to 600 ml of water.
d solution was added with vigorous stirring. After stirring for a while, the mixture was allowed to stand and was separated into two layers. Water this upper layer with 2
The resulting yellow precipitate was filtered and dried to obtain 36 g of dodecylbenzenesulfonate, a condensate of 4-diacysyl-4'-methoxydiphenylamine and 3-dihydroxyphosphinylpropanal formaldehyde. (Diazo resin 3 of the present invention) was obtained.

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight was measured using GPC and found to be 2,090.

Synthesis Example 4 29.3 g of 4-diazodiphenylamine hydrogen sulfate (
0,100 mol) was dissolved in 10 ml of 96% sulfuric acid. To this was added 4.04 g (0,0200 mol) of 4-dihydroxyphosphinyloxybenzaldehyde, and the mixture was stirred at 5°C for 2 hours. Next, 2.53 g of paraformaldehyde (95%) was added to the reaction mixture.
(0,0800 mol) was added thereto, and the mixture was further stirred at 5°C for 2 hours. Thereafter, the reaction solution was poured into 1.5 ml of ice water with stirring, and 210 g of a 50% zinc chloride aqueous solution was added to precipitate a yellow precipitate. This yellow precipitate was filtered to obtain a zinc chloride double salt of a condensate of 4-diazodiphenylamine and 4-dihydroxyphosphinyloxybenzaldehyde/formaldehyde.

Add the above condensate to 800 J of water! i! 44.4 g of sodium dioctylnaphthalene sulfonate (0
, 0960 mol) in 600 In1 of water was added with vigorous stirring. The produced yellow precipitate was collected by filtration and dried to obtain 35 g of dioctylnaphthalene sulfonate, a condensate of 4-diazodiphenylamine and 4-dihydroxyphosphinyloxybenzaldehyde/formaldehyde (diazo resin 4 of the present invention).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight was measured using GPC and found to be 1,970.

Synthesis Example 5 24.9 g of 4-diazodiphenylamine hydrogen sulfate (
0,0850 mol) and phenyl phosphoric acid 2.61 g
(0,0150 mol) was dissolved in 96% sulfuric acid 70ae. Add to this paraformaldehyde (95%) 3.1
Add 6g (0,100mol) and incubate at 5°C for 2 hours.
Stir for hours. Thereafter, the reaction solution was poured into 1.54% of ice water with stirring, and further 22% of a 50% aqueous solution of zinc chloride double salt.
A yellow precipitate was deposited by adding 0 g. This yellow precipitate was filtered off to obtain a zinc chloride double salt of a condensate of 4-diazodiphenylamine/phenylphosphoric acid and formaldehyde.

The above condensate was dissolved in 800 g of water, and 34.8 g (0.100 m
A 600 d solution of ol) in water was added with vigorous stirring. The generated yellow precipitate was collected by filtration and dried to obtain 32 g of dodecylbenzenesulfonate, a condensate of 4-diazodiphenylamine/phenylphosphoric acid and formaldehyde (
Diazo resin of the present invention 5).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight was measured using GPC and found to be 2,320.

Synthesis Example 6 25.9 g (0,0800 mol) of 4-diazo-4'-methoxydiphenylamine hydrogen sulfate and 3.44 g (0,0 mol) of α-dihydroxyphosphinyltoluene
200 mol) was dissolved in 70 ml of 85% phosphoric acid. Add to this 3.16 g of paraformaldehyde (95%) (0
, 100 mol) and stirred at 40°C for 20 hours. After that, the reaction solution was mixed with isopropyl alcohol 1
A yellow precipitate was deposited.

This yellow precipitate was filtered and washed with isopropyl alcohol to obtain a condensate of 4-diazo-4'-methoxydiphenylamine/α-dihydroxyphosphinyltoluene and formaldehyde.

The above condensate was suspended in a mixture of 200 d of water and 500 d of MEK, and 2
7.9 g (0,0800 mol) of water 600 m
The fl solution was added with vigorous stirring. After stirring for a while, the mixture was allowed to stand and was separated into two layers. This upper layer was poured into water 21 with stirring, and the yellow precipitate formed was filtered.
By drying, 33 g of dodecylbenzenesulfonic acid salt of a condensate of 4-diazo-4'-methoxydiphenylamine/α-dihydroxyphosphinyltoluene and formaldehyde was obtained (diazo resin 6 of the present invention).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with pyrazolone, the weight average molecular weight was measured using GPC and found to be 2,350.

After the surface of an aluminum plate with a thickness of 0.30 mm was grained using a nylon brush and a water suspension of 400 mesh bumiston, it was thoroughly washed with water.

After etching by immersing in 10% sodium hydroxide aqueous solution at 70°C for 60 seconds, washing with running water and 20% HNO!
It was neutralized and washed with an aqueous solution and then washed with water. This is vA= 12.7
Electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of V with an anode special electric charge of 160 corons/dm''.The surface roughness was measured. , 0.6 μ (in Ra), after subsequent immersion in 30% H2SO, aqueous solution and desmant treatment for 2 minutes at 55°C, 20%) H2SO, aqueous solution at a current density of 2 A/dn+2. It was anodized for 2 minutes so that its strength was 2.7 g/nl.After step 1, it was immersed in a 2.5% aqueous solution of sodium silicate at 70'C for 1 minute, washed with water, and dried.

Next, the following photosensitive composition I was prepared.

Sensitizer represented by the following structural formula Diazo resin 5 of the present invention (Synthesis Example 5) 0, Log Methyl ethyl ketone copper phthalocyanine pigment (CI PigmentBlue
15) 10% plasticizer dispersion 1.0 μm of the photosensitive composition was applied onto the aluminum support using a spin coater so that the weight after drying was 1.2 g/rrf. It was coated and dried at 80° C. for 2 minutes to obtain a photosensitive planographic printing plate (A).

Comparative Example 1 A photosensitive lithographic printing plate (B) was obtained in the same manner as in Example 1 except that the diazo resin 5 of the present invention was not used in the photosensitive composition (1).

Comparative Example 2 A photosensitive lithographic printing plate ( C) was obtained.

Diazo resin (a) PF of a condensate of P-diazodiphenylamine and formaldehyde, using a salt vacuum baking frame apparatus, the above photosensitive lithographic printing plate (A,)
~ [C] A step wedge (density step 0.15, number of density steps 15) and halftone negative original were brought into close contact with each other, and exposed by irradiating it with a - ultra-high pressure mercury lamp for 60 seconds.
The film was developed by immersing it in a 5% by weight aqueous sodium silicate solution for about 1 minute.

After washing with water and drying, the obtained lithographic printing plates (A) and (B)
and (C) were printed using a KOR-D type printing machine manufactured by Heidelberg.

The results of the printing plate sensitivity, printing performance, etc. are as shown in Table 1 below.

Table 1 ○: No stain ×: Stain From Table 1, it can be seen that the lithographic printing plate (A) of the present invention has high sensitivity, is resistant to scratches during development, and has excellent performance during printing.

Example 2 The following photosensitive composition (2) was coated on an aluminum support in the same manner as in Example 1, and dried to obtain a photosensitive lithographic printing plate (D).
I got it.

43 g of the following exacerbating agent Diazo resin 6 of the present invention (Synthesis Example 6) Dipicolinic acid 0.1 g 0.05 g Propylene glycol monomethyl ether 0 g Methyl ethyl ketone 50 g Megafac F-1, 770,03 g (manufactured by Dainippon Ink ■, Fun yarn) Surfactant) Oil Blue #603 (manufactured by Orient Chemical Industry ■) 0.15g Comparative Example 3 Photosensitive composition was prepared in the same manner as in Example 2, except that the diazo resin 6 of the present invention was not blended into the photosensitive composition ■. Lithographic printing plate (
E-3 was obtained.

Photosensitive lithographic printing plate CD obtained in the same manner as in Example 1
) and (E) were exposed, developed and printed and the results are shown in Table 2 below.

Table 2 ○: No stain From Table 2, it can be seen that the lithographic printing plate [D] of the present invention has high sensitivity, is resistant to scratches during development, and has poor performance during printing.

Example 3 After treating an aluminum support in the same manner as in Example 1, the following diazo resin solution was prepared.

Diazo resin 3 of the present invention (Synthesis example 3) 0.1g methanol 180g pure water
20g of this liquid using a spin coater, the weight after drying is 1
Coat it on an aluminum support so that it is 0 ■/bo,
It was dried at 80°C for 1 minute to form an intermediate layer.

Next, the following photosensitive composition (2) was prepared.

0.4g of sensitizer with the following structural formula 0.5g of diethyl phthalate Copper phthalocyanine pigment (CI PigmentBlue)
15) 10% plasticizer dispersant 1.0 g Megafanoku F-177 (manufactured by Dainippon Ink ■, Hun thread surfactant) Methyl ethyl ketone methanol 0.02 g 0 g 2 g This photosensitive composition ■ was applied to a support having an intermediate layer. It was applied onto the body using a rotary coating machine so that the weight after drying was 1.0 g/rd, and then dried at 80'C for 2 minutes.
A photosensitive planographic printing plate CF) was obtained.

Comparative Example 4 Example 3 except that dodecylbenzenesulfonate, a condensate of 4-diazodiphenylamine and formaldehyde, was used in place of the diazo resin 3 of the present invention in the diazo resin solution in Example 3. A photosensitive lithographic printing plate CG) was obtained in the same manner as above.

Further, Example 3 was repeated except that the diazo resin of the present invention was not used to obtain a photosensitive planographic printing plate (H).

The obtained photosensitive planographic printing plates (F) to (H) were exposed, developed and printed in the same manner as in Example 1, and the results obtained are shown in Table 3.

Table 3 ○: No dirt × :Dirty From Table 3, Lithographic printing plate (F) of the present invention teeth, High sensitivity Easy to clean, no stains during development, Has sufficient rigidity I understand.

Claims (2)

[Claims] (1) A photosensitive lithographic printing plate having a photosensitive layer containing an alkaline water-soluble or swellable photodimerizable photocrosslinkable polymer on a support having a hydrophilic surface, the photosensitive layer comprising at least one A photosensitive lithographic printing plate characterized by containing a diazo resin having a phosphorus oxygen acid group. (2) A photosensitive lithographic printing plate comprising, on a support having a hydrophilic surface, an intermediate layer and a photosensitive layer containing an alkaline water-soluble or swellable photodimerizable photocrosslinkable polymer, wherein the photosensitive layer and A photosensitive lithographic printing plate characterized in that/or the intermediate layer contains a diazo resin having at least one phosphorous oxyacid.