JPH05158231A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the photosensitive composition for forming a planographic printing plate superior in developability to an aqueous alkaline developing solution and good in photocross-linking performance and high in printing resistance of the obtained printing plate. CONSTITUTION:The photosensitive resin composition for forming the planographic printing plate comprises a diazo resin synthesized through the courses of (1)-(3), a polyurethane resin substituted by acidic hydrogen atoms and a modified polyvinyl acetal. In (1), an oligomer is synthesized by ring- opening polymerization reaction of a compound having 2 oxirane rings in one molecule with a compound represented by formula in which each of R<1> and R<2> is H, alkyl alkoxy, or halogen; W is a single bond or a divalent organic group; and Y is a group convertible into an amino group. In (2), the substituent Y of the oligomer is converted into the amino group. In (3), this amino group is converted into a diazonium salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-working photosensitive composition, more specifically, a photosensitive composition which can be developed with an aqueous alkaline developer, has good photocrosslinking property, and has high printing durability. It relates to a sex lithographic printing plate.

[0002]

2. Description of the Related Art A photosensitive lithographic printing plate is generally prepared by coating a photosensitive composition on a support such as an aluminum plate and irradiating it with an actinic ray such as an ultraviolet ray through a negative image to polymerize the exposed portion. Alternatively, it may be crosslinked to make it insoluble in a developing solution, and the non-irradiated areas are eluted in the developing solution, and each part repels water to receive an oil-based ink, and water to repel an oil-based ink. It is obtained by setting the non-image portion.

In this case, the photosensitive composition is
Diazo resins such as condensates of p-diazodiphenylamine and formaldehyde have been widely used. The method for producing the diazo resin is described in, for example, US Pat.
3,050,502, 3,311,605 and 3,277,074. In the diazo resin, when the counter anion of the diazonium salt is an inorganic anion such as a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid or a double salt with zinc chloride, it is water-soluble and unstable to moisture. Therefore, there is a problem that storage stability deteriorates. Therefore, in order to improve storage stability, a water-soluble diazo resin is used as a water-insoluble resin by reacting it with an organic coupling agent such as a phenolic hydroxyl group-containing aromatic compound, acidic aromatic compound or acidic aliphatic compound. The method is described in Japanese Patent Publication No. 47-1167 and U.S. Pat. No. 3,300,309.

However, this type of diazo resin is not sufficiently soluble in organic coating solvents such as alcohols, ketones and glycol ethers. Therefore, in order to make the diazo resin insoluble in water and soluble in organic solvents, halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid, and perhalogenic acids such as perchloric acid and periodic acid are used as counter anions. Use of resin is disclosed in JP-A-54-9.
No. 8613 and No. 56-121031.

Further, regarding the use of an anionic surfactant, that is, a diazo resin having a sulfonic acid having a long-chain alkyl group as a counter anion, JP-A Nos. 58-209733 and 62-175731 disclose the same. 63-2626
No. 43 publication. However, since these diazo resins have low molecular weights, when a lithographic printing plate obtained using these diazo resins is applied to a printing machine, a problem that a large number of printed sheets cannot be obtained, that is, a problem that printing durability is low was there.

The composition of the photosensitive layer of the photosensitive lithographic printing plate using the diazo resin is a diazo resin alone as described in US Pat. No. 2,714,066,
In other words, one that does not use a binder is disclosed in, for example, JP-A-50-
As described in 30604, it can be classified into a mixture of a binder and a diazo resin, but in recent years, many of photosensitive lithographic printing plates using a diazonium compound have high printing durability. It is composed of a diazonium compound and a polymer that serves as a binder to hold it.

As such a photosensitive layer, JP-A-50-3 is used.
As described in JP-A-0604, a so-called alkali development type in which an unexposed portion is removed (developed) by an aqueous alkaline developer and a so-called solvent development type in which an unexposed portion is removed by an organic solvent-based developer are known. However, the alkali development type is drawing attention from the viewpoint of occupational safety and health. Binders useful for such an alkali-developable photosensitive layer are described in JP-A-50-30.
Polymers prepared by copolymerizing 2-hydroxyethyl (meth) acrylate with a carboxylic acid-containing monomer such as methacrylic acid as described in US Pat. No. 4,604,058, as described in US Pat. There is one in which a carboxylic acid is introduced into a polymer by reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride, but the obtained polymer has poor abrasion resistance because of its structure. From the photosensitive lithographic printing plate containing such a binder in the photosensitive layer, only a lithographic printing plate having low printing durability was obtained. On the other hand, polyvinyl acetal has a drawback that it forms a tough film and has abrasion resistance, but only an organic solvent developing type photosensitive lithographic printing plate can be obtained.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to overcome the above-mentioned drawbacks, to provide a novel photosensitive composition having excellent developability in an aqueous alkaline developer, good photocrosslinking property, and high printing durability. Is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that, as a diazo resin, a crosslinking reaction between an epoxy compound and an amino compound containing a specific primary amino group-containing aromatic compound is carried out. After that, a novel diazo resin synthesized by converting a substituent to a diazonium group is used, and as a binder, a polyurethane resin having a substituent having an acidic hydrogen atom or a modified polyvinyl acetal resin is used as a photosensitive composition. As a result, they have found that the above object can be achieved, and completed the present invention.

That is, the present invention is characterized by containing a diazo resin synthesized by the following procedures (1) to (3) and a polyurethane resin having a substituent having an acidic hydrogen atom or a modified polyvinyl acetal resin. It is a photosensitive composition. Synthetic procedure of diazo resin (1) An oligomer is synthesized by a ring-opening polymerization reaction of a compound having two oxirane rings in one molecule and an amino compound containing a compound represented by the following general formula (I).

[0011]

[Chemical 2]

In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, W represents a single bond or any divalent organic group, and Y is convertible into an amino group. An optional substituent is shown. (2) The substituent Y of the oligomer obtained in (1) is converted to an amino group. (3) The amino group of the oligomer obtained in (2) is converted into a diazonium salt.

The present invention will be described in more detail below. The compound (epoxy compound) containing two oxirane rings (so-called epoxy group) in one molecule according to the present invention can be used as long as it is a compound containing two oxirane rings in one molecule, but is preferably It has a molecular weight of 170 to 1,000. Specifically, for example, compounds represented by the following general formulas (II) to (VII) are particularly preferably used.

[0014]

[Chemical 3]

R ⁹ O- (R ¹¹ -O) _n -R ¹⁰ (V) R ⁹ O-CO-R ¹¹ -CO-R ¹⁰ (VI) R ⁹ -N (R ¹² ) -R ¹⁰ (VII) In the formula, R ³ , R ⁴ , R ⁵ , and R ^{6, which} may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group,
R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group which may have a substituent,
R ⁹ and R ¹⁰ may be the same or different and each is a group having one oxirane ring, preferably a group represented by the following general formula (VIII) or (IX).

[0016]

[Chemical 4]

Further, R ¹¹ represents an alkylene group which may have a substituent, a phenylene group or a cycloalkylene group, n represents a natural number of 1 or more, and R ¹² represents a phenyl which may have a substituent. R ¹³ represents a hydrogen atom or a methyl group. However, the present invention is not limited to these compounds, and any compound having two oxirane rings in one molecule can be used.

Specific examples of these epoxy resins include bisphenol A-epihalohydrin resin (for example, bisphenol A diglycidyl ether) and bisphenol A.
-Butadiene dioxide resin, brominated bisphenol A
-Epihalohydrin resin (eg brominated bisphenol A diglycidyl ether), 4,4'-diglycidyloxydiphenylmethane, 4,4'-diglycidyloxybiphenyl, 4,4'-diglycidyloxy-3,
5,3 ', 5'-tetramethylbiphenyl, 2,2'-
Bis (4-glycidyloxyphenyl) ethane, hydrogenated bisphenol A diglycidyl ether, 2,2'-dimethyl-1,3-propanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4 -Butanediol diglycidyl ether, 1,2-propanediol diglycidyl ether, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, diesterification product of phthalic acid with epihalohydrin, epihalohydrin of hexahydrophthalic acid Diester compounds, diester compounds of tetrahydrophthalic acid with epihalohydrin, diester compounds of 4-methyltetrahydrophthalic acid with epihalohydrin, 3,4-epoxycyclohexyl It can be exemplified Le (3,4-epoxy) cyclohexane carboxylate, and 2- (3,4-epoxy) cyclohexyl -5,1- spiro (3,4-epoxy) cyclohexyl -m- dioxane.

On the other hand, the compound to be reacted with the epoxy resin according to the present invention is an amino compound including the compound represented by the general formula (I). In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, W represents a single bond or any divalent organic group, and Y represents a substituent convertible to an amino group. Show. Preferably R ¹ ,
R ² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
It represents an alkoxy group, a chlorine atom or a bromine atom, W represents a single bond, and Y represents an acylamide group (for example, a formamide group or an acetamide group) or a nitro group. Specific examples of the compound represented by the general formula (I) include 4-aminoacetanilide, 4-aminoformanilide, 4-nitroaniline, 4-amino-2-methoxyacetanilide, 4-amino-2-ethoxyacetanilide, 4 -Amino-2,5-dimethoxyacetanilide, 4-amino-2,5-dibutoxyacetanilide, 4-amino-2
-Methylacetanilide, 4-amino-3-methylacetanilide, 4-amino-3-chloroacetanilide,
4-amino-3-bromoacetanilide, 4-amino-
2-methoxyformanilide, 4-amino-2-propoxyformanilide, 4-amino-2,5-dimethoxyformanilide, 4-amino-3-ethylformanilide, 4-amino-3-bromoformanilide, 3-methoxy -4-nitroaniline, 3-butoxy-4-nitroaniline, 2-methyl-4-nitroaniline, 2-chloro-4-nitroaniline, 2,5-dimethoxy-4-nitroaniline, 4-amino-4 '. Examples thereof include, but are not limited to, -nitrodiphenylamine and 4-acetylamino-4'-aminodiphenylamine.

The diazo resin of the present invention is synthesized by the following method. (1) Ring-opening polymerization reaction of an epoxy compound and an amino compound containing the compound of the general formula (I), that is, the epoxy compound, the compound of the general formula (I) and optionally another amino compound in a suitable solvent ( For example, acetic acid, phenol, water, methanol, ethanol,
Isopropanol, propanol, butanol, 2-methoxyethanol, 1-methoxy-2-propanol,
Acetone, ethyl acetate, methyl ethyl ketone, dimethylformamide, dimethylsulfoxide or a mixture thereof) for a short time, ie, 1 to 20 hours, 0 ° C. to 150 ° C.
An oligomer is formed by reacting at an arbitrary temperature of ° C. In order to shorten the reaction time, higher temperature,
That is, it is preferable to carry out the reaction while heating the solvent under reflux.

At this time, the epoxy compound and the compound of the general formula (I) may be used alone or in combination of two or more kinds. The molar ratio of the epoxy resin and the compound charged is 0.1: 1 to 1: 0.1, preferably 0.1.
It is more preferably 2: 1 to 1: 0.2, and more preferably 1: 1 to 1: 0.5. (2) The substituent Y of the oligomer obtained in (1) is converted to an amino group.

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

The conversion reaction of amino group to diazonium group is carried out according to a known method in a acidic solvent such as hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid, nitrous acid, sodium nitrite,
It is possible by reacting with cerium nitrite, ammonium nitrite and the like. The diazo resin used in the present invention preferably uses as the counter anion an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. The acid forming the counter anion includes
Organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid and sulfonic acids are included, and typical examples are hydrohalic acids such as hydrofluoric acid, hydrochloric acid and bromide. Hydroic acid; sulfuric acid, nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid, inorganic iso- and heteropolyacids,
For example, phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acid or its half ester, arsonic acid, phosphinic acid, fluorocarboxylic acid such as trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoric acid, hexa Fluorophosphoric acid, tetrafluoroboric acid, perchloric acid, and further aliphatic and aromatic sulfonic acids, for example, methanesulfonic acid, fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, Camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, diamylphenoxy-3-p Bread sulfonic acid, dinonyl phenoxy-3-propane sulfonic acid, dibutyl phenoxy -4
-Butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 3-sulfophthalic acid, 4-sulfophthalic acid,
2-sulfoterephthalic acid, 5-sulfoisophthalic acid,
2,5-Dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5 -Nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid , Butylnaphthalenesulfonic acid, Hexylnaphthalenesulfonic acid, Octylnaphthalenesulfonic acid, Butoxynaphthalenesulfonic acid, Dodecyloxynaphthalenesulfonic acid, Dibutylnaphthalenesulfonic acid, Geo Tylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6 -Disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4
-Sulfonic acid, 1,2-naphthoquinone-2-diazide-
Included are the anions of 5-sulfonic acid and 1,2-naphthoquinone-1-diazide-4-sulfonic acid, or a mixture of these anions. Among these anions, particularly preferable ones are hexafluorophosphoric acid, dibutylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, or 2
-Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid anion.

The diazo resin of the present invention further enhances developability and enables development with alkaline water, so that a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus,
It may contain an alkali-soluble group such as a phenolic hydroxyl group. The oxygen acid group of phosphorus is represented by the following general formula
The groups represented by (X) to (XV) are shown.

[0025]

[Chemical 5]

In the formula, R ¹⁴ is a hydrogen atom, R ¹⁵ is a hydrogen atom,
An alkyl group or an aryl group, R ¹⁶ represents a hydrogen atom, an alkyl group or an aryl group. Preferably, R ¹⁵ represents a hydrogen atom, and R ¹⁶ represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. Further, particularly preferable oxygen acid group of phosphorus is a group represented by (X) or (XII). There are the following two methods for introducing the alkali-soluble group. (i) Method of using the compound (I) in combination with a compound represented by the following general formula (XVI) NH ₂ —R ¹⁷ —Z (XVI) In the formula, R ¹⁷ may have a single bond or a substituent. A good alkylene group, a phenylene group, a naphthylene group, a cycloalkylene group or a group in which they are arbitrarily combined by a single bond, an ether bond or the like is shown, Z is a carboxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, It represents an alkali-soluble group such as a hydroxyaryl group which may have a substituent.

Specific examples of the compound represented by the above general formula (XVI) include glycine, alanine, 2-amino-n-butanoic acid, 3-amino-n-butanoic acid, 4-amino-n-butanoic acid, 2 -Amino-iso-butanoic acid, 3-amino-is
o-butanoic acid, norvaline, valine, 6-amino-n-
Caproic acid, isoleucine, leucine, norleucine, 4
-Aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, 3-amino-2-naphthoic acid, 3-amino-1
-Naphthoic acid, sulfamic acid, aminomethanesulfonic acid, taurine, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-phosphorylethanolamine, o-phosphoserine, aminomethylphosphonic acid, 1 -Aminoethylphosphonic acid, 2-aminophenylphosphonic acid, 3-aminophenylphosphonic acid, 4-aminophenylphosphonic acid, 2-
Aminophenol, 3-aminophenol, 4-aminophenol, etc. are mentioned.

The compounds of the general formula (XVI) may be used alone or in combination of two or more. When synthesizing a diazo resin containing an alkali-soluble group, the compound of the general formula (I) and the compound of the general formula (XVI) are mixed and used at an arbitrary ratio. However, if the purpose of containing an alkali-soluble group is to improve the developability with respect to an alkaline developing solution containing an organic solvent as described in JP-A-53-44202, the compound of the general formula (I) and The molar ratio of the compound of the general formula (XVI) is 1: 0.01 to 0.1: 1,
Preferably it is 1: 0.05-0.5: 1, more preferably 1 :.
It is 0.05 to 1: 1. If the purpose of introducing an alkali-soluble group is to develop with alkaline water containing no organic solvent as described in JP-A-62-24263, the molar ratio of both is 0.1: 1-1. : 0.1, preferably 0.2: 1 to 1: 0.2, more preferably 0.5: 1 to 1:
It is 0.5. After the ring-opening polymerization reaction, they can be synthesized in exactly the same manner according to the above-mentioned synthetic procedures (1) to (3) of the diazo resin containing no alkali-soluble group. (ii) As an epoxy compound, an epoxy compound having an alkali-soluble group is used in combination with an epoxy compound not containing an alkali-soluble group, or is used alone. Specific examples of the epoxy compound having such an alkali-soluble group include, for example, US Patent Nos. 2933471 and 29334
No. 72 epoxy resin or a few
-Diglycidyloxypropionic acid, 2,3-diglycidyloxypropyl-1-phosphoric acid, 2,3-diglycidyloxy-1-phosphonic acid, 1,3-diglycidyloxypropyl-2-phosphoric acid, 1, Examples thereof include 3-diglycidyloxy-2-phosphonic acid and 2,3-diglycidyloxypropyl-1-sulfonic acid, but are not limited thereto.

When synthesizing a diazo resin containing an alkali-soluble group, an epoxy compound having an alkali-soluble group is used alone or in combination with an epoxy compound having no alkali-soluble group, and an amino compound containing a compound of the above general formula (I) is used. Used for ring-opening polymerization reaction with compounds. However, if the purpose of introducing the alkali-soluble group is to improve the developability for an alkaline developer containing an organic solvent, the molar ratio of the epoxy compound containing the alkali-soluble group to the epoxy compound containing no alkali-soluble group is 1 : 0.1-0.01, preferably 1: 0.5-0.05: 1, more preferably 1: 1
If the purpose of introducing an alkali-soluble group is to develop with alkaline water containing no organic solvent, the molar ratio of both is 1: 0 to 0.1: 1, preferably 1: 0 to 0.2: 1, more preferably 1: 0 to 0.5: 1
Is. After the ring-opening polymerization reaction, the same synthesis can be performed according to the above-mentioned synthesis (1) to (3) of the diazo resin containing no alkali-soluble group.

If desired, the compound of the general formula (I) and the compound having the alkali-soluble group of the general formula (XVI) may be used in combination. When synthesizing the diazo resin of the present invention, the compound containing 3 or more oxirane rings in one molecule has two compounds in one molecule for the purpose of increasing the molecular weight of the diazo resin in order to further improve printing durability. You may use together with the compound containing an oxirane ring.

Specific examples of the compound containing three or more oxirane rings in one molecule include 1,3,5-triglycidyl isocyanuric acid, phenol novolac type epoxy resin, brominated novolac type epoxy resin, orthocresol novolac. -Type epoxy resin, meta-cresol-type epoxy resin, para-cresol-type epoxy resin, tetrakis (glycidyloxyphenyl) ethane, N, N,
Examples thereof include N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, mN, N-diglycidylaminophenylglycidyl ether, and triglycidyl ether of 2,2-dihydroxymethyl-n-butanol. It is not limited to these.

At this time, the charging ratio of the compound containing three or more oxirane rings in one molecule to the compound containing two oxirane rings in one molecule is arbitrary, but is generally 0 to 50 mol%, preferably 0 to 50 mol%. It is 20 mol%. Further, the total number of moles of the oxirane ring is preferably twice or more that of the compound of the general formula (I). Further, for the purpose of increasing the molecular weight, a compound having two or more amino groups in one molecule may be used in combination with the compound of the general formula (I).

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

At this time, the charging ratio of the compound having two or more amino groups in one molecule to the compound of the general formula (I) is arbitrary, but is generally 0 to 40 mol%, preferably 0.
Is about 20 mol%. Further, the total number of moles of the oxirane ring is preferably 2 times or more that of the primary amine and 1 time or more of that of the secondary amine. The diazo resin of the present invention is
By varying the molar ratio of each monomer and the reaction conditions in the crosslinking reaction, the molecular weight can be obtained as an arbitrary value, but in order to effectively serve the intended purpose of the present invention, the weight average molecular weight is Is about 1000 to 100,0
00 can be used, but preferably about 1,50
Those of 0 to 20000 are suitable.

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

Next, the white solid obtained was mixed with 80 m of ethanol.
l, dissolved in a mixed solvent of 80 ml of water, added concentrated hydrochloric acid, and heated to 75 ° C
The mixture was heated to reflux for 6 hours. By sampling a part of the reaction solution, it was confirmed by NMR and IR spectra that the acetylamide group was converted to an amino group. The reaction solution was ice-cooled and sodium nitrite 6.56
g (0.0950 mol) of 20 ml aqueous solution, the internal temperature of the reaction solution is 1
The solution was slowly added dropwise so as not to exceed 0 ° C. Then, stirring was continued for 30 minutes under ice cooling. Then, the reaction solution is mixed with water 4
Pour into 200 ml of 200 ml MEK (methyl ethyl ketone) and, with vigorous stirring, 32.7 g (0.0950 mol) of water 100 of sodium di-n-butylnaphthalenesulfonate.
The ml solution was injected and stirring was continued for 30 minutes. After the reaction was completed, the reaction solution was allowed to stand, and it was separated into two layers. This upper layer is water 1000
When poured into ml with vigorous stirring, a yellow-green solid precipitated. This was filtered, washed with water and dried to obtain a diazo resin (diazo resin 1 of the present invention).

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

The weight average molecular weight was 4,260. (Synthesis Example 3) A diazo resin was obtained in the same manner as in Synthesis Example 1 except that 61.8 g (0.0950 mol) of tetrabromobisphenol A diglycidyl ether was used instead of the ethylene glycol diglycidyl ether in Synthesis Example 1. (Diazo resin 3 of the present invention).

The weight average molecular weight was 4780. (Synthesis Example 4) 871 g (0.0500 mol) of ethylene glycol diglycidyl ether was used instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1.
l) and bisphenol A diglycidyl ether 16.6
It was synthesized in exactly the same manner as in Synthesis Example 1 except that g (0.0500 mol) was used (the diazo resin 4 of the present invention).

The weight average molecular weight was 7320. (Synthesis example 5) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether
And bisphenol A diglycidyl ether 16.6g
(0.0500 mol) was used, and 31.4 g (0.0900 mol) of sodium dodecylbenzenesulfonate was used in place of sodium dibutylnaphthalenesulfonate. Synthesis was conducted in the same manner as in Synthesis Example 1 (diazo resin of the present invention). 5).

The weight average molecular weight was 7320. (Synthesis Example 6) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
l), 16.6 g of bisphenol A diglycidyl ether
Synthesis Example 1 except that (0.0500 mol) was used, and 18.4 g (0.100 mol) of potassium hexafluorophosphate was used instead of sodium dibutylnaphthalenesulfonate.
Was synthesized in exactly the same manner as the above (the diazo resin 6 of the present invention).

The weight average molecular weight was 7320. (Synthesis Example 7) 4-aminoacetanilide 12.0 g (0.0800 mol) 4-aminobenzoic acid 2.19 g instead of 4-aminoacetanilide 0.0950 mol in Synthesis Example 1
Synthesis was carried out in exactly the same manner as in Synthesis Example 1 except that (0.0160 mol) was used (the diazo resin 7 of the present invention).

The weight average molecular weight was 5,300. (Synthesis Example 8) 4-aminoacetanilide was replaced by 4-aminoacetanilide in place of 0.0950 mol of Synthesis Example 1.
6.01 g (0.0400 mol), 4-aminobenzoic acid 7.95
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that g (0.05800 mol) was used (the diazo resin 8 of the present invention).

The weight average molecular weight was 5,250. (Synthesis Example 9) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
l), 16.6 g of bisphenol A diglycidyl ether
(0.0500 mol) was added to 4-aminoacetanilide 0.09
4-aminoacetanilide 11.3 g instead of 50 mol
(0.0750 mol), 4-aminobenzoic acid 2.74 g (0.0
Synthesis was carried out in exactly the same manner as in Synthesis Example 1 except that 200 mol) was used (the diazo resin 9 of the present invention).

The weight average molecular weight was 7,110. (Synthesis Example 10) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 8.71 g (0.0500 mol) of ethylene glycol diglycidyl ether was used.
l), 16.6 g of bisphenol A diglycidyl ether
(0.0500 mol) was added to 4-aminoacetanilide 0.09
5.71 g of 4-aminoacetanilide instead of 50 mol
(0.0380 mol), 4-aminobenzoic acid 8.23 g (0.0
Synthesis was carried out in exactly the same manner as in Synthesis Example 1 except that 600 mol) was used (the diazo resin 10 of the present invention).

The weight average molecular weight was 7,280. (Synthesis example 11) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis example 1, 10.5 g (0.0600 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 13.3g
(0.0400 mol), instead of 4-aminoacetanilide, 6.65 g of 4-amino-2-methoxyformanilide
(0.0400 mol), glycine 4.13 g (0.0550 mol)
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that was used (Diazo resin 11 of the present invention).

The weight average molecular weight was 6410. (Synthesis Example 12) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 7.00 g (0.0400 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 19.9g
(0.0600 mol) was added to 4-aminoacetanilide 0.09
4-aminoacetanilide 11.3 g instead of 50 mol
(0.0750 mol), aminomethanesulfonic acid 2.22 g
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that (0.0200 mol) was used (the diazo resin 12 of the present invention).

The weight average molecular weight was 4830. (Synthesis Example 13) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 7.00 g (0.0400 mol) of ethylene glycol diglycidyl ether was used.
l), bisphenol A diglycidyl ether 19.9g
(0.0600 mol) was added to 4-aminoacetanilide 0.09
5.71 g of 4-aminoacetanilide instead of 50 mol
(0.0380 mol), aminomethanesulfonic acid 6.44 g
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that (0.0580 mol) was used (the diazo resin 13 of the present invention).

The weight average molecular weight was 5020. (Synthesis Example 14) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 12.2 g of ethylene glycol diglycidyl ether (0.0700 mol) was used.
l), tetrabromobisphenol A diglycidyl ether 19.5 g (10.0300 mol), 4-aminoacetanilide 10.5 g (0.0700 mol) instead of 4-aminoacetanilide 0.0950 mol, o-phosphorylethanolamine 3. Synthesis was carried out in exactly the same manner as in Synthesis Example 1 except that 53 g (0.025 mol) was used (Diazo resin 1 of the present invention 1
4).

The weight average molecular weight was 5,470. (Synthesis Example 15) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 12.2 g of ethylene glycol diglycidyl ether (0.0700 mol) was used.
l), bisphenol A diglycidyl ether 9.97g
(0.0300 mol) was added to 4-aminoacetanilide 0.09
6.76 g of 4-aminoacetanilide instead of 50 mol
(0.045 mol), o-phosphonylethanolamine 7.3
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that 4 g (0.052 mol) was used (diazo resin 15 of the present invention).

The weight average molecular weight was 5530. (Synthesis Example 16) Instead of 0.10 mol of ethylene glycol diglycidyl ether in Synthesis Example 1, 13.9 g (0.0800 mol) of ethylene glycol diglycidyl ether was used.
l) and 4,4-bis (4-glycidyloxyphenyl) pentanoic acid (7.81 g, 0.0200 mol) were used, and the synthesis was carried out in the same manner as in Synthesis Example 1 (the diazo resin 1 of the present invention 1
6).

The weight average molecular weight was 4920. (Synthesis Example 17) 4,4-bis (4-glycidyloxyphenyl) pentanoic acid 39.0 instead of 0.100 mol of ethylene glycol diglycidyl ether in Synthesis Example 1
Synthesis was performed in exactly the same manner as in Synthesis Example 1 except that g (0.100 mol) was used (diazo resin 17 of the present invention).

The weight average molecular weight was 5,220. (Synthesis example 18) 2,3-diglycidyloxypropionic acid 21.8 g (0.100 mol) was used instead of ethylene glycol diglycidyl ether 0.100 mol in synthesis example 1.
Synthesis was carried out in exactly the same manner as in Synthesis Example 1 except that was used (diazo resin 18 of the present invention).

The weight average molecular weight was 3,980. The diazo resins synthesized in Synthesis Examples 1 to 18 above are shown in Table 1 below.
Shown in.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

The diazo resin of the present invention is usually 1 to 70% by weight, preferably 3 to 40% by weight in the solid content of the photosensitive composition.
Include. In addition to the diazo resin of the present invention, a conventional diazo resin synthesized by polycondensation may be added to the photosensitive layer of the present invention in an amount of 0 to 50% by weight based on the total weight of the diazo resin.

Next, the polyurethane resin used together with the diazo resin in the photosensitive composition of the present invention will be described. The polyurethane resin used in the present invention has a substituent having an acidic hydrogen atom. A substituent having an acidic hydrogen atom is its acid dissociation constant (pKa) in water.
There refers to those below 7, for example -COOH, -SO ₂ NHCOO-,
_{-CONHSO 2 -, - CONHSO 2 NH} -, - it includes the like - NHCONHSO _2. Particularly preferred is -COOH. The acid content per 1 g of the polyurethane resin is preferably 0.05 to 6 meq. If it is less than 0.05 meq, the developability with an alkali developing solution will be insufficient, and if it is more than 6 meq, abrasion resistance will deteriorate. More preferably, it is 0.2 to 4 meq.

The polyurethane resin can be manufactured by various methods. For example, in the case of a suitable polyurethane resin having a carboxyl group as a substituent having an acidic hydrogen atom, a diisocyanate compound represented by the following general formula (XVII) and a general formula (XVIII), (XIX) or (XX)
A polyurethane resin having a basic skeleton as a reaction product with a diol compound having a carboxyl group represented by

[0063]

[Chemical 6]

In the formula, R ¹⁹ is a substituent (for example, alkyl,
Alkenyl, aralkyl, aryl, alkoxy and halogeno groups are preferred. ) Represents a divalent aliphatic or aromatic hydrocarbon which may have. If necessary, R ¹⁹ may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, ureido group, or carbon-carbon unsaturated bond.

R ¹⁹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent (eg, alkyl, aryl, alkoxy, ester, urethane, amide, ureido and halogeno groups are preferable). , Alkoxy, aryloxy group, preferably hydrogen atom, alkyl group having 1 to 8 carbon atoms or 2 to 2 carbon atoms
8 alkenyl groups and 6-15 carbon aryl groups are shown.

R ²⁰ , R ²¹ and R ²² may be the same or different and each represents a single bond, a substituent (for example, alkyl,
Alkenyl, aralkyl, aryl, alkoxy and halogeno groups are preferred. ) Represents a divalent aliphatic or aromatic hydrocarbon which may have. Preferably 1 carbon
To alkylene groups having 6 to 15 carbon atoms, arylene groups having 6 to 15 carbon atoms, and more preferably alkylene groups having 1 to 8 carbon atoms. If necessary, R ²⁰ , R ²¹ , and R ²² may have other functional groups that do not react with the isocyanate group, such as ester group, urethane group, amide group, ureido group, and carbon-carbon unsaturated bond. Good. In addition, R ¹⁹ , R ²⁰ ,
Two or three of R ²¹ and R ²² may form a ring.

Ar represents a trivalent aromatic hydrocarbon which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms. Specific examples of the diisocyanate compound represented by the general formula (XVII) include those shown below. That is, 2,4-tolylene diisocyanate, 2,4
Dimer of tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'- Dimethylbiphenyl-4,
Aromatic diisocyanate compounds such as 4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate,
4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6)-
Diisocyanate, 1,3- (isocyanate methyl)
Alicyclic diisocyanate compounds such as cyclohexane; diisocyanate compounds which are reaction products of diols and diisocyanates such as adducts of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

Specific examples of the diol compound having a carboxyl group represented by formula (XVIII), (XIX) or (XX) include those shown below. That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl)
Propionic acid, 2,2-bis (2-hydroxyethyl)
Propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4
-Hydroxyphenyl) pentanoic acid, tartaric acid, N, N-
Examples thereof include bis (2-hydroxyethyl) -3-carboxy-propionamide.

As the polyurethane resin having a substituent having an acidic hydrogen atom other than the carboxyl group, a diisocyanate compound represented by the general formula (XVII) and the following general formula (XXI), (XXII), (XXIII) or (XXIV Polyurethane resin having a structure represented by the reaction product with the diol compound (1) as a basic skeleton.

[0070]

[Chemical 7]

In the formula, R ¹⁹ , R ²⁰ , R ²¹ , R ²² and Ar are as defined above. R ²³ represents a monovalent aliphatic or aromatic hydrocarbon which may have a substituent (eg, each group of alkyl, alkoxy and halogeno is preferable). Preferably an alkyl group having 1 to 20 carbon atoms or 2 to 20 carbon atoms
Represents an alkenyl group, an aryl group having 6 to 15 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms. More preferably, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms are shown.

A is an N-sulfonylamide group (-CO-NH-
SO ₂ -), N- sulfonyl ureido group (-NH-CO-NH-S
O ₂ -), N- aminosulfonyl amide group (-CO-NH-S
O ₂ —NH—) or sulfonyl urethane group (—O—CO—NH
-SO ₂ -) show a. The diol compound represented by the general formula (XXI), (XXII), (XXIII) or (XXIV) is, for example, a hydroxy group of a diol compound having a carboxyl group represented by the general formula (XVIII), (XIX) or (XX). After protecting the compound, the compound of the general formula (XXV), (XXVI), (XXVII) or (XXVII
It is synthesized by the reaction with the compound of I). Furthermore, after reacting with chlorosulfonyl isocyanate, the compound of the general formula (XX
It is synthesized by reacting with an amine compound of (IX).

R ²³ --SO ₂ --NCO (XXV) X--R ²⁰ --CO--NH--SO ₂ --R ²³ (XXVI) X--R ²⁰ --NH--CO--NH--SO ₂ --R ²³ (XXVII) X _{^{-R 20 -CO-NH-SO 2}} -NH-R 23 (XXVIII) R 23 -NH 2 (XXIX) wherein, X is a chlorine atom or a bromine atom.

In the case of a sulfonyl urethane group, it can be synthesized by reacting one hydroxy group of a trihydroxy compound with a compound of the general formula (XXV). In addition, the compound of the general formula (XXVI) is, for example, the compound represented by the following general formula (XXX) and (XXX
The compound of the general formula (XXVII) can be obtained by reacting the compound of the following general formulas (XXXII) and (XXXI)
The compound of the formula (VIII) is synthesized by reacting the following general formula (XXXIII) with chlorosulfonyl isocyanate and then reacting with the amine compound of the general formula (XXIX).

X-R ²⁰ -COCl (XXX) R ²³ -SO ₂ -NH ₂ (XXXI) X-R ²⁰ -NCO (XXXII) X-R ²⁰ -COOH (XXXIII) Further, in general formula (XXIV) The diol compound shown is, for example, a reaction of the general formula (XXX) with a compound of the following general formula (XXXIV), a reaction of a general formula (XXXII) with a compound of the following general formula (XXXIV), a general formula (XXXIV) and a chlorosulfonyl group. After the reaction of the isocyanate, it is synthesized by reacting with a compound of the following general formula (XXXV) to hydroxylate each of the obtained compounds.

X-R ²¹ -SO ₂ -NH ₂ (XXXIV) X-R ²¹ -NH ₂ (XXXV) Specifically, the compounds of the general formulas (XVIII), (XIX), (XX) and (XXI)
Examples of the diol compound represented by include those shown below.

[0077]

[Chemical 8]

[0078]

[Chemical 9]

[0079]

[Chemical 10]

[0080]

[Chemical 11]

[0081]

[Chemical 12]

[0082] _{(No. 22) HO-CH 2} CO -NH-SO 2 -C 3 H 6 -OH (No. 23) HO-CH 2 CO -NH-SO 2 -NH-C 2 H 4 -OH ( No. 24) a polyurethane resin used in the _{HO-C 3 H 6 CO-} NH-SO 2 -NH-C 2 H 4 -OH invention, diisocyanate compounds of the general formula (XVII) and formula (XXII), (XXIII ) Or (XXIV) in a polyurethane resin having a carboxyl group which is a reaction product with a diol compound, in the presence of a base,
By reacting a compound of general formula (XXV), (XXVI), (XXVII) or (XXVIII), and further after reacting the resin with chlorosulfonyl isocyanate, reacting an amine compound of general formula (XXIX) Can also be synthesized.

Further, a diol compound which does not have a carboxyl group and may have another substituent which does not react with isocyanate may be used in combination to the extent that alkali developability is not deteriorated. Specific examples of such diol compounds include those shown below. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 2,2,4-trimethyl-1,
3-pentanediol, 2,2-diethyl-1,3-propanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol,
Hydrogenated bisphenol A, diethyl 2,2-dimethylol malonate, bis- (2-hydroxyethyl) sulfide, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene of bisphenol F Oxide adduct, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2 -Hydroxyethyl) -2,4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m
-Xylylene dicarbamate, bis (2-hydroxyethyl) isophthalate, etc. are mentioned.

The polyurethane resin used in the present invention is prepared by reacting the residual --OH group with a compound of the general formula (XXV),
It is possible to introduce a substituent -SO ₂ NHCOO- having an acidic hydrogen atom. The polyurethane resin used in the present invention contains the above-mentioned diisocyanate compound and diol compound in an aprotic solvent and has a known active catalyst such as diethylaniline, 2,2,2-diazabicyclooctane, n- It is synthesized by adding dibutyltin dilaurate or the like and heating. The molar ratio of the diisocyanate and diol compound used is preferably 0.
When it is 8: 1 to 1.2: 1 and an isocyanate group remains at the polymer terminal, it is finally synthesized in a form in which the isocyanate group does not remain by treating with an alcohol or an amine.

The molecular weight of the polyurethane resin used in the present invention is preferably 1,000 or more in weight average, and more preferably in the range of 5,000 to 150,000. These polyurethane resins may be used alone or in combination.
The content of these polyurethane resins contained in the photosensitive layer is 50% by weight or more, preferably 50 to 99% by weight,
More preferably, it is about 60 to 95% by weight.

Other resins may be mixed in the photosensitive layer of the present invention in an amount of 50% by weight or less based on the polyurethane resin. Examples of the mixed resin include polyamide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, polystyrene resin, and novolac type phenol resin. Next, typical synthetic examples of the polyurethane resin of the present invention will be shown. (Synthesis example 19) 500 ml equipped with condenser and stirrer
In a three-necked round-bottomed flask of No. 1, 2,2-bis (hydroxymethyl) propionic acid 11.5 g (0.0860 mole), diethylene glycol 7.26 g (0.0684 mole) and 1,4-butanediol 4.11 g (0 0.0456 mole) was added and dissolved in 118 g of N, N-dimethylacetamide. To this, 3,4 g (0.123 mole) of 4,4'-diphenylmethane diisocyanate, 13.8 g (0.0819 mole) of hexamethylene diisocyanate and 0.1 g of di-n-butyltin dilaurate as a catalyst were added, and the mixture was stirred. It heated at 90 degreeC for 7 hours. N, N
-Dimethylacetamide (100 ml), methanol (50 ml) and acetic acid (50 ml) were added, and after stirring, the mixture was put into 4 liters of water with stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under reduced pressure to obtain 62 g of a polymer (polyurethane (a) of the present invention).

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 70000. The carboxyl group content was measured by titration to be 1.12 meq / g
Met. (Synthesis Examples 20 to 31) The diisocyanates shown in Table 2,
Using a diol compound, a polyurethane resin was synthesized in the same manner as in Synthesis Example 19 (polyurethane (b) of the present invention).
~ (M)). The molecular weight was measured by GPC and the acid content was measured by titration. The results are also shown in Table 2.

[0088]

[Table 6]

[0089]

[Table 7]

[0090]

[Table 8]

(Synthesis example 32) 125 g (0.50 mol) of 4,4'-diphenylmethane diisocyanate and 67 of 2,2-bis (hydroxymethyl) propionic acid were placed in a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer.
g (0.50 mol) was added and dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst, and the mixture was heated under reflux for 6 hours with stirring. Then, the reaction solution was poured into a solution of 4 liters of water and 40 ml of acetic acid while stirring to precipitate a white polymer. The polymer was filtered off, washed with water and dried under vacuum to yield 185
g of polymer was obtained.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 28,000. Further, the carboxyl group content was measured by titration to be 2.47 meq / g.
Met. Further, 40 g of this polymer was placed in a 300 ml three-neck round bottom flask equipped with a condenser and a stirrer, and D
It was dissolved in 200 ml of MF. To this solution was added 6.3 g (0.062 mol) of triethylamine, and after heating to 80 ° C, 7.7 g of ethylene bromohydrin (0.062 mol) was added under stirring to 10
It was dripped over a period of minutes. Then, stirring was continued for 2 hours.

After completion of the reaction, the reaction solution was poured into a solution of 4 liters of water and 200 ml of acetic acid while stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under vacuum to obtain 42 g of a polymer. N
It was confirmed by MR measurement that the hydroxyethyl group had been introduced into the carboxyl group, and the residual carboxyl group content was measured by titration to find that it was 1.21 meq /
It was g (polyurethane (n) of the present invention). (Synthesis example 33) 500 ml equipped with condenser and stirrer
In a 3-necked round bottom flask, 125 g (0.50 mol) of 4,4'-diphenylmethane diisocyanate and 2,2-
67 g of bis (hydroxymethyl) propionic acid (0.50
Mol) was added and dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst and stirred under stirring 6
Heated to reflux for hours. Then, the reaction solution was poured into a solution of 4 liters of water and 40 ml of acetic acid while stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 185 g of a polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 28,000. Further, the carboxyl group content was measured by titration and it was 2.47 meq / g. Further, 40 g of this polymer was placed in a 300 ml three-necked round bottom flask equipped with a condenser and a stirrer, and DM was added.
It was dissolved in 200 ml of F. To this solution was added triethylamine (10.0 g, 0.099 mol) and after heating to 80 ° C., toluenesulfonyl isocyanate (19.5 g) ((0.099 mol)) was added.
Mol) was added. Then, stirring was continued for 2 hours.

After the reaction was completed, the reaction solution was poured into a solution of 4 liters of water and 200 ml of acetic acid while stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under vacuum to obtain 49 g of a polymer.
It was confirmed by NMR measurement that an N-toluenesulfonylamide group was formed, and the acid value was measured by titration to find that it was 2.01 meq / g (polyurethane (o) of the present invention).

Next, the modified polyvinyl acetal resin used together with the diazo resin in the photosensitive composition of the present invention will be described. The modified polyvinyl acetal resin used in the present invention has a substituent having an acidic hydrogen atom. Here, the definition of the substituent having an acidic hydrogen atom and the acid content of the resin are the same as in the case of the polyurethane resin.

Specific examples of such modified polyvinyl acetal resin include, for example, JP-A-61-267042.
No. 61-128123 and No. 62-58242, and polymers represented by the following general formula.

[0098]

[Chemical 13]

Wherein R ²⁴ is an alkyl group which may have a substituent or a hydrogen atom, R ²⁵ is an alkyl group which does not have a substituent, and R ²⁶ is an aliphatic or aromatic carbon atom having a carboxylic acid group. A hydrogen group, R ²⁷ , represents an aliphatic and / or aromatic hydrocarbon group which has at least one hydroxyl group or nitrile group and may further have other substituents, and n ₁ , n ₂ , n ₃ , n ₄ and n ₅ represent mol% of each repeating unit, and are in the following ranges. n ₁ = 5-85, n ₂ = 0-60, n ₃ = 0-20, n
_{4 = 3~60, n 5 = 0~60} .

The polymers described in JP-A-60-182437 are also preferably used. Further, a polymer having an alkenylsulfonyl urethane side group described in JP-A-57-94747 is also preferably used. Hereinafter, synthetic examples of the modified polyvinyl acetal resin will be shown. (Synthesis Example 34) Polyvinyl formal (Vinilec B-
20 g of 2 Chisso) was dissolved in 240 ml of acetic acid. Further, the reaction temperature was set to 100 ° C., and then maleic anhydride 16.9 was added.
g and 18.0 g of sodium acetate were added and reacted for 4 hours. This solution was gradually added to a 4 liter solution of methanol-water 1: 3 to precipitate a polymer. The solid was vacuum dried to obtain 21.5 g of polymer. Acid content is 1.
It was 5 meq / g. (The modified polyvinyl acetal resin (p) of the present invention). (Synthesis Example 35) Polyvinyl butyral (Denka Butyral # 4000 manufactured by Denki Kagaku Kogyo Co., Ltd.) was placed in a three-necked round bottom flask with a capacity of 1 liter equipped with a thermometer, a reflux condenser and a stirrer.
-2) 60 g was dissolved by heating in 720 ml acetic acid. After the reaction temperature was further raised to 100 ° C., 89.8 g of phthalic anhydride and 60.5 g of sodium acetate were added and the reaction was carried out for 3 hours. After the reaction, this solution was added little by little to a 10-liter solution of methanol-water (1: 3) to precipitate a polymer. The solid was vacuum dried to obtain 64.8 g of polymer. The acid content was 2.72 meq / g.

Next, 45 g of the modified polyvinyl butyral synthesized above was dissolved in 450 ml of N, N-dimethylformamide by heating in a 3-neck round bottom flask having a capacity of 1 liter equipped with a thermometer, a reflux condenser and a stirrer. Furthermore, the internal temperature is 80 ° C.
After that, 6.91 g of potassium carbonate was added, and 6.24 g of ethylene bromhydrin was further added, and the mixture was reacted for 3 hours. After the reaction, this solution was added little by little to a 5 liter solution of water-acetic acid 19: 1 to precipitate a polymer. The solid was vacuum dried to obtain 38.4 g of polymer. Acid content
It was 1.48 meq / g (modified polyvinyl acetal resin (q) of the present invention). (Synthesis Example 36) Polyvinyl butyral (Denka Butyral # 4000 manufactured by Denki Kagaku Kogyo Co., Ltd.) was placed in a three-necked round bottom flask having a capacity of 1 liter equipped with a thermometer, a reflux condenser, and a stirrer.
-2) 40 g was dissolved in 600 ml of anhydrous tetrahydrofuran. A mixture of 18 g of propenylsulfonyl isocyanate and 100 g of tetrahydrofuran was added, and the mixture was reacted at room temperature for 4 hours. After the reaction, this solution was gradually added to 10 liters of water to precipitate a polymer. The solid was vacuum dried to obtain 49.8 g of polymer. Acid content is 2.
It was 51 meq / g (modified polyvinyl acetal (r) of the present invention).

A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development. As the dye, those which change color tone by reacting with free radicals or acids can be preferably used. Here, "the color tone changes" includes both a change from colorless to a color tone and a change from a colored to a colorless or a different color tone. Preferred dyes are those which form a salt with an acid to change the color tone.

For example, Victoria Pure Blue BOH
(Hodogaya Chemical Co., Ltd.) and its naphthalene sulfonate,
Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin, Malachite Green, Oil Red, m-cresol purple, rhodamine B,
Colored triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes represented by auramine, 4-p-diethylaminophenyliminaphthoquinone, and cyano-p-diethylaminophenylacetanilide From a colorless to a different color tone.

On the other hand, as the discoloring agent which changes from colorless to colored, there are leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p. ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p ″ -tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, Examples thereof include primary or secondary arylamine dyes represented by p ′, p ″ -triaminotriphenylmethane.

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, more preferred are triphenylmethane-based dyes, and particularly Victoria Pure Blue BOH and its naphthalene sulfonate. The above dye is usually used in the photosensitive composition in an amount of about 0.5 to about 1.
It is preferably 0% by weight, more preferably about 1 to 5% by weight.

Various additives can be further added to the photosensitive composition of the present invention. For example, alkyl ethers (eg ethyl cellulose, etc.) for improving the coating property.
Methylcellulose), fluorine-based surfactants, nonionic surfactants (especially JP-A-62-170950 and JP-A-6-170950).
2-226143, U.S. Pat. No. 3,787,351.
Fluorosurfactant as described in the specification (for example, Megafac F-171, 173, 177, Defencer MCF300, 312, 313 [all manufactured by Dainippon Ink and Chemicals, Incorporated], Modiper F-100. , 1
02,110 (all manufactured by Nippon Oil & Fats Co., Ltd.)), a plasticizer for imparting flexibility and abrasion resistance to the coating film (eg, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, Dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,
Tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid oligomers and polymers, of which tricresyl phosphate is particularly preferred), stabilizers (phosphoric acid, phosphorous acid, pyrophosphoric acid) , Phenylphosphonic acid, oxalic acid, boric acid,
p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, 3-sulfophthalic acid, 4-sulfophthalic acid, 2-sulfoterephthalic acid, 5- Sulfoisophthalic acid, isopropylnaphthalenesulfonic acid, t-butylnaphthalenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and copolymers thereof, polyvinylphosphonic acid and copolymers thereof, polyvinylsulfonic acid and copolymers thereof , 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, citric acid, propane-1,2,3-tricarboxylic acid, 2-phosphonobutane-1,2,4- Tricarboxylic acid, 1-ho Honoetan 1,2,2-tricarboxylic acid, 1-hydroxyethane-1,1-disulfonic acid, etc.), development accelerators (such as higher alcohols, acid anhydrides,
Anionic surfactant, etc.), an oil-sensitizing agent for improving the oil-sensitivity of the image area (for example, a half-esterified product of alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527, p. -T-butylphenol-
A novolak resin such as formaldehyde resin, a fluorochemical surfactant, a fatty acid ester of p-hydroxystyrene, etc.) are preferably used. The amount of these additives added varies depending on the intended use and purpose, but is generally 0.01 to 30% by weight based on the total solid content.

Such a photosensitive composition is coated on a suitable support to obtain a photosensitive lithographic printing plate. Examples of such a support include paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloy), zinc,
Plates of metal such as copper, films of plastic such as cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl acetal, etc. Metals such as those mentioned above are laminated or vapor deposited. Examples thereof include paper or a plastic film, aluminum or a chrome-plated steel plate, and among these, aluminum and an aluminum-coated composite support are particularly preferable.

As the aluminum material, 1S material is preferable. In addition, the surface of the aluminum material enhances water retention,
Surface treatment is desirable for the purpose of improving the adhesion to the photosensitive layer. For example, as a roughening method, generally known brush polishing method, ball polishing method, electrolytic etching,
Methods such as chemical etching, liquid honing, sandblasting and the like and combinations thereof are mentioned, preferably brush polishing, electrolytic etching, chemical etching and liquid honing are included, among which the use of electrolytic etching is particularly included. The roughening method is preferred.

Further, as described in JP-A-54-63902, a method of brush-polishing and then electrolytic etching is also preferable. Further, as the electrolytic bath used in the electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof or an aqueous solution containing an organic solvent is used. Liquids are preferred. Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary. The aluminum plate thus obtained is preferably anodized, and particularly preferably, a method of treating with a bath containing sulfuric acid or phosphoric acid can be mentioned.

Further, as required, US Pat. No. 2,714,
Silicate treatment (sodium silicate, potassium silicate) described in US Pat. No. 066 and US Pat. No. 3,181,461, potassium zirconium fluoride treatment described in US Pat. No. 2,946,638, US Patent No. 3,201,24
The phosphomolybdate treatment described in No. 7,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent No. 1,091,433, described in German Patent Nos. 1,134,093 and British Patent No. 1,230,447 Polyvinylphosphonic acid treatment described in JP-B-44-6409, U.S. Pat. No. 3,307,
Phytic acid treatment described in Japanese Patent No. 951 and salts of a hydrophilic organic polymer compound and a divalent metal described in JP-A Nos. 58-16893 and 58-18291. And a hydrophilic treatment by undercoating of a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651, JP-A-60-
Those colored with an acid dye described in Japanese Patent No. 64352 are particularly preferable. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can also be mentioned.

It is also preferable that after the graining treatment and the anodic oxidation, the sealing treatment is performed. Such sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. To further elaborate on the support suitable for use in the present invention, first, iron is added to 0.1
~ 0.5% by weight, 0.03 to 0.3% by weight of silicon, 0.0% of copper
03-0.03% by weight and titanium 0.01-0.1% by weight
1S aluminum plate containing alkali is preferably 1 to
20-80 in an aqueous solution of 30 wt% sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, etc.
Etching is performed by immersing at a temperature of ℃ for 5 seconds to 250 seconds. In the etching bath, use 1 / aluminum of aluminum
About 5 may be added.

Then, it is immersed in a 10 to 30% by weight aqueous solution of nitric acid or sulfuric acid at a temperature of 20 to 70 ° C. for 5 to 250 seconds to carry out neutralization and smut removal after alkali etching. After cleaning the surface of this aluminum alloy plate, the following roughening treatment is performed. As the roughening treatment, brush polishing and / or electrolytic etching treatment is suitable.

The temperature of the electrolytic solution is usually 10 to 60 ° C. The alternating current used at this time may be a rectangular wave, a trapezoidal wave, or a sine wave as long as the positive and negative polarities are exchanged alternately. Phase alternating current can be used. Further, the current density is 5 to 100 A / dm ² , and it is desirable to perform the treatment for 10 to 300 seconds.

The surface roughness of the aluminum alloy support in the present invention is adjusted to 0.2 to 0.8 μm by adjusting the amount of electricity. Aluminum alloy grained like this,
It is preferable that the smut adhering to the surface is removed by 10 to 50% hot sulfuric acid (40 to 60 ° C.) or a dilute alkali (sodium hydroxide or the like). When removed with an alkali, it is subsequently immersed in an acid (nitric acid or sulfuric acid) for neutralization for cleaning.

After removing the surface smut, an anodized film is provided. As the anodizing method, a conventionally well-known method can be used, but sulfuric acid is used as the most useful electrolytic solution. Following that, phosphoric acid is also a useful electrolyte. Further, JP-A-55-28400
The mixed acid method of sulfuric acid and phosphoric acid disclosed in the publication is also useful.

In the sulfuric acid method, the treatment is usually carried out with a direct current, but it is also possible to use an alternating current. The concentration of sulfuric acid is 5
It is used in an amount of 30% by weight and has a temperature range of 20 to 60 ° C.
It is electrolyzed for 250 seconds to provide an oxide film of 1 to 10 g / m ^{2 on} the surface. The electrolytic solution preferably contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A / dm ² . In the case of the phosphoric acid method, the treatment is carried out at a concentration of 5 to 50% by weight, a temperature of 30 to 60 ° C., and a current density of 1 to 15 A / dm ² for 10 to 300 seconds.

The aluminum support thus treated is preferably further surface treated with silicates as described in US Pat. No. 2,714,066. In order to provide the above-mentioned photosensitive composition on a support, a photosensitive diazo resin, a lipophilic polymer compound, and if necessary, various amounts of various additives are added in an appropriate solvent (methyl cellosolve, ethyl cellosolve, dimethoxy). Ethane, diethylene glycol monomethyl ether, diethylene glycol-dimethyl ether, 1-methoxy-2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide,
Dimethylacetamide, cyclohexanone, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethylsulfoxide, water, etc.) to prepare a coating solution of the photosensitive composition, which is coated on a support and dried. Good. The solvent used may be a single solvent, but it is more preferable to use a mixture of a high boiling point solvent such as methyl cellosolve, 1-methoxy-2-propanol and methyl lactate and a low boiling point solvent such as methanol and methyl ethyl ketone.

The solid content concentration of the photosensitive composition upon coating is preferably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition is about 0.2 to 10 g /
It may be about m ² (dry weight), and more preferably
It is good to set it to 0.5 to 3 g / m ² . On the photosensitive layer, there is preferably a mat layer composed of protrusions provided independently of each other.

The purpose of the matte layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuuming time and further crushing fine halftone dots during exposure due to poor adhesion. Is to prevent. As a method for applying the matte layer, there is disclosed in JP-A-55-129.
There is a method of heat-sealing powdered solid powder described in JP-A-74, a method of spraying and drying polymer-containing water described in JP-A-58-182636, and the like. However, it is desirable that the matte layer itself be soluble in the alkaline developer or be removable by it.

The photosensitive composition of the present invention coated on a support is exposed through a transparent original image having a line image, a halftone image or the like, and then developed with an aqueous alkaline developing solution.
A negative relief image is given to the original picture. Suitable light sources for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, and laser beams.

The developing solution used for the developing treatment of the photosensitive lithographic printing plate according to the present invention may be any known one, but preferably the developing solution contains at least one alkaline agent and water. Contains as an ingredient. As the alkaline agent contained as an essential component in the developer, sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of secondary or tertiary phosphoric acid, sodium metasilicate, Inorganic alkaline agents such as sodium carbonate and ammonia, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono,
Examples thereof include organic amine compounds such as di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, and ethylenediimine. The content of these alkaline agents in the developer is 0.05 to 10% by weight.
It is preferably 0.5 to 5% by weight. If it is less than 0.05% by weight, the development will be poor, and if it exceeds 10% by weight, the printing performance as a lithographic printing plate will be adversely affected.

The developing solution for developing the photosensitive lithographic printing plate according to the present invention may contain a specific organic solvent, if necessary. Such an organic solvent is capable of dissolving or swelling the non-exposed portion (non-image portion) of the above-mentioned photosensitive composition layer when it is contained in a developing solution, and moreover, it can be dissolved in water at room temperature (20 ° C.). An organic solvent having a solubility of 10% by weight or less. Any such organic solvent may be used as long as it has such characteristics.
The following may be mentioned, but the present invention is not limited thereto. That is, for example, carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone, and the like. Ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol; alkyls such as xylene. Substituted aromatic hydrocarbons; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, monochlorobenzene and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is generally 0 to 20% by weight, and particularly 2 to 10% by weight.
In this case, more favorable results are obtained.

The developing solution for developing the photosensitive lithographic printing plate according to the present invention may contain a water-soluble sulfite salt, if necessary. As such a water-soluble sulfite,
Alkali or alkaline earth metal salts of sulfite are preferred,
Examples include sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the developer composition is 0 to 4% by weight, preferably 0.1 to 1% by weight.

Further, instead of the above water-soluble sulfite, an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or a hydroxy aromatic compound such as methylresorcin may be contained. Of course, these compounds may be used in combination with a water-soluble sulfite. Further, if necessary, additives such as a defoaming agent and a water softener can be contained. As a water softener, for example,
Examples thereof include polyphosphate salts and aminopolycarboxylic acids. The optimum amount of such a water softener varies depending on the hardness of the hard water used and the amount used, but if the general amount is shown, it is 0.01 to 5% by weight in the developing solution at the time of use. , And more preferably in the range of 0.01 to 0.5% by weight.

Further, a certain solubilizing agent may be contained in order to assist the dissolution of the above-mentioned organic solvent in water. As such a solubilizing agent, in order to realize the effects of the present invention, it is preferable to use low molecular weight alcohols and ketones which are more soluble in water than the organic solvent used. Further, anionic surfactants, amphoteric surfactants and the like can also be used. Examples of such alcohols and ketones include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxy-4-methylbutanol, N. It is preferable to use -methylpyrrolidone or the like. Examples of the surfactant include sodium isopropyl naphthalene sulfonate, sodium n-butyl naphthalene sulfonate, N-
Methyl-N-pentadecylaminoacetic acid sodium salt, lauryl sulfate sodium salt and the like are preferable. In general, the amount of the solubilizing agent such as alcohol or ketone used is preferably about 30% by weight or less based on the whole developing solution.

However, when an organic solvent or the like is contained, there are toxicity at work, hygiene problems such as odor, safety problems such as fire and gas explosion, workability problems such as foam generation, pollution due to waste liquid, etc. Therefore, it is more preferable that the organic solvent does not substantially contain the organic solvent. Incidentally, "substantially free of organic solvent" means the above-mentioned environmental hygiene, safety,
It means that the organic solvent is not contained to the extent that it causes inconvenience in terms of workability, and in the present invention, the proportion of the organic solvent in the composition is 2% by weight or less, preferably 1 It is less than or equal to weight%.

Such an aqueous alkaline developer containing substantially no organic solvent is disclosed in, for example, JP-A-59-84241.
JP-A-57-192952 and JP-A-62-2.
It is possible to use the developer composition described in JP-A No. 4263, etc., which is used when the positive type lithographic printing plate is imagewise exposed and then developed. However, as described in the synthesis of the diazo resin, a diazo resin suitable for an aqueous alkaline developer containing substantially no organic solvent is a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphorus group among the diazo resins of the present invention. It is limited to diazo resins having alkali-soluble groups such as oxygen acid groups and phenolic hydroxyl groups. In this case, the acid value of the lipophilic polymer compound is preferably 100 to 200.

Photosensitive lithographic printing plates using the photosensitive composition of the present invention are disclosed in JP-A-54-8002 and JP-A-55-1150.
Needless to say, the plate-making process may be carried out by the methods described in JP-B No. 45-45, JP-A No. 59-58431 and JP-A-59-58431. That is, after the development treatment, it may be washed with water and then subjected to a desensitizing treatment, or a desensitizing treatment as it is, or a treatment with an aqueous solution containing an acid, or a desensitizing treatment after a treatment with an aqueous solution containing an acid. Further, in the developing step of this type of photosensitive lithographic printing plate, the alkaline solution is consumed depending on the processing amount to reduce the alkali concentration, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity is lowered, in this case, JP-A-54-6200
A replenisher may be used to restore throughput as described in No. 4. In this case, it is preferable to supplement by the method described in US Pat. No. 4,882,246.

The plate making process as described above is described in JP-A-2
It is preferable to use an automatic processor as described in JP-A Nos. 7054 and 2-32357. In addition, as the desensitizing gum which is optionally applied in the final step of the plate making process, Japanese Patent Publication Nos. 62-16834 and 62-251.
18, 63-52600, JP-A-62-7595.
Nos. 62-11693 and 62-83194 are preferable.

[0130]

The photosensitive lithographic printing plate using the photosensitive composition of the present invention has excellent developability in an aqueous alkaline developer, good photocrosslinking property, and high printing durability.

[0131]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the contents of the present invention are not limited thereto. In the examples,% means% by weight. Example 1 99.5% aluminum, 0.01% copper, 0.0% titanium
JIS A1 containing 3%, 0.3% iron and 0.1% silicon
A rolled plate of 050 aluminum material with a thickness of 0.24 mm is
The surface was grained with a 20% aqueous suspension of 0 mesh pumice stone (manufactured by Kyoritsu Kiln Co., Ltd.) and a rotating nylon brush (6-10 nylon), and then thoroughly washed with water.

This was immersed in a 15% aqueous sodium hydroxide solution (containing 5% of aluminum) for etching so that the amount of aluminum dissolved was 5 g / m ² , and then washed with running water. Further, it is neutralized with 1% nitric acid, and then in a 0.7% nitric acid aqueous solution (containing 0.5% aluminum ions), a rectangular wave with a voltage at the cathode of 9.3 volts and an anode voltage of 10.5 volts. Alternating waveform voltage (current ratio r = 0.90, Japanese Patent Publication No. 58-5796)
16) by using the current waveform described in the example of the publication
The electrolytic surface roughening treatment was carried out with the amount of electricity at the anode of 0 coulomb / dm ² . After washing with water, the plate was immersed in a 10% aqueous sodium hydroxide solution at 40 ° C. to perform etching so that the amount of aluminum dissolved was 1 g / m ² , and then washed with water. Then 30 at 50 ℃
% Sulfuric acid aqueous solution, desmutted, and then washed with water.

Further, a porous anodic oxide film forming treatment was carried out in a 20% sulfuric acid aqueous solution (containing 0.8% of aluminum ions) at 35 ° C. using direct current. Ie current density 1
Electrolysis was carried out at 3 A / dm ² , and the electrolysis time was adjusted to prepare a substrate having an anodized film weight of 2.0 g / m ² . After washing with water, 70 ℃
Was dipped in a 3% aqueous solution of sodium silicate for 30 seconds, washed with water and dried.

The aluminum support thus obtained had a reflection density of 0.28 as measured by a Macbeth RD920 reflection densitometer and a center line average roughness of 0.5 μ. Apply the following undercoat liquid-1 to the above aluminum plate,
It was dried at 30 ° C. for 30 seconds. The dry weight was 20 mg / m ² . Undercoat liquid-1 Yellow dye AY-25 0.075 g Water 100 g Next, the following photosensitive liquid-1 was applied using a bar coater,
It was dried at 120 ° C. for 30 seconds. Dry coating amount is 1.5g
/ M ² .

Photosensitive Solution-1 Diazo Resin 1 of the Invention 1 1.2 g Polyurethane (a) of the Invention 5.0 g Oil-soluble Dye 0.15 g (Victoria Pure Blue BOH) Fluorine-based Surfactant 0.02 g (Megafuck F) -177 Dainippon Ink and Chemicals, Inc. tricresyl phosphate 0.2 g malic acid 0.03 g 2-methoxypropanol 50 g methanol 20 g methyl ethyl ketone 20 g methyl lactate 10 g H ₂ O 1 g surface after coating photosensitive layer A liquid having the following composition was applied by electrostatic spraying to the surface, and exposed to an atmosphere of 60 ° C. for 5 seconds to be dried, thereby matting the surface.

Spray Liquid Compound A of the following formula: 0.5 g

[0137]

[Chemical 14]

Tartrazine 0.01 g Water 100 g Each mat has a height of 2 to 6 μm and a width of 20 to 150 μm, and the mat as a whole has a number of about 100 pieces / m ² and a coating amount of 0.1 g / m 2. ^{Was 2} . A PS plate manufactured by Fuji Photo Film Co., Ltd. was added to the photosensitive lithographic printing plate thus obtained.
The image was exposed with a light from a distance of 1 m for 1 minute.

Further, development processing was performed under the following conditions.
That is, first of all, Fuji Photo Film Co., Ltd.'s automatic machine Stablon 9
The following developing solution-1 and Finisher FN-2 manufactured by Fuji Photo Film Co., Ltd. were charged to 00N respectively, and the developing solution temperature was 25
The development treatment was performed under the conditions of the temperature of 20 ° C. and the development time of 20 seconds. Developer-1 Benzyl alcohol 30 g Triethanolamine 10 g Sodium sulfite 5 g Sodium isopropylnaphthalene sulfonate 10 g Water 1000 g The obtained lithographic printing plate was used as a printer SOR manufactured by Heidelberg.
When printing was performed over 10 minutes, 100,000 or more clear prints with no stain were obtained. Example 2 The following undercoat liquid-2 was applied on an aluminum support obtained in the same manner as in Example 1 and dried at 100 ° C for 20 seconds. The dry weight was 15 mg / m ² .

Undercoat Liquid-2 Compound A (used in Example 1) 0.1 g Water 100 g Next, the following Photosensitive Solution-2 was applied using a bar coater, and 1
It was dried at 20 ° C. for 30 seconds. Dry coating amount is 1.5g /
It was m ² .

Photosensitive solution-2 Diazo resin 2 of the present invention 2.0 g Polyurethane (b) of the present invention 5.0 g Oil-soluble dye 0.15 g (Victoria Pure Blue BOH naphthalene sulfonate) Fluorine-based surfactant 0 0.02 g (Megafac F-177) Tricresyl phosphate 0.2 g Phosphoric acid 0.03 g 4-Sulfophthalic acid 0.03 g Styrene-maleic anhydride copolymer n-0.05 g Hexyl alcohol half ester 2-methoxy Propanol 50 g Methanol 20 g Methyl ethyl ketone 20 g Methyl lactate 10 g H ₂ O 1 g After applying the photosensitive layer, the surface was matted by the same method as in Example 1.

The photosensitive lithographic printing plate thus obtained was exposed, developed and printed in the same manner as in Example 1. As a result, 100,000 or more clear prints free of stains were obtained. Examples 3 to 18 The same procedure as in Example 2 was carried out except that the diazo resin and the polyurethane resin in the photosensitive solution 2 in Example 2 were changed to those shown in Table 3, respectively. In each case, 100,000 or more clear prints free of stains were obtained.

Table 3 ────────────────────────────── Example Diazo resin of the present invention Polyurethane resin of the present invention or modified polyvinyl Alcohol resin ────────────────────────────── 3 3 c 4 4 d 5 5 e 6 6 f 7 7 7 g 8 8 h 9 9 i 10 10 j 11 11 k 12 12 l 13 13 m 14 14 n 15 15 o 16 16 16 p 17 17 q 18 18 r r ─────────────────── ───────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Let dry for seconds. Dry coating amount is 1.0
It was g / m ² .

Photosensitive liquid-19 Diazo resin (8) of the present invention 1 g Polyurethane (e) 5 g of the present invention 5 g Oil-soluble dye 0.2 g (Victoria Pure Blue BOH) Fluorosurfactant 0.02 g (Megafuck) F-177) Tricresyl phosphate 0.5 g Phenylphosphonic acid 0.05 g Tartaric acid 0.05 g P-hydroxystyrene pivalate S 0.1 g Tell (esterification rate 50%) 2-methoxypropanol 40 g Methanol 30 g Methyl ethyl ketone 20 g H ₂ O 1 g After coating the photosensitive layer, the surface was matted in the same manner as in Example 1.

The photosensitive lithographic printing plate thus obtained was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. for 1 minute from a distance of 1 m. Further, development processing was performed under the following conditions. That is, first, the following developing solution-2 was added to the first bath of Fuji Photo Film Co., Ltd.'s automatic developing machine Stablon 900D.
Water was charged in the bath, and Finisher FP-2 manufactured by Fuji Photo Film Co., Ltd. was charged in the third bath, and the development processing conditions were a developer temperature of 30 ° C. and a development time of 12 seconds. Next, the lithographic printing plate and the imagewise exposed positive type P manufactured by Fuji Photo Film Co., Ltd.
30 sheets of S-plate FPS-3 were alternately processed in a size of Kiku format and developed for 6 hours at appropriate time intervals.

Developer-2 1K Potassium silicate 60 g Potassium hydroxide 12 g Boron-based surfactant (Emulbon T-20) 0.1 g Chelating agent (EDTA) 0.1 g Silicon-based defoamer (Toshiba Silicone Co., Ltd.) 0.01 g TSA-731) Cobalt acetate 0.04 g Water 1200 g Developer-2 had a pH of 13.1.

When Developer-2 was fatigued by these treatments or with the passage of time and the developing ability was deteriorated, Replenisher-1 below was replenished. Replenisher-1 K potassium silicate 120 g Potassium hydroxide 25 g Chelating agent (0.3 g NTA-C manufactured by Kirest Chemical Co., Ltd.) Water 1200 g The lithographic printing plate thus obtained was printed on a printing machine SOR. However, clear printed matter with no stains is 50,000
0 or more sheets were obtained. Examples 20 to 25 The same procedure as in Example 19 was carried out except that the diazo resin and the polyurethane resin in the photosensitive liquid-19 in Example 19 were changed to those shown in Table 4, respectively. 50,000 or more clear prints with no stain were obtained.

Table 4 ────────────────────────────── Example Diazo resin of the present invention Polyurethane resin of the present invention ─── ─────────────────────────── 20 (10) (g) 21 (11) (i) 22 (15) (j) 23 ( 16) (l) 24 (17) (m) 25 (18) (o) ────────────────────────────── It is further understood that the photosensitive composition of the present invention is excellent in that it is possible to obtain a large number of clear printed matter which can be developed with aqueous alkali and have no stain.

Claims (1)

[Claims] 1. A photosensitive material comprising a diazo resin synthesized by the following procedures (1) to (3) and a polyurethane resin having a substituent having an acidic hydrogen atom or a modified polyvinyl acetal resin. Composition. Diazo resin synthesis procedure (1) An oligomer is synthesized by a ring-opening polymerization reaction of a compound containing two oxirane rings in one molecule and an amino compound containing a compound represented by the following general formula (I). [Chemical 1] In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, W represents a single bond or any divalent organic group, and Y represents any substituent capable of being converted into an amino group. Indicates. (2) The substituent Y of the oligomer obtained in (1) is converted to an amino group. (3) The amino group of the oligomer obtained in (2) is converted into a diazonium salt.