JPH03290663A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obviate the staining of printing even after long-term preservation as the photosensitive compsn. for planographic printing plates and to improve the printing resistance, producibility and solubility in org. solvents of the compsn. by incorporating a high-polymer compd. and a diazo resin having a fluorine atom in the main skeleton into this compsn. CONSTITUTION:The fluorine atom is introduced into the main skeleton of the diazo resin by the condensation or cocondensation reaction of an arom. diazonium compd. having the fluorine atom with aldehyde or ketone or the equiv. compd. of the active carbonyl compd. thereof or the arom. diazonium compd. with the arom. compd. having the fluorine atom or the aldehyde or ketone or the equiv. compd. of the active carbonyl compd. thereof. An alkaline- soluble or swellable high-polymer compd. is combined as a binder resin with this resin and further dyes, etc., are added thereto. The compsn. is dissolved in a suitable solvent and the soln. is coated on a base having a lipophilic surface. The coating is then dried to obtain the photosensitive planographic printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition, and particularly to a photosensitive composition suitably used in a photosensitive lithographic printing plate.

More specifically, the present invention relates to a photosensitive composition containing the novel diazo resin that does not cause printing stains.

[Conventional technology]

The majority of those conventionally used as photosensitive substances in negative-working printing materials (so-called 28 plates) are diazonium compounds, especially those in which two or more diazonium salt skeletons are linked together. It is a polymeric diazonium salt (so-called diazo resin).

When such a diazo resin is coated on a suitable support such as paper, plastic or metal and exposed to actinic light through a transparent negative, the diazo resin in the exposed areas decomposes and becomes insoluble and lipophilic. Changes to

On the other hand, the surface of the support is exposed by dissolving and removing the unexposed areas with water. If a support having a surface that has been previously subjected to a hydrophilic treatment is used, the hydrophilic layer will be exposed in the unexposed areas through development. Therefore, when performing offset printing, this portion receives water and repels ink.

On the other hand, the decomposed portion of the diazo resin exhibits lipophilic properties, repelling water and accepting ink. Such printing materials thus give so-called negative-positive printing plates.

Conventionally, the method for linking diazonium salt skeletons in such diazo resins is to condense an aromatic diazonium compound and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes or acetals such as formaldehyde and acetaldehyde, in an acidic medium. The method was used to

The most typical example is a formaldehyde condensate of 4-diazodiphenylamine. A method for producing a diazo resin by the coupling method is described, for example, in U.S. Pat. No. 2,679.498.
No. 3,050,502, No. 3.311.60
No. 5, and No. 3,277.074.

In the diazo resin linked by the reactive carbonyl group, when the counter anion of the diazonium salt is a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid, or an inorganic anion such as a double salt with zinc chloride, water-soluble There is a problem that it becomes unstable against moisture and its storage stability deteriorates. Therefore,
In order to improve storage stability, there is a method in which a water-soluble diazo resin is reacted with an organic coupling agent such as a phenolic hydroxyl group-containing aromatic compound, an acidic aromatic compound, or an acidic aliphatic compound and used as a water-insoluble resin. Special Public Service 1977-
No. 1167 and US Pat. No. 3,300,309.

However, this type of diazo resin does not have sufficient solubility in organic coating solvents such as alcohols, ketones, and glycol ethers. Therefore, in order to make the diazo resin water-insoluble and organic solvent-soluble, halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid,
and JP-A-54-98 on the use of diazo resins with perhalogen acids such as perchloric acid and periodic acid as counter anions.
It is described in Japanese Patent No. 613 and Japanese Patent No. 56-121031.

However, these diazo resins still do not have sufficient solubility in organic coating solvents. Therefore, in order to make the resin insoluble in water and increase the solubility in organic solvents, a study was published in Japanese Patent Application Laid-Open No. 58209733 regarding the use of an anionic surfactant, that is, a diazo resin with a sulfonic acid having a long-chain alkyl group as a counter-anion. No. 62-175731, and No. 63-262643.

However, these diazo resins have poor storage stability because of insufficient hydrophobicity. In other words, after a photosensitive lithographic printing plate using a photosensitive composition containing these diazo resins is stored in the presence of moisture, the plate-made lithographic printing plate produces printing stains and has low rigidity resistance. There are problems.

In addition, regarding the use of diazo resins in which an anion having a long chain fluorinated alkyl group is used as a counter anion,
This method has been proposed in Japanese Patent No. 12029, Japanese Patent No. 51-141003, and British Patent No. 1501128. When these diazo resins are applied onto a support and exposed to light, the exposed areas exhibit oil repellency due to the fluorine contained in the diazo resin and thus repel ink. That is, these diazo resins are used as dryographic ink plates, that is, waterless planographic plates. However, since the diazo resin itself is inherently hydrophilic, the (θ) inkability of the exposed area is not sufficient and print stains are likely to occur.

[Problem to be solved by the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition containing a novel diazo resin that provides a lithographic printing plate that is free from printing stains even after long-term storage and has excellent rigidity resistance. That is, the object of the present invention is to provide a film that has good developability when developing a non-image area even when imagewise exposed after long-term storage in a high-humidity place, does not cause printing stains, and can be obtained after development. The object of the present invention is to provide a photosensitive composition containing a diazo resin that provides a lithographic printing plate with excellent film strength in the image area and good rigidity resistance.

Another object of the present invention is to provide a photosensitive composition containing a diazo resin that has excellent manufacturability.

Yet another object of the present invention is to improve solubility in organic solvents;
Another object of the present invention is to provide a photosensitive composition containing a diazo resin with improved storage stability.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventor discovered that the above object could be achieved by using a new diazo resin, and thus arrived at the present invention.

That is, the present invention provides a photosensitive composition characterized by containing a polymer compound and a diazo resin having a fluorine atom in its main skeleton.

In the present invention, the main skeleton of the diazo resin refers to all parts of the diazo resin other than the counter anion.

The present invention will be explained in detail below.

As a method for introducing a fluorine atom into the main skeleton of the diazo resin of the present invention, any method possible in terms of organic synthesis can be used, but the main methods include, for example, the following methods. .

(i) Condensation reaction between an aromatic diazonium compound having a fluorine atom and an aldehyde or ketone or an equivalent individual of an active carbonyl compound thereof.

(ii) A condensation reaction between an aromatic diazonium compound and a fluorine atom-containing aldehyde or ketone or an active carbonyl compound thereof.

(iii) A co-condensation reaction between an aromatic diazonium compound, an aromatic compound having a fluorine atom, and an aldehyde or ketone or an equivalent individual of an active carbonyl compound thereof.

Hereinafter, methods (i) to (iii) will be explained in detail in order.

The method (i) is based on a condensation reaction between an aromatic diazonium compound having a fluorine atom and an aldehyde or ketone or an active carbonyl compound thereof, and the aromatic diazonium compound having a fluorine atom is preferably 4-diazodiphenylamine skeleton, 4
Examples include compounds having a -diazodiphenyl ether skeleton and a 4-diazodiphenyl sulfide skeleton. A fluorine atom may be directly bonded to the aromatic ring, or a substituent having a fluorine atom may be bonded to the aromatic ring. Examples of the substituent having a fluorine atom include a fluorinated alkyl group or a fluorinated alkoxy group having 1 to 20 carbon atoms, preferably a perfluoroalkyl group or a perfluoroalkoxy group having 1 to 20 carbon atoms. . Other substituents, such as an alkyl group, an alkoxy group, a hydroxy group, a carboxy ester group, a carboxyl group, a sulfonyl group, or a phosphorus oxygen acid group, may be bonded to the aromatic ring, but aldehyde or ketone Or, in order to condense with equivalent individuals of these active carbonyl compounds, it is necessary to have at least two unsubstituted sites on the aromatic ring.

Specifically, the aromatic diazonium compounds having a fluorine atom include, for example, 4-diazo-3-fluorodiphenylamine, 4-diazo2-fluorodiphenylamine, 4-diazo-2'fluorodiphenylamine,
4-Diazo-3'fluorodiphenylamine, 4-diazo-4'fluorodiphenylamine, 4-diazo-3゜5-difluorodiphenylamine, 4-diazo2.5-
Difluorodiphenylamine, 4-diazo-2,6-difluorodiphenylamine, 4-diazo-3',5'-difluorodiphenylamine, 4-diazo-3',4'-
Difluorodiphenylamine, 4-diazo-2,4'-
Difluorodiphenylamine, 4-diazo-3,5,4
'Trifluorodiphenylamine, 4-diazo-2゜3
．． 5.6-tetrafluorodiphenylamine, 4-diazo-2,6,3',5'-tetrafluorodiphenylamine, 4-diazo-2,3,5°6.3',5'-hexafluorodiphenylamine, 4 -Diazo-4'-trifluoromethyldiphenylamine, 4-diazole4'-
Trifluoromethoxydiphenylamine, 4-diazo-
3'trifluoromethyldiphenylamine, 4-diazo-2'-trifluoromethoxydiphenylamine, 4-
Diazo-2-trifluoromethyldiphenylamine, 4
-Diazo-3-trifluoromethoxydiphenylamine, 4-diazo-4'-pentafluoroethyldiphenylamine, 4-diazo-4'-pentafluoroethoxydiphenylamine, 4-diazo-3-pentafluoroethyldiphenylamine, 4-diazo-2 '-Pentafluoroethoxydiphenylamine, 4-diazo-4'-hebutafluoropropyldiphenylamine, 4-diazo-4
'-nonafluorobutyldiphenylamine, 4-diazo-4'-perfluoropentyldiphenylamine, 4-
Diazo-4'-perfluorohexyldiphenylamine, 4-diazo4'-perfluorohebutyldiphenylamine, 4-diazo-4'-perfluorooctyldiphenylamine, 4-diazo-4'-perfluorododecyldiphenylamine, 4-diazo- 4'-perfluorooctyloxydiphenylamine, 4-diazo-3-perfluorododecyldiphenylamine, 4-diazo-2,
4'-bis(perfluorooctyl)diphenylamine, 4-diazo3.4'-bis(perfluorododecyl)
Diphenylamine, 4-diazo-2-fluorodiphenyl ether, 4-diazo-4'-fluorodiphenyl ether, 4-diazo-3-fluorodiphenyl ether, 4-diazo-2,3,5', 6-titrafluorodiphenyl ether, 4 -Diazo 4'-trifluoromethyl diphenyl ether, 4-diazo-3-trifluoromethoxydiphenyl ether, 4-diazo-21-fluorodiphenylsulfide, 4-diazo-3-fluorodiphenylsulfide, 4-diazo-4'-fluorodiphenyl Sulfide, 4-diazo-4'-trifluoromethoxydiphenyl sulfide, 4-sia'/'-2-trifluoromethyldiphenyl sulfide, and the like.

The method for synthesizing the diazo resin in method (i) used in the present invention includes, for example, a diazonium compound having a fluorine atom and formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 1so-butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone, or acetophenone. and an active carbonyl compound having no carboxyl group or an acetal thereof, respectively, preferably in a molar ratio of 1 g 1oo to 1:0.2,
More preferred is a method of condensation in an acidic medium at a ratio of 1:10 to 1:0.5.

When carrying out the condensation reaction, a diazonium compound that does not have a fluorine atom and/or an aromatic compound that does not have a diazonium group can be used in combination to adjust the fluorine atom content of the diazo resin to be produced. . Examples of the diazonium compound having no fluorine atom include aromatic diazonium compounds preferably having 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, 41 r-propoxy-4-diazodiphenylamine, 4'-methyl-4
-diazodiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-propyl-4-diazodiphenylamine, 4'-1-propyl-4diazodiphenylamine, 4'-ne-butyl-4diazodiphenyl Amine, 4'-hydroxymethyl-4-diazodiphenylamine, 4'-β-hydroxyethyl-4-diazodiphenylamine, 4'-γ-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-diazo-3-methoxy-6-methyldiphenylamine, 3.3'dimethyl-
4-diazodiphenylamine, 3'n-butoxy-4-
Diazodiphenylamine, 3゜4'-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, 3°3'-dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl 4 -diazodiphenyl sulfide, 4'-methyl-2,5-dimethoxy-4-diazodiphenyl sulfide, and the like.

Examples of the aromatic compound having no diazonium group include 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,
It is also possible to use methylol derivatives as described in Japanese Patent Publication No. 49-45322 and Japanese Patent Publication No. 49-45323, or olefinically unsaturated compounds as described in Japanese Patent Publication No. 58-187925.

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 5°C.
It is 0°C.

Method (ii) is based on a condensation reaction between an aromatic diazonium compound and an aldehyde having a fluorine atom or an individual thereof, and the synthesis method includes, for example, a 4-diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl ether skeleton. The molar ratio of the diazo monomer having a 4-diazodiphenyl sulfide skeleton and the aldehyde or its acetal having a fluorine atom is preferably 1:10 to 1:1.
A method of condensation in an acidic medium at a ratio of 0.05, more preferably 1:2 to 1:0.2 can be mentioned. When carrying out the condensation reaction, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, is.

- Use active carbonyl compounds or their acetals without fluorine atoms such as butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone, or acetophenone as condensing agents, or co-condense aromatic compounds without diazonium groups. be able to. As the above-mentioned active carbonyl compound having no fluorine atom, formaldehyde is most preferable, and its charging ratio is preferably in molar ratio to the diazo monomer:
θ~5, more preferably O11~1.

When using an aldehyde having a fluorine atom and an active carbonyl compound not having a fluorine atom, first, the diazo monomer and the aldehyde having a fluorine atom are condensed in an acidic medium, and then a more reactive Higher molecular weight diazo resins can be obtained by carrying out the post-condensation with active carbonyl compounds or their acetals which do not contain fluorine atoms, such as formaldehyde.

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 above-mentioned active carbonyl compounds having no fluorine atom or their acetals,
Methylol derivatives as described in JP-A-45322 and JP-A-49-45323, or JP-A-58-1
Olefinically unsaturated compounds such as those described in Japanese Patent No. 87925 can also be used.

The diazo monomer used in the method (ii) of the present invention is a compound having an aromatic ring substituted with at least one diazonium group, and is preferably a compound having an aromatic ring substituted with at least one diazonium group.
) aromatic diazonium compounds represented by:

In the formula, R1 represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a hydroxyl group, a carboxy ester 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.

R2 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.

R3 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 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.

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

Specific examples of the aromatic diazonium compounds shown in the above-mentioned total (1) include 4-diazodiphenylamine, 4'-hydroxy-4-diazodiphenylamine, 4-diazodiphenylamine, 4'-hydroxy-4-diazodiphenylamine,
'-Methoxy-4-diazodiphenylamine, 4'-ethoxy-4-diazodiphenylamine, 4' n-propoxy-4-diazodiphenylamine, 4'-1-pucoboxy4-diazodiphenylamine, 4'-methyl 4-
Diazodiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-propyl 4-diazodiphenylamine, 4'-1-propyl-4-diazodiphenylamine, al, -butyl-4-diazodiphenylamine, 4'-hydroxy Methyl-4-diazodiphenylamine, 4'-β-hydroxyethyl-4-diazodiphenylamine, 4'-γ-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-diazo-3-methoxy-
6-methyldiphenylamine, 3,3'-dimethyl-4
-diazodiphenylamine, 3'-n-butoxy-4-
Diazodiphenylamine, 3,4'-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, 3.3'-
Dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl-4-diazodiphenyl sulfide, 4'-methyl-2,5-dimethoxy-
Examples include 4-diazodiphenyl sulfide.

Among these, particularly preferred aromatic diazonium compounds include 4-diazodiphenylamine, 4-diazo-4'
-methoxydiphenylamine, 4-diacy4'-ethoxydiphenylamine, and 4-diazo-3-methoxydiphenylamine.

The aldehyde having a fluorine atom or its 7-setal is preferably an aromatic aldehyde substituted with a fluorinated alkyl group and/or a fluorinated alkoxy group, an aromatic aldehyde substituted with a fluorinated atom, or an aliphatic aldehyde. or their acetals. The above aldehydes or acetals thereof include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, halogen atoms other than fluorine atoms, hydroxy groups, substituted or unsubstituted amine groups, carboxy ester groups, amide groups, or carboxyl groups. May be replaced.

Specific examples of these fluorine atom-containing aldehydes or their acecules include 2-fluoroacetaldehyde, 2,2-difluoroacetaldehyde, 2,
2.2-) Lifluoroacetaldehyde, 2-fluoropropylaldehyde, 2.2,3,3,3. -pentafluoropropylaldehyde, 2-fluorobutyraldehyde, 3-fluorobutyraldehyde, 4-fluorobutyraldehyde, 4.4.4-)lifluorobutyraldehyde, 2,3.4-)lifluorobutyraldehyde,
Perfluorobutyraldehyde, perfluoropentylaldehyde, perfluorohexylaldehyde, perfluoroheptylaldehyde, perfluorooctylaldehyde, perfluorododecylaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde,
4-fluorobenzaldehyde, 2,3-difluorobenzaldehyde, 2,4-difluorobenzaldehyde,
2,3.4-Trifluorobenzaldehyde, perfluorobenzaldehyde, 2.3゜5.6-tetrafluoro-4-methoxy-, nzaldehyde, 4-trifluoromethylbenzaldehyde, 4-trifluoromethoxybenzaldehyde, 4-per Fluoroethylbenzaldehyde, 4-perfluoroethylbenzaldehyde, 3
-Perfluoroethylbenzaldehyde, 4-perfluoropropylbenzaldehyde, 4-perfluoropropoxybenzaldehyde, 4-perfluorohexylbenzaldehyde, perfluorohexyloxyhenzaldehyde, perfluorooctylbenzaldehyde, perfluorooctyloxybenzaldehyde, or their acetals, etc. can be mentioned.

Specific examples of the acidic medium used when synthesizing the diazo resin used in the present invention by method (ii) 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 the condensation is about 0-70°C, preferably about 0-5
It is 0°C.

The method (iii) is based on a co-condensation reaction between an aromatic diazonium compound, an aromatic compound having a fluorine atom, and an aldehyde or ketone or an active carbonyl compound thereof.

Preferable examples of the aromatic ring of the above-mentioned aromatic compound having a fluorine atom include an aryl group, such as a phenyl group and a naphthyl group.

The above-mentioned fluorine atom may be directly bonded to the aromatic ring, or a substituent having a fluorine atom may be bonded to the aromatic ring.

In addition, the aromatic ring of the aromatic compound having a fluorine atom may include other substituents other than the fluorine atom or the substituent having a fluorine atom, such as an alkyl group, an alkoxy group, a hydroxyl group, or a carboxy ester group. , carboxyl group,
A sulfonyl group or a phosphorus oxygen acid group may be bonded, but in order to condense with an aldehyde or ketone or an active carbonyl compound thereof, one or more aromatic rings of the aryl group may be bonded. It is necessary to have at least two unsubstituted sites on the top.

Specific examples of the aromatic compound having a fluorine atom include fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-)lifluorobenzene, 1,2
．． 4-) Lifluorobenzene, 1.3.5-trifluorobenzene, 2゜3-difluoroanisole, 3.5-
Difluoroanisole, 3,5-difluorotoluene,
Trifluoromethoxybenzene, trifluoromethylbenzene, 4-pentafluoroethylanisole, 3-pentafluoroethoxyanisole, 3-perfluorohexylanisole, 4-perfluorooctyloxyphenol, ■-fluoronaphthalene, 2-fluoronaphthalene, 1.2,3゜4-tetrafluoronaphthalene,
2,3,4,5゜6-pentafluorodiphenylamine, 2,3゜4.5.6-pentafluorodiphenyl ether, 2.3.4,5.6-pentafluorodiphenyl sulfide, 2,3,4,5 .6-pentafluorobiphenyl, 2.3.4.5.6-pentafluorobenzophenone, and the like.

On the other hand, the aromatic diazonium compound used in the method (iii) is a compound having an aromatic ring substituted with at least one diazonium group, and preferably has an aromatic ring substituted with at least one diazonium group. Examples include diazonium compounds.

The condensation type resin with an active carbonyl compound (hereinafter referred to as diazo cocondensation resin) containing an aromatic compound having a fluorine atom and an aromatic diazonium compound as constituent units synthesized by the method (iii) of the present invention is a known methods, such as photographic ink science
and Engineering (Photo, Sci, +E
ng, ) Volume 17, Page 33 (1973), U.S. Patent Nos. 2,063,631 and 2,679,498, and Japanese Patent Publication No. 49-48001, sulfuric acid or phosphoric acid or diazonium salts, fluorine-containing aromatic compounds and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 1so-butyraldehyde, benzaldehyde or ketones such as acetone, methyl ethyl ketone, acetophenone, etc. It is obtained by polycondensing carbonyl compounds or their acetals.

Further, these aromatic compounds having fluorine atoms in their molecules, aromatic diazonium compounds, and active carbonyl compounds or their acetals can be freely combined with each other,
Furthermore, it is also possible to co-condense a mixture of two or more of each. Furthermore, co-condensation can be carried out by adding a co-condensable aromatic compound which does not have a fluorine atom. Examples of such co-condensable aromatic compounds include aromatic compounds described in Japanese Patent Publication No. 49-48001.

In addition, instead of the active carbonyl compound or their acecur, Japanese Patent Publication No. 49-45322 and No. 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-58187925.

The fluorine atom content of the resulting diazo resin can be adjusted by changing the molar ratio of these cocondensation components.

At that time, the molar ratio of the aromatic compound having a fluorine atom and the aromatic diazonium compound was 1:0.1-0.1.
: 1 i is 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 fluorine atom and the aromatic diazonium compound to the active carbonyl compound is usually 1:0.6 to 1.5, preferably 1:0.7 to
A diazo cocondensation resin can be obtained by charging 1 and 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 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 θ to 5
It is 0°C.

Above, the synthesis methods (i) to (iii) have been explained in detail in order, but the synthesis method of the fluorine atom-containing diazo resin of the present invention is not limited to (i) to (iii), and for example, , the following methods (iv), (v), etc. may be used.

(iv) A condensation reaction between an aromatic diazonium compound having a fluorine atom and an aldehyde or ketone having a fluorine atom or an active carbonyl compound thereof.

(v) A cocondensation reaction between an aromatic diazonium compound, an aromatic compound having a fluorine atom, and an aldehyde or ketone having a fluorine atom, or an active carbonyl compound thereof.

The weight average molecular weight of the diazo resin used in the present invention is approximately 5
A range of 00 to 100,000 is suitable, preferably a range of about L000 to 10,000.

The counter anion of the diazo resin used in the present invention is
It contains an anion that 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, chlorinated aqueous acid, etc. , 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 semi-acids. Esters, fluorocarboxylic acids such as arsonic acid, phosphinic acid, trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoroboric acid, hexafluorophosphoric acid, perchloric acid, as well as aliphatic and aromatic sulfonic acids, such as methane. Sulfonic acid, fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonyl Phenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, diaminophenoxy-
3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzene Sulfonic acid, 2,5
Dichlorobenzenesulfonic acid, sulfosalicylic acid, 2.
5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-〇-toluenesulfonic acid,
2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-nichloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid , dodecyloxybenzenesulfonic acid, 2-methoxy4-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-I-sulfonic acid, naphthalene-2-sulfonic acid, 1.
8-dinitronaphthalene 3.6-disulfonic acid, 4.4
'-Diazidostilbene-3,3'-disulfonic acid, I
, 2-naphthoquinone-2-diazide-4-sulfonic acid,
Included are anions of 1.2-naphthoquinone-2-diazido-5-sulfonic acid and 1.2-naphthoquinone-1-diazido-4-sulfonic acid, or a mixture of these anions. Particularly preferred among these anions are hexafluorophosphoric acid, methanesulfonic acid, dibutylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid,
Or it is an anion of 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid.

The diazo resin used in the present invention can also be used in combination with conventional diazo resins that do not contain fluorine atoms. As a representative example, US Patent No. 267949
No. 8, No. 3050502, No. 3311605,
and a condensate of 4-diazodiphenylamine and formaldehyde as described in each specification of 3277074. Also, JP-A-1-10245
No. 6, No. 1-102457, No. 1-245246,
It may be used in combination with a diazo resin having an alkali-soluble group or a diazo resin having a phosphorus oxygen acid group described in Patent Publications No. 2-66 and No. 2-29650. The mixing molar ratio of the diazo resin having a fluorine atom and the diazo resin not containing a fluorine atom is 1:0 to 20, preferably 1:α to 10.

Next, a synthesis example of the diazo resin of the present invention will be shown.

Mu 1 (diazo 1) 2.3,5.6-tetrafluoro-4-diazodiphenylamine hydrogen sulfate 36.5 g (0,100 mol
) was dissolved in 90 ml of 96% sulfuric acid. To this, 3.16 g (0,100 g) of rose formaldehyde (95%)
mol) and stirred at 5°C for 3 hours. Then,
The reaction solution was poured into 1.5 ml of ice water with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with water to give 2,3,5,6-tetrafluoro-4-
A hydrogen sulfate salt of a condensate of diazodiphenylamine and formaldehyde was obtained.

Add the above condensate to 200 ml of methyl ethyl ketone (MEK).
To? 2-methoxy-4hydroxy-5-
Henzoyl Sodium Henzensulfonate 39.6 g
(0,120 mol) of water 600 m! ! The solution was added with vigorous stirring. After stirring for 30 minutes and standing still, the mixture separated into two layers. This upper layer was poured into water 21 with stirring, and the yellow precipitate formed was collected by filtration and dried.
2-methoxy-4-hydroxy-condensate of tetrafluoro-4-diazodiphenylamine and formaldehyde
41 g of 5-benzoylbenzenesulfonate was 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 (GPC) and found to be 2,420.

Entering 2 (diazo 2 people) 4-diazo-4'-perfluorooctyloxydiphenylamine hydrogen sulfate 36.4 g (0,050 On
+ol) was dissolved in 9 Qml of 96% sulfuric acid. to this,
Paraformaldehyde (95%) 1.58g (0,
0500 mol) was added thereto, and the mixture was stirred at 5°C for 4 hours.

Next, the reaction solution was poured into ice water 11 with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with water to obtain a hydrogen sulfate salt of a condensate of 4-diazo-4'-perfluorooctyl diphenylamine and formaldehyde.

The above condensate was suspended in a mixture of 200 mf of water and 200 ml of MEK, and 17.4 g (0,0500 mol) of sodium dodecylbenzenesulfonate was added to 300 mf of water.
mJ solution was added with vigorous stirring.

After continuing to stir for 30 minutes, 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'
- 38 g of dodecylbenzenesulfonate of a condensate of perfluorooctyloxydiphenylamine 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 (polystyrene standard) was measured using Gpc.2
It was 100.

Person 3 (Diazo 3 person) 4-diazodiphenylamine hydrogen sulfate 29.3g (
0,100 mol) was dissolved in 70 ml of 96% sulfuric acid.

To this was added 11.8 g of pentafluorobenzaldehyde (0
, 0,600 mol) and stirred at 5°C for 2 hours.

This reaction mixture was then treated with rose formaldehyde (95
%) 1.26 g (0,0400 mol) was added thereto, and the mixture was further stirred at 5°C for 2 hours. Thereafter, the reaction solution was poured into ice water 11 with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered off to obtain a hydrogen sulfate salt of a condensate of 4-diazodiphenylamine and pentafluorobenzaldehyde/formaldehyde.

The above condensate was dissolved in MEK20 Qml, and 41.8 g of sodium dodecylbenzenesulfonate (0,
A solution of 120 mol) in 600 ml of water was added with vigorous stirring. After stirring for 30 minutes, the mixture was allowed to stand and was separated into two layers. Inject this upper layer into water 21 while stirring,
The produced yellow precipitate was collected by filtration and dried to obtain 39 g of dodecylbenzenesulfonate, a condensate of 4-diazodiphenylamine and pentafluorobenzaldehyde/formaldehyde (diazo resin 3 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 (polystyrene standard) was measured using GPC.1
It was 890.

4 (diazo 4 people) 32.3 g (0,100 mol) of 4-diazo-4'-methoxydiphenylamine hydrogen sulfate was dissolved in 96% sulfuric acid 7
It was dissolved in 5ml. In this, perfluorooctanal 3
9.8 g (0,100 mol) was added and stirred at 5°C for 4 hours. Next, the reaction solution was poured into ice water 11 with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered off to obtain a hydrogen sulfate salt of a condensate of 4-diazo-4'methoxydiphenylamine and perfluorooctanal.

MEK200rr+j! of the above condensate! Sodium dioctylnaphthalene sulfonate 55,5
A solution of g (0.120 mol) in 600 ml of water was added with vigorous stirring. After stirring for 30 minutes and standing still, the mixture separated into two layers. This upper layer was poured into water 21 with stirring, and the generated yellow precipitate was collected by filtration and dried to obtain 47 g of dioctylnaphthalene sulfonate of a condensate of 4-diazo-4'-methoxydiphenylamine and perfluorooctanal. (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 (polystyrene standard) was measured using Gpc.
It was 900.

4-diazodiphenylamine hydrogen sulfate 14.7 g (diazo 5)
0,050 On+ol) and 13.0 g of 2,3,4.56-pentafluorodiphenylamine (0,050
0 mol) was dissolved in 70 ml of 96% sulfuric acid. to this,
Paraformaldehyde (95%) 3.16 g (0
, 100 mol) and stirred at 5°C for 2 hours.

Thereafter, the reaction solution was poured into 1.5 ml of ice water with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered off,
A hydrogen sulfate salt of a condensate of 4-diazodiphenylamine/2,3,4,5°6-pentafluorodiphenylamine and formaldehyde was obtained.

The above condensate was dissolved in MEK200mA, and 20.9g of sodium dodecylbenzenesulfonate (0,0
A solution of 600 nl of water (600 o+ol) was added with vigorous stirring. After stirring for 30 minutes and standing still, the mixture separated into two layers. This upper layer was poured into water 21 with stirring, and the yellow precipitate formed was collected by filtration and dried, and the resulting product was dodecylbenzene, a condensate of 4-diazodiphenylamine/2.3,4.5.6-pentafluorodiphenylamine and formaldehyde. 32 g of sulfonate were obtained (diazo resin 5 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 GPC.2
It was 100.

Person 6 (diazo 6) 4-diazodiphenylamine hydrogen sulfate 17.6g (
0,060 On+ol) and l'J-pencyl perfluorooctylamide 21.4 g (0,0400
mol) was dissolved in 90 ml of 96% sulfuric acid. To this, paraformaldehyde (95%) 3.16 g (0.1
01) was added and stirred at 5°C for 3 hours. Next, the reaction solution was poured into 1.5 ml of ice water with stirring to precipitate a yellow precipitate. By filtering this yellow precipitate and washing with water, 4-diazodiphenylamine/N
-Pendyl A condensate of perfluorooctylamide and formaldehyde was obtained.

The above condensate was suspended in 300 ml of MEK, and 25.1 g of sodium dodecylbenzenesulfonate (0,0
A solution of 72 On+ol) in 600 ml of water was added with vigorous stirring. After stirring for 30 minutes, the mixture was allowed to stand and was separated into two layers. This upper layer is poured into water 21 with stirring, and the generated yellow precipitate is filtered and dried.
38 g of dodecylbenzenesulfonate, a condensate of diazodiphenylamine/N-hensyl perfluorooctylamide 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 (polystyrene standard) was measured using GPC.2
It was 270.

The diazo resin used in the present invention is preferably used in combination with an alkali-soluble or swellable polymer compound as a binder resin.

As this polymer compound, the following (usually 2 to 2
A copolymer having a molecular weight of 0,000,000,000 is mentioned.

(11 Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes having an aromatic hydroxyl group, such as N-(4-
hydroxyphenyl)acrylamide or N-(4-hydroxyphenyl)methacrylamide, o-, m-, p
-hydroxyphenylacrylate or methacrylate, o -mp-hydroxystyrene, (2) m-aminosulfonylphenyl methacrylate,
Unsaturated sulfonamides such as N-(p-aminosulfonylphenyl)methacrylamide, N-(p-aminosulfonylphenyl)acrylamide, N-(p-toluenesulfonyl)methacrylamide, (3) Acrylic acid having an aliphatic hydroxyl group esters and methacrylic esters, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (4) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, (5) methyl acrylate , ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (6) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate,
Substituted methacrylates such as 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (7) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (8) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (9) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, αe styrene, α-methylstyrene, methylstyrene, chloromethylstyrene Styrenes such as αυ methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. @ Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, 031N-vinylpyrrolidone, N-vinylcarbazole , 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., maleimide, N-acryloyl acrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N-(p-chlorohendiyl)methacrylamide, etc. Imide.

Furthermore, a monomer that can be copolymerized with the above-mentioned hexamer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

Particularly suitable polymer compounds include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl acrylate as described in JP-A-50118802. - multi-component copolymers of hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, acrylic acid or methacrylic acid and optionally other copolymerizable monomers, such as those described in JP-A-53-120903; Acrylic acid or methacrylic acid which has a hydroxyl group at the end and is esterified with a group containing a dicarboxylic acid ester residue, acrylic acid or methacrylic acid and, if necessary, a multi-component copolymerization with other copolymerizable monomers. A monomer having an aromatic hydroxyl group (for example, N
-(4-hydroxyphenyl)methacrylamide, etc.)
, a multicomponent copolymer of acrylic acid or methacrylic acid and optionally other copolymerizable monomers, JP-A-56-4
A multi-component copolymer of alkyl acrylate, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid as described in Publication No. 144, EP-330
Examples include multi-component copolymers having sulfonamide groups described in 239(A2). In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. In addition, Japanese Patent Publications No. 54-19773, Japanese Patent Publication No. 57-94747, Japanese Patent Application Publication No. 60-182437, Japanese Patent Application Publication No. 62-58242, Japanese Patent Application Publication No. 62-123452, Japanese Patent Publication No. 62-123453 disclose polyvinyl acetal and polyurethane solubilized with alkali. , Japanese Patent Application No. 1-171734 are also useful.

Examples of solvents used when synthesizing such polymeric compounds include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1- Methoxy-2-propertool, 1-
Examples include methoxy-2-propyl acetate, N,N-dimethylformamide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.

These solvents may be used alone or in combination of two or more.

These polymer compounds may be used alone or in combination.

Further, if necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, Soborafuku resin, natural resin, etc. may be added.

The polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. Further, the photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

Next, a synthesis example of the above polymer compound will be shown.

(Synthesis of Polymer Compound 1) p-Aminobenzenesulfonamide 170, . 2
g (1,O饋o1) and tetrahedral o7 run 700
d was added and stirred under an ice water tower. 52.3 g (0.5 mol) of methacrylic acid chloride was added dropwise to this mixture using a dropping funnel over about 1 hour. After the dropwise addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and further stirred for 1 hour while heating to 60° C. using an oil bath. After the reaction was completed, the reaction mixture was poured into 3jl' of water with stirring,
After stirring for 30 minutes, a white solid of N-(p-aminosulfonylphenyl) methacrylamide was obtained by filtration. This white solid can be purified by recrystallization from a mixed solvent of 7 tons of ethanol (
Yield 39.3g).

Next, N-(p-aminosulfonylphenyl)methacrylic)Li7mide 4.57 g (0,0192 mol
), acrylonitrile 2.55 g (0,0480 m
o! ), methacrylic acid 1.66 g (0,0192
mol), ethyl acrylate 11.3 g (0,1
136+eol), 0.41 g of α3α' azobisisobutyronitrile and N.

25 g of N-dimethylformamide was placed in a 100-Mitsuro flask equipped with a stirrer and a cooling tube, and stirred for 5 hours while warming to 64°C. This reaction mixture was added to water 21 with stirring, stirred for 30 minutes, filtered, and dried to give 1
6 g of polymer compound 1 was obtained. The weight average molecular weight (polystyrene standard) of this polymer compound 1 was determined by GPC.
When measured, it was 35,000.

(Synthesis of polymer compound 2) N-(p-aminosulfonylphenyl) methacrylamide 4.57 g (0,0192 mol), 2-hydroxyethyl methacrylate 6.25 g (0,0
480 mol), methacrylic acid 1.66 g (0
, 0192 mol), ethyl acrylate 11.36
g (0,1136 mol), α,α'-azobisisobutyronitrile 0.41 g and N,N-dimethylformamide 29 g in a 100W1 equipped with a stirrer and a cooling tube.
The mixture was placed in a three-piece flask and stirred for 5 hours while warming to 64°C. This reaction mixture was poured into water 21 with stirring, and 30
After stirring for a minute, filtration and drying yielded 20 g of polymer compound 2. By GPC, this polymer compound 2
The weight average molecular weight (polystyrene standard) was measured and found to be 44,000.

(Synthesis of polymer compound 3) N-(4-hydroxyphenyl) methacrylamide 18
g, acrylonitrile 13g1 hensyl acrylate 6
6 g 1 methacrylic acid 8.6 g and azobisisobutyronitrile 1.642 g acetone-methanol:
1 Mixed solution 112w & 60℃ after replacing with nitrogen.
It was heated for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 88 g of polymer compound 3.

When the molecular weight of this polymer compound 3 was measured by GPC, the weight average molecular weight (polystyrene standard) was 75,
It was 000.

(Synthesis of polymer compound 4) 2-hydroxyethyl methacrylate 50.0 g, acrylonitrile 20 g 1 methyl methacrylate 25 g,
A mixture of 5 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise over 2 hours to 300 g of ethylene glycol monomethyl ether heated to 100°C. After the dropwise addition was completed, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, the mixture was diluted with methanol and poured into water 51 with stirring, and the white precipitate that had formed was collected by filtration and dried to obtain 90 g of polymer compound 4.

When the molecular weight of this polymer compound 4 was measured by GPC, the weight average molecular weight (polystyrene standard) was 65,
It was 000.

(Synthesis of Polymer Compound 5) 40 g (0,298 mol) of 2,2-bis(hydroxymethyl)propionic acid and 100 g of acetic anhydride were placed in a 500-meter flask equipped with a stirrer, a cooling tube, and a dropping funnel.
Add N& and stir on an ice water bath. 100w1 of pyridine was added dropwise to this mixture using a dropping funnel over about 30 minutes. After dropping, remove the ice water bath and place in an oil bath.
The mixture was stirred for 2 hours while heating to 60°C. After the reaction was completed, hydrochloric acid was added to make the mixture acidic, and the mixture was extracted with chloroform using a separating funnel. After washing the chloroform layer with water, it was dehydrated with anhydrous sodium sulfate. By distilling off the solvent from this chloroform solution under reduced pressure, 2
, 57 g of a white solid of 2-bis(acetoxymethyl)propionic acid was obtained.

Next, 30 g (0,137+wol) of 2,2-bis(acetoxymethyl)propionic acid and 20 d of thionyl chloride were added to a 300 d tube equipped with a stirrer, a cooling tube, and a dropping funnel.
The mixture was placed in a Mitsuro flask and stirred for 2 hours while heating to 80°C.

After the reaction was completed, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and then the reaction product was sufficiently cooled by placing it in an ice water bath. A mixture of 46.6 g (0,274 mol) of p-aminobenzenesulfonamide and 150 g of tetrahydrofuran was added dropwise to this reaction product using a dropping funnel over about 1 hour. After dripping, in an oil bath,
The mixture was stirred for 2 hours while heating to 60°C. After the reaction, the reaction mixture was poured into water 21 with stirring, stirred for 30 minutes, and filtered to obtain a white solid of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide. Obtained. This white solid can be purified by recrystallization from ethanol (yield: 26 g).

Next, 22 g of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)henzensulfonamide
(0,06+wol), sodium hydroxide 4.8g (0
, 12 mol), 50 - of ethanol, and 50 - of water were placed in a 300w1 Mitsuro flask equipped with a stirrer and a cooling tube, and heated under reflux for 2 hours. This reaction mixture was added to water 11 with stirring, stirred for 30 minutes, and then filtered to obtain a white image of p-1,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide.

This white compound can be purified by recrystallization from ethanol (yield: 11 g).

Next, 3.44 g of p-(1,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide
(0,012+++ol), 2,2-dihydroxymethylpropionic acid 1.07 g (0,008 mo
l), 4.4'-diphenylmethane diisocyanate 5
26 g (0,021 mol) and 18 g of N,N-dimethylacetamide were placed in a 100-Mitsuro flask equipped with a stirrer and a cooling tube, and stirred for 4 hours while heating to 100°C. The reaction mixture was cooled and diluted with methanol 5N.
1 was added and stirred for a while, then poured into 500 g of water with stirring, and stirred for 30 minutes. The precipitate was filtered and dried to obtain 9 g of white solid polymer compound 5. The weight average molecular weight (polystyrene standard) of this polymer compound 5 was measured by GPC and found to be 64,000.

(Synthesis of Polymer Compound 6) 98.5 g of 0-aminobenzyl alcohol (
Add 0.8 mol) and 500 m of acetone, and add NaCl
- Stirred on water bath. A solution of 27.5 g (0.1 mol) of m-benzenedisulfonyl chloride dissolved in 20 (ld) acetone was added dropwise into this flask using a dropping funnel over a period of about 1 hour. After the addition was complete, the NaCl ice bath was removed. The mixture was stirred at room temperature for 2 hours. After the reaction, most of the acetone was distilled off under reduced pressure, and the mixture was poured into water 11 with stirring, and further acidified with hydrochloric acid.

The precipitate was collected by filtration and dissolved in an aqueous sodium hydroxide solution. After filtering off insoluble materials, the filtrate was placed in a separating funnel and washed twice with ethyl acetate. The aqueous layer was made acidic by adding hydrochloric acid, and the precipitate was collected by filtration. N by thoroughly washing with water and drying.

A solid of N'-bis(O-hydroxymethylphenyl)benzene-m-disulfonamide was obtained (yield: 30.6 g).
).

Next, N,N'-bis(0-hydroxymethylphenyl) was added to a 100i Mitsuro flask equipped with a stirrer and a cooling tube.
Benzene-m-disulfonamide 6,28 g (0
,014 mol), 2,2-dihydroxymethylpropionic acid 0.80 g (0,006 mol), 4°4'
-diphenylmethane diisocyanate 5.26g (0
, 021 mol) and 18 g of N,N-dimethylacetamide were added thereto, and the mixture was stirred for 3 hours while heating to 100°C. After the reaction was completed, 10 g of methanol was added and stirred for a while, and then the mixture was poured into 500 g of water with stirring and stirred for 30 minutes. The precipitate was filtered and dried to obtain 12 g of polymer compound 6 as a white solid. The weight average molecular weight (polystyrene standard) of this polymer compound 6 was measured by GPC and found to be 55.000.

Various additives can be further added to the photosensitive composition of the present invention.

For example, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), surfactants (e.g. JP-A-62-170950, JP-A-62-2) to improve coating properties.
26143; fluorosurfactants such as those described in U.S. Pat. No. 3,787.351), membrane flexibility;
Plasticizers to impart wear resistance (e.g. tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), making the image area of the developer visible Pigments such as acridine dyes, cyanine dyes, styryl dyes, triphenylmethane dyes, and phthalocyanines are used as coloring substances for imaging, and other common stabilizers for diazo resins (phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, Boric acid, p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5
-benzoylbenzenesulfonic acid, malic acid, tartaric acid,
Dipicolinic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl- Methyl-pyrazolone sulfonate,
2-phosphonobutane-1,2,4 tricarboxylic acid, ■-
Phosphonoethane-1.2°2-tricarboxylic acid, 1-hydroxyethane-1°1-disulfonic acid, etc.) can be added.

The amount of these additives added varies depending on the purpose of use, but is generally 0.1 to 3% of the total solid content of the photosensitive layer.
It is 0% by weight.

The photosensitive composition of the present invention is dissolved in a suitable organic solvent and coated on a support having a lipophilic surface at a dry coating weight of 0.2 to 10%.
g/m to obtain a photosensitive planographic printing plate. The concentration of the photosensitive composition during application is 1 to 5.
A range of 0% by weight is desirable. The coating solvent used is methyl cellosolve, ethyl cellosolve, 1
-Methoxy-2-propatol, dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, methyl lactate, ethyl lactate, ethylene dichloride, cyclohexanone , dioxane, tetrahydrofuran and the like. A mixed solvent of these or a mixed solvent obtained by adding a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or polymer compound to these solvents or mixed solvents is also suitable. When a photosensitive liquid dissolved in these solvents is applied to a support and dried, it is desirable to dry at 50°C to 120°C.

The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature.

Examples of the support to which the photosensitive composition of the present invention is applied include paper,
Various materials such as plastics and metals can be used, but when used in photosensitive planographic printing plates, hydrophilic aluminum plates are particularly preferred.

The surface of the aluminum plate can be processed by mechanical methods such as wire brush graining, brush graining in which the surface is roughened with a nylon brush while pouring slurry of abrasive particles, ball graining, or by mechanical methods such as HF, AlIC &, H (where l is an etchant). After graining the surface by chemical graining, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining that combines these surface roughening methods, etching treatment with acid or alkali as necessary. Then, the aluminum is anodized in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a DC or AC power source to form a strong passive film on the aluminum surface. is preferred.

Although such a passive film itself makes the aluminum surface hydrophilic, if necessary, U.S. Patent No. 2.714,
No. 066 specification and U.S. Patent No. 3. ．． 18L461 (sodium silicate, potassium silicate), potassium fluorozirconate treatment as described in U.S. Pat. No. 2,946,638,
Phoshomolybdate treatment as described in U.S. Patent No. 3,201,247, British Patent No. 1,108,5
Alkyl titanate treatment described in German Patent No. 59, polyacrylic acid treatment described in German Patent No. 1,091,433, German Patent No. 1,134,093 and British Patent No. 1. Polyvinylphosphonic acid treatment described in , 230.447, Japanese Patent Publication No. 44-64
Phosphonic acid treatment described in No. 09, phytic acid treatment described in U.S. Patent No. 3,307,951, JP-A-58-16893 and JP-A-58-1
Treatment with a salt of a hydrophilic organic polymer compound and a divalent metal described in each publication of No. 8291, JP-A-59-1
Particularly preferred are those which have been subjected to hydrophilic treatment by undercoating with a water-soluble polymer having a sulfonic acid group as described in Japanese Patent No. 01651. Other hydrophilic treatment methods include silicate electrodeposition as described in US Pat. No. 3,658,662.

Moreover, it is also preferable to perform a sealing treatment after graining and anodizing. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like, followed by development with an aqueous alkaline developer, provides a negative relief image on the original.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes,
Examples include ultraviolet rays and laser beams.

The developer used for developing the photosensitive composition according to the present invention contains a specific organic solvent, an alkaline agent, and water as essential components. The specific organic solvent herein refers to the non-exposed area (
An organic solvent that can dissolve or swell the non-image area) and has a solubility in water of 10% by weight or less at room temperature (20°C). Such organic solvents only need to have the above-mentioned characteristics, and are not limited to the following, examples of which include ethyl acetate, propyl acetate, and acetic acid. Carboxylic acid esters such as butyl, amyl acetate, hensyl acetate, ethylene glycol motuputyl acetate, butyl lactate, butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; engineered ethylene glycol monobutyl ether, ethylene glycol Alcohols such as benzyl ether, ethylene glycol monophenyl-thyl, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; methylene dichloride, ethylene dichloride, mono These include halogenated hydrocarbons such as chlorobenzene. These organic solvents may be used alone or in combination. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developing solution is approximately 1 to 20% by weight, and particularly preferable results are obtained when the content is 2 to 10% by weight.

On the other hand, the alkaline agents contained as essential components in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium dibasic or tertiary phosphate, or Inorganic alkaline agents such as ammonium salts, sodium metasilicate, sodium carbonate, ammonium, etc., (B) mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, diisopropylethylamine, n-butylamine, mono, di or triethanol Examples include organic amine compounds such as amines, mono-, di- or tri-isopropanolamines, ethyleneimine, and ethylenediamine.

The content of these alkaline agents in the developer is usually 0.
05 to 4% by weight, preferably 0.5 to 2% by weight.

Further, in order to further improve storage stability, rigidity resistance, etc., it is preferable to include a water-soluble sulfite in the developer. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the image solution composition is usually 0.05 to 4% by weight, preferably 0.11 to 1% by weight.

If such a developer is brought into contact with the photosensitive composition after development exposure or rubbed with a pad containing the developer, the photosensitive composition layer will be removed after 5 to 40 seconds at approximately room temperature to 40°C. The photosensitive composition in the non-exposed areas is completely removed without adversely affecting the exposed areas, and a photosensitive lithographic printing plate is obtained.

〔Effect of the invention〕

The photosensitive composition of the present invention has good developability when developing non-image areas, does not cause printing stains, and does not produce any stains after development, even when imagewise exposed after long-term storage in a humid place. It is possible to provide a lithographic printing plate with excellent film strength in the image area and good stiffness resistance. Furthermore, the photosensitive composition of the present invention has improved solubility in organic solvents and improved storage stability.

[Actual] L pull 1 Aluminum plate with a thickness of 0.24n and a nylon brush 4
The surface was grained using an aqueous suspension of 00 mesh pumice stone, and then thoroughly washed with water. 10% of this
After etching by immersing in an aqueous sodium hydroxide solution at 70°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, the electrochemical surface roughening method described in JP-A-53-67507, i.e. , VA = 12.7 V, Vc = 9, using a sinusoidal alternating waveform current of I, electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution at an anode special electricity amount of 160 chrome/dm''. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted for 2 minutes at 55°C, and then anodized in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g/m. 3% of sodium silicate in °C
It was immersed in an aqueous solution for 1 minute, washed with water and dried. The photosensitive solution shown below was applied to the aluminum plate obtained as described above using a wheeler, and dried at 80° C. for 2 minutes. The dry weight was 2.0 g/nf.

Further, the diazo resin and polymer compound used in the photosensitive solution shown below are shown in Table 1.

(Photosensitive liquid) Next, as a comparative example, a photosensitive liquid using the following diazo resin was applied to the above photosensitive liquid and dried. Dry weight is 2.0g/
It was rrr.

(Diazo resin used in Comparative Example 1.2) Comparative Example 1 Dodecylbenzenesulfonic acid salt of a condensate of 4-diazodiphenylamine (0.1 mol) and formaldehyde (0.1 mol) Comparative Example 2 4-diazodiphenylamine (0.05 mol), phenoxyacetic acid (0.05 mol) and formaldehyde (0.1
dodecylbenzenesulfonate (evaluation of printing stains and printing durability), a condensate with mol) [Evaluation of printing stains and printing durability] Each of the photosensitive lithographic printing plates thus obtained was exposed to a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m for 1 minute. After exposing the image and immersing it in the following developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed area to obtain lithographic printing plates (1) to (XV) with bright blue images. .

(Developer) Each printing plate was printed on high-quality paper with a commercially available ink using a KOR printing machine manufactured by Heidelberg.

The printing stain and stiffness resistance of the lithographic printing plates (I) to (XV) were examined, and the results were as shown in Table 1.

On the other hand, each photosensitive lithographic printing plate obtained was subjected to forced fatigue for one week at a temperature of 45° C. and a humidity of 75%, and then subjected to image exposure, development, and printing in the same manner. The printing stains and printing durability of the lithographic printing plates (1) to (XV) subjected to forced fatigue in this manner were similarly examined, and the results are as shown in Table 1.

As can be seen from Table 1, the lithographic printing plate (
1) to (l1lr) give images with no printing stains and excellent rigidity resistance during printing before forced fatigue, but there is no noticeable difference compared to the comparative examples (XIV) and (XV). . However, the lithographic printing plates (1) to (
XI[I] gives an image that does not cause printing stains and does not have a decrease in rigidity even when subjected to image exposure and aqueous development before forced fatigue, and compared with the comparative example (XIV
) and (XV).

That is, the image forming method of the present invention is very excellent in that even when the printing plate is subjected to forced fatigue and then processed, printing stains do not occur during printing and images are produced without deterioration in printing durability.

Claims (1)

[Claims] A photosensitive composition comprising a polymer compound and a diazo resin having a fluorine atom in its main skeleton.