JPS63287943A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having satisfactory developability for aq. alkaline developing soln. and superior durability for printing by incorporating a water-insoluble and aq. alkali-soluble poly(urethane-urea)resin having carboxyl groups into the compsn. CONSTITUTION:The title photosensitive compsn. contains a water-insoluble and aq. alkali-soluble poly(urethane-urea)resin having carboxyl group. Also, a mixture of o-quinonediazide as a photosensitive compd., a negatively acting diazonium compd., a polymerizable monomer in combination with a photopolymn. initiator, or a mixture of a negatively active diazonium compd., a photopolymerizable monomer in combination with a photopolymn. initiator, etc. may be used for a photosensitive compsn. Therefore, either a positive photosensitive compsn. or a negative photosensitive compsn. can be obtd. Such compsn. has superior coatability when it is coated on a base. Moreover, the developability of the compsn. when its exposed part is developed with aq. alkaline developing soln. after coating, drying, and image exposing the composition is also superior. In addition, since a relief image has high abrasion resistance and high adhesion to a base, a great number of satisfactory printed matters can be obtd. when the compsn. is used for the prepn. of a printing form.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits and photomasks.

More specifically, the present invention relates to a photosensitive composition comprising a photosensitive compound that acts on a positive or negative tone and a polymer compound with excellent abrasion resistance.

[Conventional technology]

In a positive-acting system, a photosensitive composition consisting of an 0-naphthoquinonediazide compound and a novolac type phenol resin is an extremely excellent photosensitive composition that is used industrially in the production of lithographic printing plates and as a photoresist. Ta.

However, due to the nature of the novolac type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor coating properties, poor abrasion resistance, and insufficient stiffness when used in lithographic printing plates. However, there were some points that needed to be improved, such as the fact that it was difficult to use, and there were limits to its application.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Although the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 did have improved film properties, it had the drawback of poor abrasion resistance. Furthermore, in JP-A-51-34711, it is proposed to use a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder; There were problems such as a narrow range and insufficient wear resistance.

Furthermore, polyurethane resins are known as polymers having excellent wear resistance, and Japanese Patent Publication No. 49-36961 discloses a combination system of a positive-acting diazo compound and a substantially linear polyurethane resin. However, the polyurethane resin does not have an alkali-soluble group and has essentially insufficient solubility in an aqueous alkaline developer. It was extremely difficult to do so.

Furthermore, in JP-A No. 61-20939 ta,
A photosensitive composition using an anionic polyurethane resin is described. Such anionic polyurethane resins are water-based and are essentially different from the water-insoluble polyurethane resins of the present invention.

Since the anionic polyurethane resin is water-based, its solubility in organic coating solvents was insufficient. Moreover, it was undesirable because it deteriorated the stability of the diazo compound.

In addition, the majority of substances used as photosensitive substances in negative-acting systems are diazonium compounds.
The most commonly used resins include diazo resins represented by formaldehyde condensates of p-diazodiphenylamine.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin may be a diazo resin alone, i.e. without a binder, as described, for example, in U.S. Pat. No. 2,714,066. For example, JP-A-50-3060
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years, many photosensitive lithographic printing plates using diazonium compounds have a high printing durability. It is made of a diazonium compound and a polymer that acts as a binder.

As described in JP-A No. 50-30604, such a photosensitive layer is of the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the photosensitive layer is developed with an organic solvent developer. Although the so-called solvent-developed type is known, from the viewpoint of occupational safety and health, the alkaline-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkaline developability to the binder is to copolymerize a carboxylic acid-containing monomer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861,058. There is a method of introducing carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride, but the resulting polymer has poor abrasion resistance due to its structure. However, from photosensitive lithographic printing plates containing such a binder in the photosensitive layer, only lithographic printing plates with low printing durability could be obtained. On the other hand, polyvinyl acetal forms a tough film and is abrasion resistant, but it has the disadvantage that only organic solvent-developable photosensitive lithographic printing plates can be obtained.

In addition, polyurethane resin is a known polymer with excellent abrasion resistance;
and JP-A-56-94346 disclose a combination system of a diazonium compound and a substantially linear polyurethane resin, and a combination system of a diazonium salt polycondensate and a branched polyurethane resin, respectively. . However, as mentioned above, none of these polyurethane resins has an alkali-soluble group, and their solubility in an aqueous alkaline developer is essentially insufficient.
It was very difficult to carry out development without leaving a residual film. Furthermore, since it does not have a site that causes a photoreaction with the combined diazonium compound during exposure and crosslinks efficiently, it has the disadvantage that it does not form images with sufficient strength.

On the other hand, there have been many attempts to use a photopolymerizable composition as a photosensitive image forming layer of a negative-working photosensitive lithographic printing plate.
A basic composition consisting of a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in Japanese Patent Publication No. 32714, a polymer as a binder as disclosed in Japanese Patent Publication No. 34041/1983, Composition with improved curing efficiency by introducing bonds, 1973-
Publications No. 38403 and Special Publication No. 53-27605,
Compositions using novel photopolymerization initiators, such as those disclosed in British Patent No. 1.388.492, are known, and some have been put into practical use. Photosensitive compositions also have drawbacks in that their sensitivity is greatly affected by the surface temperature of the photosensitive lithographic printing plate during image exposure, and polymerization is strongly inhibited by oxygen during image exposure.

[Problem that the invention seeks to solve]

An object of the present invention is to overcome the above-mentioned drawbacks and to provide a novel photosensitive composition that has excellent developability with an aqueous alkaline developer and high stiffness resistance.

As a result of intensive study by the present inventors to achieve the above object,
It has been discovered that these objects can be achieved by using a novel photosensitive composition, and the present invention has been achieved.

That is, the present invention provides a photosensitive composition containing a poly(urethane-urea) resin having a carboxyl group and being insoluble in water and soluble in alkaline water.

The photosensitive compounds contained in the photosensitive composition of the present invention include the following (i), (ii), (iii) or (iv).
): (i) 0-quinonediazide compound.

(ii) Negative-acting diazonium compounds.

(iii) A combination of a polymerizable heptamer and a photopolymerization initiator.

(iv) A combination of a negative-acting diazonium compound, a polymerizable monomer and a photoinitiator.

Photosensitive compounds selected from can be used.

Below, poly(urethane-urea) used in the present invention
The resin and other components, and the method for producing and using the photosensitive composition of the present invention will be explained in detail.

(1) Poly (urethane-urea) resin The poly (urethane-urea) resin suitably used in the present invention is as follows -
A diisonanate compound represented by m formula (1), and -
C at least one diol compound of formula (II), (I), or (IV) and general formula (V), (■), or (■)
It is a poly(urethane-urea) resin whose basic skeleton is a structure represented by a reaction product with at least one type of compound.

0CN-Ill-NCO(1) [ R.

C00I+ 110-R3-^r -Ra -Oi1Rs
(n[)OOH OOH 11N-Ry O)1
(Vl) In the formula, R1 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, and halogeno groups are preferred). Depending on the requirements, R1 may contain other functional groups that do not react with isocyanate groups, such as ester, urethane, and amide groups.

R is a hydrogen atom, a substituent (e.g., cyano, nitro, halogen atom (-F, -C/!, Brs I), -
CONHL, -COORe, ORq,
N HCON HR9, N HCOORq, N H
CORv, OCON HRq, -CONHR.

(Here, R9 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms.). ), preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 6 to 15 carbon atoms.
represents an aryl group. Rx, R4, and Rs may be the same or different, and may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, or halogen groups are preferred). represents an aliphatic or aromatic hydrocarbon. Preferably carbon number 1~
20 alkylene groups, arylene groups having 6 to 15 carbon atoms, more preferably alkylene groups having 1 to 8 carbon atoms, and if necessary, does not react with isocyanate groups in R, R, Rs. It may also have other functional groups, such as carbonyl, ester, urethane, amide, and ether groups. Note that two or three of Rz, Rz, Ra, and Rs may form a ring. R6 and R11 may be the same or different, and each represents a hydrogen atom, a substituent (e.g. alkoxy, a halogen atom (-F, -C1, -Br,
-■), ester, and carboxyl group. ), preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group as a substituent, and an alkyl group having 6 to 15 carbon atoms which may have a carboxyl group as a substituent. Indicates an aryl group. R7 is a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (-F, -CI, -
Brs I ), carboxyl groups, and other groups are included. ), a divalent aliphatic hydrocarbon which may have
Indicates an aromatic hydrocarbon or a heterocyclic group.

If necessary, R1 may contain other functional groups that do not react with incyanate groups, such as carbonyl, ester, urethane, and amide groups. Note that Rh, R'l
, Rm may form a ring.

^r represents a trivalent aromatic hydrocarbon which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms.

The diisocyanate compound represented by the -C formula (+) specifically includes those shown below.

That is, 2,4-tolylene diisocyanate, a dimer of 2゜4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3°3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; isophorone diisocyanate, 4.4
'-methylenebis(cyclohexyl isocyanate),
Methylcyclohexane-2,4 (or 2,6) diisocyanate, ■.

Alicyclic diisocyanate compounds such as 3-(isocyanatomethyl)cyclohexane; diisocyanate compounds which are reaction products of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate; It will be done.

Specifically, the diol compound having a carboxyl group represented by the general formula (II), (III) or (rV) includes those shown below.

That is, 3,5-dihydroxybenzoic acid, 2,2-bis(
hydroxymethyl)propion, 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 M, N, N-'; hydroxyethylglycine , N
, N-bis(2-hydroxyethyl)-3-carboxy-propionamide, and the like.

Further, specific examples of the compound represented by the general formula (V), (Vl) or (■) include those shown below.

Namely, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, dodecamethylene diamine, propane-1
, 2-diamine, bis(3-aminopropyl)methylamine, 1.3-bis(3-aminopropyl)tetramethylsiloxane, piperazine, 2.5-dimethylpiperazine, N-(2-aminoethyl)piperazine, 4 -amino-2,2,6,6-titramethylpiperidine, N,N-
Aliphatic diamine compounds such as dimethylethylenediamine, lysine, L-cystine, etc.; 〇-phenylenediamine,
m-phenylenediamine, p-phenylenediamine 1.
2.4-) lylenediamine, benzidine, 0-diI-luidine, O-dianisidine, 4-nitro-m-phenylenediamine, 2.5-dimethoxy-p-phenylenediamine, bis-(4-aminophenyl)sulfone, 4-carboxy〇-phenylenediamine, 3-carboxy-
Aromatic diamine compounds such as m-phenylenediamine, 4,4'-diaminodiphenyl ether, 1,8-naphthalenediamine, etc.; 2-aminoimidazole, 3-aminotriazole, 5-amino-IH-tetrazole, 4
-aminopyrazole, 2-aminobenzimidazole,
2-amino-5-carboxy-triazole, 2,4-
Heterocyclic amine compounds such as diamino-6-methyl-S-) riazine, 2゜6-diamitubiridine, L-histidine, DL-tryptophan, adenine, etc.; ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1 -amino-2-propatur, 1-amino-3-propatol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, 2-amino-2
-Methyl-1-propanol, p-aminophenol,
m-aminophenol, 0-aminophenol, 4-methyl-2-aminophenol, 2-chloro-4-aminophenol, 4-methoxy-3-aminophenol, 4
-Hydroxybenzylamine, 4-amino-1-naphthol, 4-aminosalicylic acid, 4-hydroxy-N-phenylglycine, 2-aminobenzyl alcohol, 4-
Amino alcohols or aminophenol compounds such as aminophenethyl alcohol, 2-carboxy-5-amino-1-naphthol, L-tyrosine, etc.; 2,4-tolylene-bis(2-hydroxyethylcarbamide), m-xylylene-bis( 2-hydroxyethylcarbamide),
Hexamethylene-bis(2-hydroxyethylcarbamide), 4,4'-diphenylmethane-bis(2-hydroxyethylcarbamide), 1,5-naphthalene-bis(
Examples thereof include urea compounds such as 2-hydroxyethyl rubberamide) and the like.

When the above poly(urethane-urea) resin is used in combination with a negative-acting diazonium compound, hydroxyl groups and/or nitrile groups are added to the poly(urethane-urea) resin in order to increase the efficiency of photocrosslinking of the diazonium compound. ) Introduction of a hydroxyl group and/or nitrile group, which may be introduced into the resin, can be carried out, for example, by adding a halogen compound having a hydroxyl group and/or nitrile group to one of the carboxyl groups of the poly(urethane-urea) resin in the presence of a base. This can be achieved by reacting with

The poly(urethane-urea) resin of the present invention is a diisocyanate compound represented by the formula (I), a diisocyanate compound represented by the general formula (I)
It may be formed from any one or two or more of the diol compound represented by I), (■), or (IV) and the compound represented by the general formula (V), (■), or (■).

Furthermore, a diol compound that does not have a carboxyl group and may have other substituents that do not react with isocyanate may be used in combination to the extent that the alkali developability is not reduced.

Specifically, such diol compounds include those shown below.

Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1.3-7' ethylene glycol, 1
．． 6-hexanediol, 2-butene-1,4-diol, 2゜2,4-trimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclode Candimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, hydrogenated bisphenol ethylene oxide adduct, propylene oxide adduct to hydrogenated bisphenol, hydroquinone dihydroxy diethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis(2-hydroxyethyl)-2,4-1-lylene dicarbamate, Screw(
Examples include 2-hydroxyethyl)-m-xylylene dicarbamate and bis(2-hydroxyethyl)isophthalate.

The poly(urethane-urea) resin of the present invention is a compound of the above diisocyanate compound, -a formula (II), (III) or (
IV) and general formulas (V) and (Vl)
Or, at least one of (■) is synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating the mixture.

For the diisocyanate compound used, the general formula (n
), (I[[) or (IV) and general formula (V), (V
The total molar ratio of compounds l) or (■) is preferably 0
．． 8:1 to 1.21, and if an isocyanate group remains at the end of the polymer, it is finally synthesized in a form in which no isocyanate group remains by treatment with alcohols or amines.

Also, monocatalytic formula (V) for diisocyanate compounds, (
The preferred amount of compound Vl) or (■) used is 1 mol%
The amount is more preferably 5 to 50 mol%. When used in an amount of 50 mol% or more, solubility in organic solvents may deteriorate.

The molecular weight of the poly(urethane-urea) resin used in the present invention is preferably 1,000 or more on weight average, and more preferably in the range of 5,000 to 200,000.

These poly(urethane-urea) resins may be used alone or in combination.The content of these poly(urethane-urea) resins in the photosensitive composition is about 5 to 95% by weight. %, preferably about 10-90% by weight.

(2) Positive type 0-quinonediazide compound On the other hand, as the positive type 0-quinonediazide compound used in the present invention, preferably there is a 0-naphthoquinonediazide compound.

The most preferred 0-naphthoquinone diazide compound used in the present invention is an ester of 1,2-diazonaphthoquinone sulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 43-28403. Other suitable O-quinonediazide compounds include 1, which is described in U.S. Pat. Nos. 3,046,120 and 3,188,210;
There are esters of 2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resins. Other useful 0-naphthoquinone diazide compounds include:
It is reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-4
No. 9-38701, Opening/closing No. 48-13354, Special Publication No. 4
No. 1-11222, No. 45-9610, No. 1973
-17481 Publication, U.S. Patent No. 2,797,213, U.S. Patent No. 3,454,400, U.S. Patent No. 3,544.323
No. 3,573,917, No. 3.674,49
No. 5, No. 3,785,825, British Patent No. 1,22
No. 7,602, No. 1,251,345, No. 1.2
No. 67.005, No. 1.329,888, No. 1.
Examples include those described in various specifications such as No. 330.932 and German Patent No. 854,890.

The amount of the 0-quinonediazide compound that acts on positive type in the photosensitive composition of the present invention is 10 to 50% by weight.
More preferably, it is 20 to 40% by weight.

(3) Negative diazonium compounds Examples of the diazonium compounds used in the present invention include the diazonium compounds described in U.S. Pat. No. 3,867,147 and the diazonium compounds described in U.S. Pat. No. 2,632,703. Diazo resins typified by condensates with carbonyl-containing compounds (for example, formaldehyde) are useful.

Preferred diazo resins include, for example, hexafluorophosphates, tetrafluoroborates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, U.S. Patent No. 330030
Sulfonates of condensates of p-diazodiphenylamine and formaldehyde as described in No. 9 (e.g. p-)luenesulfonates, dodecylbenzenesulfonates, 2-methoxy-4-hydroxy-5- Also preferred are benzoylbenzenesulfonate, etc.), phosphinates (eg, benzenephosphinate, etc.), hydroxy group-containing compound salts (eg, 2,4-dihydroxybenzophenone salt, etc.), and organic carboxylates.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4.4
Mesitylene sulfonate obtained by condensation with '-bis-methoxy-methyl-diphenyl ether is also suitable.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% by weight, preferably 3 to 20% by weight.

Moreover, two or more types of diazonium compounds may be used in combination, if necessary.

(4) Polymerizable monomer/photopolymerization initiator The monomer that can be added to the photosensitive composition of the present invention has a boiling point of 100°C or higher at normal pressure, and is preferably at least one per molecule. It is a molecule having two or more addition-polymerizable ethylenically unsaturated groups, a flo, 000 or less heptad, or an oligomer. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and phenoxyethyl (meth)acrylate; polyprolene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; Brobylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipene erythritol hexa(meth)acrylate ) acrylate, hexanediol di(meth)
Acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohol such as glycerin or trimethylolethane, which is converted into (meth)acrylate after adding ethylene oxide or propylene oxide,
Special Publication No. 41708, Special Publication No. 41708, Special Publication No. 6034, No. 50-6034,
Urethane acrylates as described in each publication of JP-A-51-37193, JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylate i prepared by reacting an epoxy resin with (meth)acrylic acid can be mentioned. Further, those introduced as photocurable monomers and oligomers in Japan Adhesive Society Journal Vol. 1.20, Tane 7. pages 300 to 308 can also be used.

These monomers or oligomers and the poly(
The composition ratio of urethane-urea resin is 5:95 to 7 by weight.
The range is preferably 0:30, and the more preferred range is 10:
The ratio is 90-50:50.

Photoinitiators that can be added to the photosensitive composition of the present invention include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367.660, U.S. Pat. No. 2,367.661 and α-carbonyl compounds disclosed in U.S. Pat. No. 2,367.670, asiroin ethers disclosed in U.S. Pat. Aromatic acyloin compounds substituted with alpha-hydrocarbons as disclosed in the specification, multi-branched quinone compounds as disclosed in U.S. Pat. Triarylimidazole dimer/p-
Combination of Aminophenyl Ketones, U.S. Patent No. 3.870
．． Penduthiadur compounds disclosed in US Pat. No. 524, acridine and phenazine compounds disclosed in US Pat. No. 3,751,259, and US Pat. No. 4,212,970. Includes oxadiazole compounds, etc.

Preferred examples include trihalomethyl-S-triazine compounds and trihalomethyloxadiazole compounds represented by the following general formula (■) or (IX).

In the formula, R11 is a substituted or unsubstituted aryl group, alkenyl LRI. represents R, -CX, or a substituted or unsubstituted alkyl group. X represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (■) include Wakabu et al., Bull, Che+m, Soc, Japan.
, Vol. 42, p. 2924 (1969), British Patent No. 1.388,492, West German Patent No. 2.
No. 718.259 and West German Patent No. 3,337.024
Examples include the compounds described in the specification of No. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis(trichloromethyl)-5-triazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-8-triazine, 2
-(p-tolyl)-4,6-bis(trichloromethyl)
-3-triazine, 2-(p-methoxyphenyl)-4
, 6-bis(trichloromethyl)-5-triazine, 2
-(2',4'-dichlorophenyl)-4,6-bis(
trichloromethyl)-3-triazine, 2゜4.6-tris(trichloromethyl)-3-triazine, 2-methyl-4,6-bis(trichloromethyl)-3-)riazine, 2-n-nonyl-4゜6-bis(trichloromethyl)-3-triazine, 2-(α,α5β-trichloroethyl)-4,6-bis(trichloromethyl)-3-triazine, 2-styryl-4,6-bis(trichloro methyl)-3-) ryazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl)-3-1-riazine, 2-(p-methoxystyryl)-4,6-bis(
trichloromethyl)-3-triazine, 2-(4-methoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3-triazine, 2-(4-ethoxy-naphth-1-yl)- 4゜6-bis(trichloromethyl)-
3-triazine, 2-(4-(2-ethoxyethyl)
-naphth-1-yl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(4,7-dimethoxy-
naphthol-1-yl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(acenaphth-5-yl)-
4,6-bis(trichloromethyl)-3-)riazine,
2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-3-1-riazine and the like are included.

Further, as the compound represented by the general formula (IX), for example, JP-A No. 54-74728, JP-A No. 55-7774
Examples thereof include compounds described in Publication No. 2 and JP-A-59-148784.

Specifically, the following compounds are included.

That is, 2-styryl-5-trichloromethyl-1,3,
4-Oxadiazole, 2-(4-chlorostyryl)-
5-1-lichloromethyl-1,3゜4-oxadiazole, 2-(4-methylstyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(4-methoxystyryl)-5 -Trichloromethyl-1,3,4-oxadiazole, 2-(4-butoxystyryl)-5-
Trichloromethyl-1,3,4-oxadiazole, 2
-(4-styrylstyryl)-5-trichloromethyl-
1,3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-
(4-methoxyphenyl)-5-trichloromethyl-1
, 3,4-oxadiazole, 2-(3,4-dimethoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(4-styrylphenyl)-5=
Trichloromethyl-1,3,4-oxadiazole, 2
-(1-naphthyl”)-5-)dichloromethyl-1,3
, 4-oxadiazole and the like.

If necessary, an aggravating agent can be added to the photosensitive composition of the present invention. Specifically, aromatic thiazole compounds shown in Japanese Patent Publication No. 59-28328, Japanese Patent Publication No. 54-1
Examples include merocyanine dyes shown in JP-A-51024, aromatic thiopyrylium salts and aromatic biryllium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, and ketocoumarins. It will be done. Furthermore, systems in which these are combined with hydrogen donors such as N-phenylglycine, 2-menicabutopenzothiazole, and ethyl N,N'-dimethylaminobenzoate are also effectively used in the present invention.

The amount of the photopolymerization initiator and/or sensitizer in the present invention is
Photopolymerizable ethylenically unsaturated compound and the polyester of the present invention
A range of 0.01% to 20% by weight based on the total amount with the (urethane-urea) resin is sufficient, and more preferably a range of 0.5% to 10% by weight gives good results.

(5) Other components In addition to the poly(urethane urea) resin, the composition of the present invention contains phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and carboxyl Known alkali-soluble polymer compounds such as group-containing epoxy resins, polyacetal resins, acrylic resins, and methacrylic resins can be included. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

In the composition of the present invention, dyes, pigments, stabilizers, surfactants, plasticizers, and other fillers can be added as print-out agents and image coloring agents to obtain a visible image immediately after exposure. .

Further, when combined with an 0-quinonediazide compound, a cyclic acid anhydride may be added to increase sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-tetrahydrophthalic anhydride, as described in U.S. Pat. No. 4,115,128. Examples include tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, phosuccinic anhydride, and pyromellitic anhydride. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times.

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223, JP-A-54-7
Examples include the combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728.

Dyes other than the above-mentioned salt-forming organic dyes can also be used as image colorants. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #10h oil yellow #130, oil pink #312, oil green BG, oil blue BO3, oil blue #603
, Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Bioleft (CT42)
535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (C
I52015).

Furthermore, when combined with a diazonium compound, stabilizers include phosphoric acid, phosphorous acid, oxalic acid, p-toluenesulfonic acid, dipicolinic acid, malic acid, tartaric acid, 2-methoxy-4-hydroxy-5-benzoyl-benzene. Examples include sulfonic acid, butylnaphthalenesulfonic acid, p-hydroxybenzenesulfonic acid, and the like.

Furthermore, when the polymerizable monomer is combined with a photopolymerization initiator, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during production or storage of the photosensitive composition. It is desirable to add Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,
Pyrogallol, t-7'-tylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-[-butylphenol), 2,2'-methylenebis(4-methyl-6
-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine cerous salt, and the like.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Methanol, ethanol, isopropanol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol Tool, ■-methoxy 2-propyl acetate, methyl lactate, ethyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, T-butyrolactone, N-methylpyrrolidone, tetramethylurea, tetrahydrofuran, dioxane, dimethyl sulfoxide, Examples include sulfolane, toluene, and ethyl acetate, and these solvents can be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight. Although the coating amount varies depending on the application, for example, for photosensitive planographic printing plates, it is generally preferable to have a solid content of 0.5 to 3.0 g/I, P! ! As the number of layers decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

Supports to which the photosensitive composition of the present invention is applied include, for example, paper, plastics (such as polyethylene,
Paper laminated with polypropylene, polystyrene, etc., such as aluminum (including aluminum alloys)
), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate,
Films of plastics such as butyric acid se) Lt loin, acetic acid a2 buty-11 cellulose, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, bopropylene, polycarbonate, polyvinyl acetal, etc., paper laminated with or vapor-deposited with metals such as those mentioned above, or This includes plastic films, etc. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.

In addition, in the case of a support having a surface made of metal, especially aluminum, surface treatment such as grain treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment, etc. It is preferable that the aluminum plate be immersed in a sodium silicate aqueous solution as described in U.S. Pat. No. 2,714,066, Aluminum plates are anodized and then immersed in an aqueous solution of alkali metal silicate, and mechanically roughened and electrolytically roughened as described in U.S. Pat. No. 11,476.006. Aluminum supports treated in combination with oxidation are also preferably used. The above-mentioned anodizing treatment may be performed using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination of two or more. It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution.

Further, it is also preferable to perform grain molding, anodic oxidation, and sealing treatment. Such pore sealing treatment is performed using a sodium silicate aqueous solution,
This is carried out by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

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

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 and subsequent development with an aqueous alkaline developer gives a positive or negative relief image to the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent coating properties when applied onto a support, and also excellent developability when developing exposed areas with an aqueous alkaline developer after coating, drying, and image exposure. The relief image obtained has good abrasion resistance and good adhesion to the support, and when used as a printing plate, many good prints can be obtained.

"Examples" The present invention will be explained in more detail with reference to synthesis examples and examples, but the content of the present invention is not limited thereto.

13.4 g (0.10 mol) of 2,2-bis(hydroxymethyl)propionic acid, 7.1 g of 1゜6-hexylene glycol in a 500 ml three-necked round-bottomed flask equipped with a condenser and a stirrer. g (0,060 mol) 1.3-bis(3-aminopropyl)tetramethylsiloxane9.
Add 9 g (0,040 mol) of N.

It was dissolved in 120 liters of N-dimethylacetamide.

To this, 4,4'-diphenylamine diisocyanate 5
0.1 g (0.20 mol) was added thereto, and the mixture was heated and stirred at 100° C. for 6 hours. Thereafter, it was diluted with N,N-dimethylformamide. The reaction solution was poured into water H with stirring to precipitate a white polymer. The polymer was filtered off, washed with water, and dried under vacuum to obtain 75 g of polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 42,000.

Furthermore, the carboxyl group content (acid value) was measured by titration and found to be 1. 22 meq/g (poly(urethane-urea) resin of the present invention + al).

2,2-bis(hydroxymethyl)propion, acid 13
．． 4g (0.10 mol), diethylene glycol 4.2
g (0.04 mol), 7.sg (0.060 mol) of 2.4-)rylene-bis(2-hydroxyethylcarba-) and 35.1 g (0.14 mol) of 4,4'-diphenylmethane diisocyanate. ) and 0.1 g (0.060 mol) of hexamethylene diisocyanate 1, the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1. 76 g of a white polymer was obtained. The molecular weight was measured by GPC, and the weight was 37,000 on average (polystyrene standard)
Met. In addition, when the carboxyl group content was measured by titration, 1. It was 20 meq/g (
Poly(urethane-urea) resin (b)) of the present invention.

The poly(urethane-urea) resin of the present invention was synthesized in the same manner using the diisocyanate compounds shown in Table 1, diol compounds, diamine compounds, aminoalcohol compounds, or urea compounds.

Furthermore, the molecular weight was measured by GPC, and the carboxyl group content was measured by titration. The measured carboxyl group content (acid value) is shown in Table 1, and the molecular weight is all weight average (polystyrene standard) is, ooo ~ 65,000.
Met. The surface of a 0.30-thick marminium plate was grained using a nylon brush and a water suspension of 400 mesh bumiston, and then thoroughly washed with water. After etching by immersing it in 10% sodium hydroxide at 70°C for 60 seconds, it was washed with running water, neutralized with 20% nitric acid, and washed with water.

This was applied to 160 clones/da'' in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of Va''12.7■.
Electrolytic surface roughening treatment was performed using a special anode electricity amount of . When the surface roughness was measured, it was 0.6μ (expressed as Ra).

Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and heated at 55°C for 2 hours.
After desmutting for a minute, it was anodized in a 20% sulfuric acid aqueous solution at a current density of 2 A/dm'' to a thickness of 2.7 g/d.

Next, five types of photosensitive liquids (A) were prepared by changing the type of poly(urethane-urea) resin used in the present invention in the following photosensitive liquid (A).
-1 to (A)-5 were prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried for 2 minutes at 100°C. )-5
was created.

The coating amount at this time was 2.5 g/rrf in dry multilayer.

The poly(urethane-urea) resins used in the present invention for photosensitive solutions (A)-1 to (A)-5 are shown in Table 2.

Photosensitive solution (A) Next, as a comparative example, the following photosensitive solution (B) was coated in the same manner as Photosensitive solution C] to prepare a photosensitive lithographic printing plate (B). The coating weight after drying was 2.5 g/rrf.

Photosensitive liquid CB) A positive lithographic printing plate (Al-1 to 5 and (B)) was placed in close contact with the positive original drawings of line drawings and halftone dot images on the photosensitive layer, and was exposed from a distance of 70 countries using a 30 ampere carbon arc lamp. Exposure was performed.

Exposed photosensitive lithographic printing plates (A)-1 to 5 and CB)
was developed with an 8-fold diluted aqueous solution of DP-4 (trade name; manufactured by Fuji Photo Film ■) at 25° C. for 60 seconds.

The obtained lithographic printing plates (A)-1 to -5 and (B) were used to print on high-quality paper with a commercially available ink using a KOR type printing machine manufactured by Heidelberg. Lithographic printing plates (A)-1 to 5 and CB
), the final number of copies printed was as shown in Table 2.

Table 2 As can be seen from Table 2, lithographic printing plates (A)-1 to 5 (Examples 1 to 5) using the photosensitive composition of the present invention were superior to Comparative Example (B). It has a large number of prints and has excellent printing durability.

In addition, instead of the resin of the present invention in the photosensitive liquid (A), Estane #5715 (B
, F, manufactured by Gutdrich), coating, exposure,
When development was performed, development was poor and a clear image could not be obtained. This shows that the resin of the present invention has extremely excellent developability in an aqueous alkaline developer compared to polyurethane resins that do not have carboxyl groups.

The surface of an aluminum plate with a thickness of 0.24 am was sanded using a nylon brush and an aqueous suspension of 400 mesh of bumiston, 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 No. 53-67507, that is, Va =12.7V, Vc=9. IV (7) Using a sinusoidal alternating current waveform, electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution with an anode specific electricity amount of 160 clones/da''.Subsequently, it was immersed in a 30% sulfuric acid aqueous solution at 55°C. After desmutting for 2 minutes in a 7% aqueous solution of sulfuric acid, anodization treatment was carried out in a 7% aqueous solution of sulfuric acid so that the amount of 11I on aluminum oxide was 2.0 g/n. The aluminum obtained as described above was coated with the following photosensitive solutions (C)-1 to (C)-5 using a wheeler, and then washed with water and dried.
It was dried at 0°C for 2 minutes. Dry weight was 2.0 g/g.

The poly(urethane-urea) resins used in the present invention for photosensitive solutions [C)-1 to [C]-5 are shown in Table 3.

Photosensitive Solution (C) Next, as a comparative example, a photosensitive solution (D) using the following polymer instead of the poly(urethane-urea) resin used in the present invention in the above photosensitive solution was applied and dried in the same manner. The dry weight was 2.0 g/m.

(Polymer used in comparative example) A polymer with H structure, a / b / c /
The molar ratio of d was 9/24158/9.

In addition, the weight average molecular weight (polystyrene standard) is 55,
It was 000.

Each of the photosensitive lithographic printing plates (C)-1 to 5 and CD) obtained using photosensitive solutions (C)-1 to 5 and [D] was coated with Fuji photographic film (at a distance of 1 m using ll PS light). from 1
After exposing the image for 1 minute 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, and the bright blue image of lithographic printing plates (C)-1 to 5 and C
D) was obtained.

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

The final number of printed sheets of lithographic printing plates (C)-1 to -5 and (D) was examined and was as shown in Table 3.

Table 3 As can be seen from Table 3, the lithographic printing plates (C)-1 to 5 (Examples 6 to 10) using the photosensitive composition of the present invention had better printing performance than the comparative example CD). It has a large number of sheets and has excellent rigidity.

The following photosensitive solution (E) was applied to the aluminum plate obtained in Example 6.
-1 to (E)-4 were applied using a boiler and dried at 80°C for 2 minutes. The dry weight was 2.0 g/bo.

The poly(urethane-urea) resins used in the present invention for photosensitive solutions (E)-1 to (E)-4 are shown in Table 4.

Photosensitive solution (E) Next, as a comparative example, benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer (
A photosensitive solution (F) having a weight average molecular weight of 45,000 (polystyrene standard) was similarly applied and dried. Is the dry weight 2.0g/ry? Met.

Each of the photosensitive lithographic printing plates (B)-1 to 4 and [F] obtained using the photosensitive solutions (E)-1 to 4 and (F) was photographed from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■. After exposing the image for 1 minute and immersing it in the developer used in Example 6 at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and a lithographic printing plate (E) with a bright blue color image was prepared. )-1 to 4
and (F) were obtained.

Each printing plate was used to print on high-quality paper using a commercially available ink on a Heidelberg KOR printing machine.

The final number of printed sheets of the lithographic printing plates (E)-1 to -4 and (F) was examined and was as shown in Table 4.

Table 4 As can be seen from Table 4, the number of printed plates for lithographic printing plates (E)-1 to 4 (Examples 11 to 14) using the photosensitive composition of the present invention was higher than that of comparative example (F). It has a high rigidity and excellent rigidity.

Examples 15-16 The following photosensitive liquid (G) was applied to the aluminum plate obtained in Example 6.
-1 to (G)-2 were applied using a boiler and dried at 80°C for 2 minutes. Dry weight was 2.0 g/rd.

The poly(urethane-urea) resins used in the present invention for photosensitive solutions (G)-1 to (G)-2 are shown in Table 5.

Photosensitive liquid [G] Next, as a comparative example, methyl methacrylate-methacrylic acid (molar ratio 80/20) copolymer (weight average molecular ff152,000 (polystyrene standard))
A photosensitive solution (11) using the same method was applied and dried in the same manner. The dry weight was 2.0 g/rrr.

The photosensitive lithographic printing plates CG)-1 to 2 and (If) obtained using the photosensitive solutions (G)-1 to 2 and (II) were each coated with a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m for 1 minute. After imagewise exposure and immersion for 1 minute at room temperature in the developer used in Examples 6 to 10, the surface was lightly rubbed with absorbent cotton.
The unexposed areas were removed and a lithographic printing plate with a bright blue image (G
)-1 to -2 and [H) were obtained.

Each printing plate was used to print on high-quality paper using a commercially available ink on a Heidelberg KOR printing machine.

The final number of printed sheets of the lithographic printing plates (G)-1 and (G)-2 and (H) was examined and was as shown in Table 5.

Table 5 As shown in Table 5, the lithographic printing plates CG)-1 and CG)-2 (Examples 15 and 16) using the photosensitive composition of the present invention were as follows:
Compared to Comparative Example (H), the number of prints was larger and the rigidity resistance was very excellent.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent developability with an aqueous alkaline developer and high rigidity resistance.

Claims (1)

[Claims] A photosensitive composition comprising a poly(urethane-urea) resin having a carboxyl group and being insoluble in water and soluble in alkaline water.