JPH0485542A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve the developability of a planographic printing plate with an aq. alkali developing soln., the printing resistance and solubility in an applied solvent by using a compd. contg. specified polyurethane. CONSTITUTION:This compsn. contains polyurethane resin having carboxyl groups, insoluble in water but soluble in an aq. alkali soln. and contg. at least 10wt.% arom. hydrocarbon moieties. The polyurethane resin is produced by adding 0.1-0.3wt.% water basing on the amt. of a polymerizable soln. to a polymn. system at the time of polymn. or polymerizing an isocyanato compd. under dropping in a diol compd. and a solvent. In the case of <0.1wt.% water in the polymn. system, solubility improving effect is not satisfactory. In the case of >0.3wt.% water, the content of urea bonds is excessively increased and satisfactory performance is not obtd. In the case of <10wt.% arom. hydrocarbon moieties, the strength of the resin as a binder and developability improving effect are not satisfactory.

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 permeability, poor abrasion resistance, and poor stiffness when used in lithographic printing plates. There were some points that needed improvement, such as inadequacies, and there were limits in terms of application.

In order to solve this problem, various polymer compounds or binders have been investigated. For example, special public relations
The polyhydroxystyrene or hydroxystyrene copolymer described in Publication No. 1050 did have the drawbacks of improved film properties and poor abrasion resistance. In addition, JP-A-5I-3471.1 proposes the use of 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, as a known polymer with excellent wear resistance, there is polyurethane resin, which is disclosed in Japanese Patent Publication No. 49-36961,
A combination system of a positive acting diazo compound and a substantially linear polyurethane resin is disclosed. However, the polyurethane resin does not have an alkali-soluble group,
Essentially, the solubility in an aqueous alkaline developer is insufficient, and it is extremely difficult to perform development to completely remove the photosensitive layer in the non-image area (N-front area).

Furthermore, JP-A-61-20939 describes a photosensitive composition using an anionic polyurethane resin. 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,
The 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 resin is a diazo resin represented by a formaldehyde condensate 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
In recent years, many photosensitive lithographic printing plates using diazonium compounds (later high printing durability It is made of a diazonium compound and a polymer as a binder to give it properties.

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. It is known that the so-called solvent-developed type is removed, but from the standpoint of occupational safety and health, attention is focused on the alkali-developed type, which 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. Is there a way to introduce carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride? 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. ing.

However, as mentioned above, none of these polyurethane resins have an alkali-soluble group, and are inherently insufficiently soluble in aqueous alkaline developing solutions, making it extremely difficult to develop them without forming a residual film. It was difficult.

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 the disadvantage 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.

In addition, the produced polyurethane resin must be separated from the polymerization solvent because it may have an unfavorable effect on the solvent used in the polymerization or other photosensitive materials.

On the other hand, a photosensitive composition containing a polyurethane resin is used by dissolving it in an organic solvent and then coating it on a support. However, once polyurethane resin is separated and dried from a solution state, its high cohesive force reduces its solubility when it is redissolved, often resulting in the formation of undissolved substances or a decrease in permeability (hereinafter referred to as turbidity). (referred to as "temperature"), clogging of the filter in the liquid delivery system, increase in liquid delivery pressure,
This may cause practical problems such as deterioration of the surface condition of the coated product. In other words, the filters installed in the liquid delivery piping system are originally installed for the purpose of removing minute amounts of solid foreign matter, so if the polymer insolubles described here adhere to them, they will become severely clogged, causing the liquid delivery pressure to drop. causes an increase in Furthermore, if the polymer is coated on an aluminum plate without removing the polymer insoluble matter, it causes uneven coating and printing, which is very inconvenient in practice.

[Problem to be solved by the invention]

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, high printing durability, and good solubility in a coating solvent. be.

[Means to solve the problem]

The above object of the present invention is to provide a polyurethane resin having a carboxyl group and being insoluble in water and soluble in alkaline water, the content of aromatic hydrocarbon moieties in the resin being at least 10% by weight.
%, and is achieved by a photosensitive composition characterized by containing a polyurethane resin produced by the following production method.

(1) A method in which 0.1% to 0.3% (wt% of the polymerization solution) of water is present in the polymerization reaction system during polymerization, or (2) Polymerization while dropping an isocyanate compound into a diol compound and a solvent. How to do it.

If the amount of water in the polymerization reaction system is less than 0.1%, the solubility improvement effect will be insufficient, and if it exceeds 0.3%, the content of the urea bonding moiety will be excessive, resulting in insufficient performance for practical use. I can't. Further, if the content of the aromatic hydrocarbon moiety is less than 10%, the strength as a binder and the effect of improving developability are insufficient.

The photosensitive compounds contained in the photosensitive composition of the present invention include the following (i), (ii), (iii) and (iv).
Photosensitive compounds selected from can be used.

(i) o-quinonediazide compound.

(ii) Negative-acting diazonium compounds.

(iii) combination of a polymerizable monomer and a photoinitiator;

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

Next, the polyurethane resin and other components used in the present invention, and the method for producing and using the photosensitive composition of the present invention will be explained in detail.

(1) Polyurethane resin The polyurethane resin suitably used in the present invention is a diisocyanate compound represented by the following general formula (I) and a diol compound represented by the general formula (II), (■), or (IV). It is a polyurethane resin whose basic skeleton is a structure represented by a reaction product with

QCN-R-NGO (I) HO-R'-C-R'-OH 0OH (In) COO)1 1i0- R''-N-R'-0f( R5(IV) OOH In the formula, R1 is Substituents (e.g. alkyl, aralkyl,
Preferred are aryl, alkoxy, and halogeno groups. )
represents a divalent aliphatic or aromatic hydrocarbon group which may have If necessary, R] is another functional group that does not react with the isocyanate group, such as ester, urethane, amide,
It may have a ureido group.

R2 is a hydrogen atom, a substituent (for example, cyano, nitro, halogen atom (-F, -C1, -Br, -I), -
CONH2, -COOR6-OR' -NHCONH
R'-N)1cOOR6, -NHCOR', -0CON
HR' -CONHR6 (Here, R6 has 1 carbon number
-10 alkyl group, C7-15 aralkyl group. ) etc. are included. ), and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R
3, R4, and R5 may be the same or different, and may have a single bond or a substituent (for example, a multigroup such as alkyl, aralkyl, aryl, alkoxy, or halogen is preferable). represents an aliphatic or aromatic hydrocarbon group. Preferably it is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. Also, if necessary, R3
, R4, and R5 may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. Note that R2
, R3, R4, and R5 may form a ring.

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

Here, it is necessary to contain an aromatic hydrocarbon group in either the diisocyanate compound or the diol compound of the above general formula, and such an aromatic hydrocarbon group has a great effect on printing durability during printing. I discovered that The content of aromatic hydrocarbon groups in the polyurethane resin must be at least 10% by weight, more preferably 20% by weight or more.

Specifically, the diisocyanate compound represented by the general formula (I) includes those shown below.

That is, 2,4-4-lylene diisocyanate, a dimer of 2°4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
~Rxylylene diisocyanate 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3°3'-dimethylbiphenyl-4,4'
- Aromatic diisocyanate compounds such as diisocyanate, etc.: 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, 1°3-(isocyanatomethyl)cyclohexane, etc.; 1,
Examples include diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of 3-butylene glycol and 2 mols of tolylene diisocyanate.

Further, the diol compound having a carboxyl group represented by the general formula (II), (■), or (IV) specifically includes those shown below.

i.e., 3,5-dihydroxybenzoic acid, 2,2-bis(
hydroxymethyl)propionic acid, 2゜2-bis(2-
hydroxyethyl)propionic acid, 22-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)nishioic acid, bis(4-hydroxyphenyl)acetic acid,
4,4-bis(4-hydroxyphenyl)pentanoic acid,
Tartaric acid, N, N-dihydroxyethylglycine, N, N
-bis(2-hydroxyethyl)-3-carboxy-propionamide and the like.

When the above polyurethane resin is used in combination with a negative-acting diazonium compound, hydroxyl groups and/or nitrile groups may be introduced into the polyurethane resin in order to increase the efficiency of photocrosslinking of the diazonium compound. Introduction of a hydroxyl group and/or a nitrile group can be achieved, for example, by reacting a halogen compound having a hydroxyl group and/or a nitrile group with a portion of the carboxyl groups of the polyurethane resin in the presence of a base.

In the case of a nitrile group, it can also be introduced into the polyurethane resin by using a diol compound having a nitrile group in combination with a diol compound of general formula (In), (III) or (IV).

The polyurethane resin of the present invention is a diisocyanate compound represented by general formula (I) and general formula (II), (■
), or (IV) may be formed from two or more diol compounds having a carboxyl group.

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 deteriorated.

Specifically, 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.
6-hexanediol, 2-butene-1,4-diol, 2゜2.4-)dimethyl-1,3-bentanediol, 1.4-bis-β-hydroxynidoxinclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A1 hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, 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-)lylene dicarbamate, 2,4. −
1 rylene-bis(2-hydroxyethylcarbamide),
Examples include bis(2-hydroxyethyl)-m-xylylene dicarbamate and bis(2-hydroxyethyl) isophthalate.

The polyurethane resin of the present invention is synthesized by adding a known catalyst having an activity according to the reactivity of each of the above diisocyanate compounds and diol compounds in an aprotic solvent and heating. .1~0.
Obtained by the presence of 3% by weight of distilled water. In this case, the entire amount of distilled water may be added into the flask at the time of preparation, or a portion may be added into the system first and the remaining amount may be added dropwise during polymerization. .

Examples of the catalyst include tertiary amines such as triethylene diamine, and organotin compounds such as di-n-butyltin dilaurate, tri-n-butyltin acetate, and di-n-butyltin diacetate.

Another method for obtaining the polyurethane resin of the present invention is to add the above-mentioned diol compound and the above-mentioned catalyst into an aprotic solvent, heat this, and dropwise add the above-mentioned diisocyanate compound before polymerizing. It will be done.

In this method, a part of the diisocyanate compound may be added during the preparation, and the rest may be added dropwise during the polymerization, or if multiple types of diisocyanate compounds are used, one type may be added in advance during the preparation, and the others may be added dropwise during the polymerization. Polymerization may be carried out without dropping the type.

According to the method of adding water according to the present invention, foreign bonds such as urea bonds are formed in a part of the polyurethane molecular chain, which makes the polymer less likely to crystallize and improves resolubility. Furthermore, according to the method of dropping a diisocyanate compound, crystallization is suppressed by randomly arranging 4゜4-diphenylmethane diisocyanate, highly crystalline hexamethylene diisocyanate, and the diol compound in the polymer molecular chain. Conceivable.

The molar ratio of diisocyanate and diol compound to be used is preferably 0.8:1 to 1.221, and if isocyanate groups remain at the end of the polymer, the final Synthesized in such a way that no isocyanate groups remain.

The molecular weight of the polyurethane resin of the present invention is preferably 1000 or more on weight average, more preferably 5.000.
The range is 200,000 to 200,000.

These polymer compounds may be used alone or in combination. The content of these polymer compounds contained in the photosensitive composition is about 5 to 95% by weight, preferably about 10 to 95% by weight.
It is 90% by weight.

(2) Positive type 0-quinonediazide compound On the other hand, the positive type Q-quinonediazide compound used in the present invention is preferably an 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 also esters of 2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins. Other useful. - As a naphthoquinone diazide compound,
It is well known and has 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, No. 13354 (1973), Special Publication No. 4 (Sho 4)
No. 1-11222, No. 1973-9610, No. 49-
No. 17481, U.S. Patent No. 2,797.213,
3.454.400, 3.544.323, 3.573.917, 3.674.495
No. 3, 785.825, British Patent No. 1.227
．． No. 602, No. 1, No. 251.345, No. 1.26
No. 7,005, 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 these positive-acting 0-quinonediazide compounds in the photosensitive composition of the present invention is 10 to 50% by weight.
The content is more preferably 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, tetrafluorophosphates, 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 (e.g., p-toluenesulfonates, dodecylbenzenesulfonates, 2-methoxy-4-hydroxy-5-benzoyl Also preferred are benzenesulfonate, etc.), phosphinate (eg, benzenephosphinate), hydroxy group-containing compound salts (eg, 2,4-dihydroxybenzophenone salt), organic carboxylates, and the like.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4,4
Menthylene 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 at least 1 per molecule, more preferably 2 monomers per molecule. A monomer or oligomer having a molecule Ji of 10,000 or less and having at least 10,000 ethylenically unsaturated groups capable of addition polymerization. Such monomers or oligomers include monofunctional acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxyethyl (meth)acrylate, methacrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Bilene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate
(meth)acrylate, pentaerythritol tetra(
meth)acrylate, dipentaerythritol hexa(
meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohols such as glycerin and trimethylolethane that are converted into (meth)acrylates after adding ethylene oxide or propylene oxide; Urethane acrylates such as those described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid, which are described in Publications No. 52-30490. In addition, Japan Adhesive Association Magazine Vol.
．． 20, Nα7. Those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

The composition ratio of these monomers or oligomers to the polyurethane resin of the present invention is preferably in the range of 5=95 to 70:30 by weight, and more preferably in the range of 10:90 to 50:5.
It is 0.

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 and U.S. Pat. No. 2,367,661. α-carbonyl compounds disclosed in U.S. Pat. Aromatic acyloin compounds substituted with a hydrocarbon at the α-position disclosed in the specification, polynuclear bovine compounds disclosed in U.S. Patent Nos. 3.046.127 and 2.951.758 , triarylimidazole dimer/as disclosed in U.S. Pat. No. 3,549,367.
Combination of p-aminophenyl ketones, U.S. Pat. No. 3.8
Benzothiazole compounds disclosed in U.S. Pat. No. 70.524, acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751.259, and U.S. Pat. No. 4.212.970. This includes oxadiazole compounds, etc.

Preferably I represented by the following formula (V) or (VI)
-Dihalomethyl-S-triazine compounds or trihalomethyloxadiazole compounds may be mentioned.

In the formula, R'' is a substituted or unsubstituted aryl group,
The alkenyl group R7 represents R8, -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 (V) include Wakabayashi et al., Bull, Chem, 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. 3.337.02
Examples include the compounds described in Specification No. 4. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis(trichloromethyl)-3-1 riazine, 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)-3-triazine,
2-(2',4'-dichlorophenyl)-4,6-bis(trichloromethyl)-3-1=riazine, 2°4.6
-1 lis(trichloromethyl)-3-triazine, 2-
Methyl-4,6-bis(trichloromethyl)-3-)riazine, 2-n-nonyl-4゜6-bis(trichloromethyl)-3-triazine, 2-(α,α,β-trichloroethyl)- 4,6-bis(trichloromethyl)-3-
Triazine, 2-styryl-4,6-bis(trichloromethyl)-8-triazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-methoxy) styryl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4-methoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4 -ethoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3
-Triazine, 2-C4-(2-ditoxyethyl)-naphth-lyl)-4,6-bis(trichloromethyl)-
s-triazine, 2-(4,7-dimethoxy-naphthol-1-yl)-4,6-bis(trichloromethyl)-3-
Triazine, 2-(acenaphth-5-yl)-4,6-
Bis(trichloromethyl)S-) riazine, 2-(4-
Styryl phenyl)-4,6-bis(trichloromethyl)-3-triazine and the like.

Further, as the compound represented by formula (VI), for example, JP-A No. 54-74728, JP-A No. 55-7774
Examples 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 cyclomethyl-1,34-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-
Contains ogisadiazole, etc.

A sensitizer can be added to the photosensitive composition of the present invention if necessary. Specifically, aromatic thiazole compounds shown in Japanese Patent Publication No. 59-28328, Japanese Patent Publication No. 54-1
Merocyanine dyes shown in JP-A No. 51024, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, and ketocoumarins. Can be mentioned. Furthermore, N-phenylglycine, 2-mercaptobenzothiazole, N N'-
Systems in combination with hydrogen donors such as ethyl dimethylaminobenzoate are also effectively used in the present invention.

The amount of the photopolymerization initiator and/or sensitizer in the present invention is
A range of 0.01% to 20% by weight based on the total of the photopolymerizable ethylenically unsaturated compound and the polyurethane resin of the present invention is sufficient, and more preferably 0.5% by weight.
Good results are obtained at 10% by weight.

(5) Other components In addition to the above-mentioned polyurethane resins, the composition of the present invention includes phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and carboxyl group-containing epoxy resin. Known alkali-soluble polymer compounds such as polyacetal resin, acrylic resin, methacrylic resin, etc. can be contained. 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, succinic 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
It is described in Publication No. 128. - Combination of naphthoquinone diazide-4-sulfonic acid halide and salt-forming organic dye, and 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 #101, 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 (CI42555L Methyl Bio I/T (CI)
42535), rhodamine B (C145170B),
Examples include malachite green (CI 42000) and methylene blue (CI 52015).

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 a polymerizable monomer and a photopolymerization initiator are combined, 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-butylcatechol, benzoquinone,
4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2'-methylenebis(4-methyl-6-
(t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine cerous salt, and the like.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. Solvents used here include 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,
1-methoxy-2-propyl acetate, methyl lactate,
Ethyl lactate, N,N-dimethylformamide, N,N-
Dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, tetramethylurea, tetrahydrofuran, dioxane, dimethylsulfoxide, sulfolane,
Examples include 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. Further, the coating amount varies depending on the application, and for example, in the case of photosensitive planographic printing plates, it is generally preferable to have a solid content of 0.5 to 3.0 g/rd. As the coating amount decreases, the photosensitivity increases or the physical properties of the photosensitive film deteriorate.

Supports to which the photosensitive composition of the present invention is coated include, for example, paper, plastics (such as polyethylene,
Polypropylene, polystyrene, etc.) or laminated paper, such as aluminum (also includes aluminum alloys).

), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate,
These include films of plastics such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., metal or laminates as mentioned above, or vapor-deposited paper or plastic films. . 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 of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable that In addition, as described in U.S. Patent No. 2.714.066, an aluminum plate immersed in a sodium silicate aqueous solution, and as described in Japanese Patent Publication No. 47-5125, an aluminum plate can be anodized. Aluminum treated and then immersed in an aqueous solution of an alkali metal silicate, treated by a combination of mechanical and electrolytic roughening as described in U.S. Pat. No. 4,476,006. Supports are also suitably 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.

It is also preferable that the material is grained, anodized, and then sealed. 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, followed by 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 obtained relief image has good abrasion resistance and good adhesion to the support, and when used as a printing plate, a large number of 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.

Synthesis Example 1 (Water Presence Method) 22.2 g (0.17 mol) of 2,2-bis(hydroxymethyl)propionic acid and 14.0 g of diethylene glycol were placed in a 11-sized round-bottom flask equipped with a condenser and a stirrer and purged with nitrogen. 0g (0.13mol), 1.4
- Add 8.0 g (0.09 mol) of butanediol,
Dissolved in 226 g of N,N-dimethylacetamide. Add 0.50 g of distilled water to this system. 4,
4-diphenylmethane diisocyanate 59.2 g
(0.24 mol), 26.6 g (0.16 mol) of hexamethylene diisocyanate, and 0.31 g (0.31 di-n-butyltin dilaure) of hexamethylene diisocyanate as a catalyst.
g (0.49 mmol) and heated at 90°C under a nitrogen stream.
The mixture was heated and stirred for 9 hours.

Thereafter, 113 g of N,N-dimethylformamide, 56.3 g of methanol, and 20.4 g of acetic acid were added to stop the reaction and diluted. The reaction solution was dropped into ion-exchanged water 21 with stirring to precipitate a white polymer. This polymer was filtered, further washed with ion-exchanged water 21, and dried to obtain 130 g of polymer (polyurethane resin (a) of the present invention).

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight was 56.0.
00 (polystyrene standard). Furthermore, the carboxyl group content (acid value) was measured by titration and was 1.4.
meq/g.

The aromatic hydrocarbon group content was calculated to be 46% by weight.

Synthesis Example 2 (Drop-dropping method) 22.2 g (0.17 mol) of 2,2-bis(hydroxymethyl)propionic acid and 14.0 g of diethylene glycol were placed in a No. 11 3-bottle round bottom flask equipped with a condenser and a stirrer and purged with nitrogen in advance. (0.13 mol), 1.4
-Butanediol8. )g (0.09 mol) was added and dissolved in 113 g of N,N-dimethylacetamide.

0.31 g (0.49 mmol) of di-n-butyltin dilaurate was added as a catalyst to this system, and 4,4-
Diphenylmethane diisocyanate 59.2 g (0
, 24 mol), hexamethylene diisocyanate 26
．． A solution prepared by dissolving 6 g (0.16 mol) in 113 g of N,N-dimethylacetamide was added dropwise, and the mixture was heated and stirred at 90''C for 9 hours under a nitrogen stream.

Thereafter, 113 g of N,N-dimethylformamide, 56.3 g of methanol, and 20.4 g of acetic acid were added to stop the reaction and diluted. The reaction solution was added dropwise into ion-exchanged water 21 with stirring to precipitate a white polymer. This polymer was filtered, further washed with ion-exchanged water 21, and then dried to obtain 128 g of polymer (polyurethane resin (b) of the present invention).

The molecular weight was measured by gel permeation chromatography and found to be 58.000 in weight average molecular weight (polystyrene standard). Furthermore, the carboxyl group content (acid value) was measured by titration and found to be 1.3 meq/
It was g. The aromatic hydrocarbon group content is calculated as 4.
It was 6% by weight.

Comparative Synthesis Example 1 A lI! equipped with a condenser and a stirrer and pre-substituted with nitrogen!
22.2 g (0.17 mol) of 2,2-bis(hydroxymethyl)propionic acid, 14.0 g (0.13 mol) of diethyl glycol, 1
．． 4-butanediol 8.0 g (0.09 mol)
was added and dissolved in 226 g of N,N-dimethylacetamide. Add 0.03 g of distilled water to this system.

To this, 4,4-diphenylmethane diisocyanate) 59
．． 2 g (0.24 mol), hexamethylene diisocyanate 26.6 g (0.16 mol), and further di-n-butyltin dilaurate 0.3 as a catalyst.
Add 1 g (0.49 mmol) and stir at 90° under nitrogen stream.
The mixture was heated and stirred at C for 9 hours.

Thereafter, 113 g of N,N-dimethylformamide, 56.3 g of methanol, and 20.4 g of acetic acid were added to stop the reaction and diluted. The reaction solution was dropped into ion-exchanged water 21 with stirring to precipitate a white polymer. After separating this polymer by filtration and further washing with ion exchange water 21,
By drying, 128 g of polymer (polyurethane resin (p)) was obtained.

When the molecular weight was measured by gel permeation chromatography, the weight average molecular weight was 57,000 (in terms of polystyrene). Furthermore, when the carboxyl group content (acid value) was measured by titration, it was 1.4 meq/
It was g. The aromatic hydrocarbon group content is calculated as 46
% by weight.

Comparative Synthesis Example 2 (-Bulk charge method) 22.2 g (0.17 mol) of 2,2-bis(hydroxymethyl)propionic acid and diethylene glycol were placed in a II 3-bottle round bottom flask equipped with a condenser and a stirrer and purged with nitrogen in advance. 14.0g (0.13mol), 1.4
-Butanediol8. Add Og (0.09 mol),
Dissolved in 226 g of N,N-dimethylacetamide. Add to this 4,4-diphenylmethane diisocyanate 59.
2 g (0.24 mol), 26.6 g (0.16 mol) of hexamethylene diisocyanate) and 0.31 di-n-butyltin dilaurate as catalyst.
g (0.49 mmol) and 90 g (0.49 mmol) was added under a nitrogen stream.
The mixture was heated and stirred at ℃ for 9 hours.

Thereafter, 1.13 g of N,N-dimethylformamide, 56.3 g of methanol, and 20.4 g of acetic acid were added to stop the reaction and diluted. The reaction solution was dropped into ion-exchanged water 21 with stirring to precipitate a white polymer.

This polymer was filtered, further washed with ion-exchanged water 21, and dried to obtain 131 g of polymer (polyurethane resin (q)).

When the molecular weight was measured by gel permeation chromatography, the weight average molecular weight was 58,000 (in terms of polystyrene). Furthermore, the carboxyl group content (acid value) was measured by titration and found to be 1.3 meq/
It was g. The aromatic hydrocarbon group content is calculated as 4.
It was 6% by weight.

Comparative Synthesis Example 3 22.2 g (0.17 mol) of 2,2-bis(hydroxymethyl)propionic acid and 14.0 g (0.1 mol) of diethylene glycol were placed in a 3-bottle round-bottomed flask equipped with a condenser and a stirrer and purged with nitrogen in advance. 13mof), 1,4
- Add 8.0 g (0.09 mol) of butanediol,
Dissolved in 226 g of N,N-dimethylacetamide. Add 0.03 g of distilled water to this system. 4.
4-diphenylmethane diisocyanate) 7.50 g
(0.03 mol), 62.2 g (0.37 mol) of hexamethylene diisocyanate), and further 0.31 g of di-n-butyltin dilaurate as a catalyst.
(0.49 mmol) and heated to 90°C under nitrogen stream.
The mixture was heated and stirred for 9 hours.

Then 113 g of N,N-dimethylformamide.

The reaction was stopped by adding 56.3 g of methanol and 20.4 g of acetic acid, and the mixture was diluted. Pour the reaction solution into ion-exchanged water 21
It was added dropwise to the solution while stirring to precipitate a white polymer. This polymer was filtered, further washed with ion-exchanged water 21, and dried to obtain 128 g of polymer (polyurethane resin (r)).

When the molecular weight was measured by gel permeation chromatography, the weight average molecular weight was 57.000 (in terms of polystyrene). Furthermore, when the carboxyl group content (acid value) was measured by titration, it was 1.4 meq/
It was g. The aromatic hydrocarbon group content is calculated as 5.
．． It was 8% by weight.

Synthesis Examples 3 to 19 In the same manner as in Synthesis Example 1 (water presence method), using the diisocyanate compounds and diol compounds shown in Table 1,
A polyurethane resin of the present invention was synthesized.

Furthermore, the molecular weight was measured by GPC, and the acid value was measured by measurement. Table 1 shows the measured acid value and the calculated aromatic hydrocarbon group content. The weight average molecular weight (polystyrene standard) was 20.00 to 58,00 in all cases.

Reference Example 1 Comparative Synthesis Example of Polyurethane Solubility The solubility of the polyurethane resin synthesized in the Comparative Synthesis Example in the cloth solvent was evaluated by the turbidity when dissolved in propylene glycol monomethyl ether. The results are shown in Table 2.

As described above, the polyurethane resin produced by the production method of the present invention has improved solubility.

Example 1 Comparison of suitability for liquid feeding The photosensitive liquids (A) and (B) were subjected to a liquid feeding circulation filtration test using a simulated piping system each equipped with a 0.4 micron filter. The results are shown in Table 3.

Photosensitive solution (A-1, 2) Table 3 *) ○: No foreign matter was observed on the filter with the naked eye.

×: Significant adhesion of foreign matter on the filter is observed with the naked eye.

Zero 20! ! As a comparative example of pressure increase in a part of the filter during liquid circulation, polyurethane resin (a) in the photosensitive liquid,
(A photosensitive solution (B) using polyurethane resin (Q) instead of BLO was prepared in the same manner.

Example 2 Comparison of coatability and printability The same photosensitive solution was coated on an aluminum plate which had undergone the pretreatment described below, and the surface condition of the tube fabric when dried was compared. Table 4 shows the results.

Thickness 0.24. The surface of the aluminum plate of the ink was gritted using a nylon brush and an aqueous suspension of 400 mesh bumiston, and then thoroughly washed with water. This is 1
After etching by immersing in a 0% aqueous sodium hydroxide solution at 7°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, VA=12.7V, V,=9. Electrolytic surface roughening treatment was carried out using a sinusoidal alternating waveform current of 1V and an anode special electricity amount of 160 corons/dm2 in a 1% nitric acid aqueous solution. Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55°C for 2 minutes, and then anodized in a 7% aqueous sulfuric acid solution so that the coating amount of aluminum oxide was 2.0 g/rd. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70°C for 1 minute, washed with water, and dried. The photosensitive liquid (A-1) was applied to the aluminum plate obtained as described above.
(A-2), CB) was applied using a wheeler, and 80″
It was dried at C for 2 minutes. Dry weight is 2.0 g/rd
Met.

Furthermore, the following treatments were performed using this coated material, and the printing characteristics were evaluated. The results are also shown in Table 4.

Each of the photosensitive planographic printing plates ('A-1), [A-2) and (B) obtained using the photosensitive solutions (A-1), CA-2) and (B) was coated with Fuji Photo Film ■. Image exposure was carried out for 1 minute from a distance of 1 m using a manufactured PS light, and after immersion in the following developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton.
The unexposed areas were removed and a bright blue image lithographic printing plate (A
-1), [:A-2) and CB) were 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.

Coating surface condition Printing characteristics were evaluated with the naked eye.○: No roughness ×: Roughness, unevenness Examples 3 to 7 An aluminum plate with a thickness of 0.24 mm was coated with a nylon brush and an aqueous suspension of 400 mesh of bumiston. After sanding the surface (washing with water)
% sodium hydroxide aqueous solution at 70°C for 60 seconds, washed with running water, and neutralized with 20% nitric acid, VA = 12.7V, V, = 9. Electrolytic surface roughening treatment was carried out using an IV sinusoidal alternating waveform current in a 1% nitric acid aqueous solution with an anode specific electricity amount of 160 corons/dm2.

Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and heated at 55°C for 2 hours.
After desmutting for a minute, anodic oxidation treatment was performed in a 7% aqueous sulfuric acid solution so that the amount of aluminum oxide coated was 2.0 g/1rd. Then 3% of sodium silicate at 70 °C
It was immersed in an aqueous solution for 1 minute, washed with water and dried. The following photosensitive solution (C) was applied to the aluminum plate obtained as above.
-1 to (C)-5 were applied using a wheeler and dried at 80°C for 2 minutes. Dry weight was 2.0 g/+11'.

Table 5 shows the polyurethane resins used in the photosensitive solutions [:C)-1 to [:C)-5.

Photosensitive liquid [CD] Next, as a comparative example, a photosensitive liquid [D] using the polyurethane resin (r) of the comparative example instead of the polyurethane resin in the above photosensitive liquid was applied and dried in the same manner.

Dry weight is 2.0g/rr? Met.

Each of the photosensitive lithographic printing plates [C)-1 to 5 and CDI obtained using the photosensitive solutions (C)-1 to 5 and CD) was imaged for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■. After exposing to light and immersing it in the following developing solution at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and the lithographic printing plates (C)-1 to (D) with bright blue images were prepared. )
I got it.

(Developer) Table 5 Each printing plate was printed on high-quality paper using a commercially available ink using a KOR type printing machine manufactured by Heidelberg.

When the final number of printed sheets of the lithographic printing plates (C)-1 to -5 and CD) was examined, they were as shown in Table 5.

As shown in Table 5, lithographic printing plates (C)-1 to (C)-5 (Examples 3 to 7) using the photosensitive composition of the present invention
The number of prints was larger than that of the comparative example (CD), and the printing durability was very excellent.

Claims (1)

[Scope of Claims] A water-insoluble, alkaline water-soluble polyurethane resin having a carboxyl group, wherein the content of aromatic hydrocarbon moieties in the resin is at least 10% by weight, and which is produced by the following manufacturing method. A photosensitive composition comprising a polyurethane resin manufactured by. (1) A method in which 0.1% to 0.3% (wt% of the polymerization solution) of water is present in the polymerization reaction system during polymerization, or (2) Polymerization while dropping an isocyanate compound into a diol compound and a solvent. How to do it.