JPS63287947A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having high developability for aq. alkali developing soln. and high durability for printing by incorporating a specified polyurethane resin into the compsn. CONSTITUTION:The title photosensitive compsn. contains polyurethane resin insoluble in water and soluble in aq. alkali, and having carboxyl groups, contg. also at least 10wt.% (basing on the total urethane bonds) urethane bond produced by the reaction between phenolic OH groups and isocyanate groups. Either a negative photosensitive compsn. or a positive photosensitive compsn. may be obtainable since an o-quinonediazide compd. or a negatively acting diazonium compd. as a photosensitive compd. can be incorporated into the compsn. Such photosensitive compsn. has superior coatability when it is coated on a base, and high developability when its exposed part is developed after coating, drying, and image-exposure. Since an obtd. 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 in a printing form. Additionally, the photosensitive compsn. is used also in a lithographic printing form, IC circuit, photomask, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, RC 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 essentially has insufficient solubility in an aqueous alkaline developer, making it difficult to completely remove the photosensitive layer in the non-image area (n-front area). It was extremely difficult to develop sea urchins.

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, 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 one is 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
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years many photosensitive planographic printing plates using diazonium compounds have high rigidity resistance. It consists of a diazonium compound and a polymer as a binder.

As described in JP-A No. 50-30 (I04), such photosensitive layers are of the so-called alkaline development type, in which the unexposed areas are removed (developed) with an aqueous alkaline developer, and of the organic solvent type. The so-called solvent-developable type, which is removed by a developer, is known, but the alkali-developable type is attracting attention from the standpoint of occupational safety and health, and this is mainly determined by the properties of the binder. As a method for this, copolymerization of carboxylic acid-containing hexamer as described in JP-A No. 50-30604, or copolymerization of polyvinyl alcohol as described in U.S. Pat. No. 2,861,058. There is a method of introducing carboxylic acid into a polymer by reacting a hydroxyl group with a cyclic acid anhydride such as phthalic anhydride, but the resulting polymer has poor abrasion resistance due to its structure, and such binders However, polyvinyl acetal forms a tough film and has abrasion resistance, but it cannot be used as an organic solvent-developed photosensitive lithographic printing plate. The drawback was that only a printed version was available.

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 cotton-like polyurethane resin, and a combination system of a diazonium salt polycondensate and a branched polyurethane resin, respectively. There is. However, as mentioned above, none of these polyurethane resins has an alkali-soluble group and essentially has insufficient solubility in an aqueous alkaline developer, making it difficult to develop without forming a residual film. was extremely 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 of them have been put into practical use. Photosensitive compositions also have the disadvantage that their sensitivity is influenced by the surface temperature of the photosensitive lithographic printing plate during image exposure, and that they are 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.

[Structure of the invention]

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 polyurethane resin that is insoluble in water and soluble in alkaline water and has a carboxyl group, in which at least urethane bonds derived from a reaction between a phenolic hydroxyl group and an isocyanate group are contained in the resin relative to the total urethane bonds. The present invention provides a photosensitive composition characterized in that it contains a polyurethane resin having a content of 1 mol %.

The photosensitive compounds contained in the photosensitive composition of the present invention include the following (1), (ii), (iii) or (iv).
): (i) o-quinonediazide compound.

(11) Negative-acting diazonium compounds.

(ii) Combination of a polymerizable monomer and a photopolymerization initiator.

(iv) Combination with a negative-acting diazonium compound, a polymerizable heptamer and a photopolymerization initiator.

Photosensitive compounds selected from can be used.

Hereinafter, 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.

(11 Polyurethane resin The polyurethane resin suitably used in the present invention is a diisocyanate compound represented by the following general formula (I) and at least one type of diol compound of the general formula (ff), (■), or (■). and a polyurethane resin whose basic skeleton is a structure represented by a reaction product with at least one type of diol compound of general formula (V) or (Vl).

0CN-R, -NCO(1) R.

s Grave 0OH 10-R, -^r r-R4-OR 耀NO-Rs -N -Ra -OH HO-^rz@Rb Artsuji TOH (V) tlo-
Art-R&-OR(Vl), where R1 is a substituent (e.g., alkyl, aralkyl, aryl, alkoxy,
each group of halogeno is preferred), optionally R1
The inside may contain other functional groups that do not react with incyanate groups, such as ester, urethane, amide, and ureido groups.

Rg is a hydrogen atom, a substituent (e.g., cyano, nitro, halogen atom (-Fs-C1sBr11), C
ON H! , -COORt, -OR? ,NHCO
NHR? , NHCORq , -NHCOOR,
, -0CONHRf, -C0NHRf (here, R1
represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, and the like. ) represents an alkyl, aralkyl, aryl, alkoxy, or aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. , Rs may be the same or different, and may have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, or halogeno groups are preferred). or an aromatic hydrocarbon, preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and if necessary, R5, R4, and Rs may have other functional groups that do not react with isocyanate groups, such as carbonyl ester, urethane, amide, ureido, and ether groups.
Note that two or three of Rz, Rs, R4, and Rs may form a ring.

R6 is a substituent (e.g., alkyl, aralkyl,
If necessary, other functional groups that do not react with isocyanate groups in R4, such as ester, urethane, It may have an amide or ureido group.

Ar1 represents a trivalent aromatic hydrocarbon which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms @Art, Ar3 may be the same or different and may be substituted Indicates a divalent aromatic hydrocarbon which may have a group, preferably an aromatic group having 6 to 15 carbon atoms.

n represents 0 or an integer from 1 to 10.

-a The diisocyanate compound represented by formula (1) 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, 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, l.

Examples include alicyclic diisocyanate compounds such as 3-(isocyanatomethyl)cyclohexane, diisocyanate compounds that 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, etc. It will be done.

Moreover, the diol compound having a carboxyl group represented by the general formula (I[), (M), or (IV) specifically includes those shown below.

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

Further, the diol compound represented by the general formula (V) or (VI) specifically includes those shown below.

Namely, catechol, resorcinol, hydroquinone, 4-
Methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-butylresorcin, 4-hexylresorcin, 4- Chlororesorcin, 4-benzylresorcin, 4-acetylresorcin, 4-carbomethoxyresorcin, 2-methylresorcin, 5-methylresorcin, t-butylhydroquinone, 2.5-di-t-butylhydroquinone, 2.5-di -t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcarboaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-diol, bisphenol A, bisphenol S, 3,3'-dichlorobisphenol S, 4.4'-dihydroxybenzophenone,
4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol, 2,2'-dihydroxydiphenylmethane, 3,4-bis(p-hydroxyphenyl)hexane, 1,4-bis(2-( p-hydroxyphenyl)propyl)benzene, bis(4-hydroxyphenyl)methylamine, l,3-dihydroxynaphthalene, 1.4-
Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3,5-di[-phthylbenzyl alcohol,
4-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenylacetate,
Examples include resorcin mono-2-hydroxyethyl ether.

When the above-mentioned polyurethane resin is used in combination with a diazonium compound that acts negatively, in order to increase the efficiency of photocrosslinking of the diazonium compound, hydroxyl groups and/or
Alternatively, a nitrile group may be introduced into the polyurethane resin of the present invention.Introduction of a hydroxyl group and/or a nitrile group can be carried out, for example, by adding a halogen compound having a hydroxyl group and/or a nitrile group to the carboxyl group of the polyurethane resin in the presence of a base. This can be achieved by reacting with a part of

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

The polyurethane resin of the present invention is made of two or more diisocyanate compounds represented by general formula (1), two or more diol compounds represented by general formula (II) (■) or (■), and (V) or (Vl). may be formed.

Furthermore, an aliphatic 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-trimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclode Candimetatool, 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-tolylene dicarbamate, 2,4-tolylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis (2-hydroxyethyl) isophthalate and the like.

The polyurethane resin of the present invention comprises at least one diisocyanate compound of the general formula (n), (III) or (IV) and at least one of the general formula (V) or (Vr) in an aprotic solvent to adjust their reactivity. It is synthesized by adding a known catalyst with appropriate activity and heating. The general formula (t
l), (I[l) or (IV) and the compound of general formula (V) or (Vl), the total molar ratio is preferably O, a:
t to t, zst, 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 treating with alcohols, amines, or the like.

Further, the molar ratio of the diol compound represented by the general formula (V) or (■) to the diisocyanate compound represented by the general formula (1) is at least 1 mol%, preferably 5 to 70%.
Used in a mole % range.

The molecular weight of the polyurethane resin of the present invention is preferably 1,000 or more on weight average, more preferably 5. OO
The range is from 0 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, 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, No. 48-13354, Tokuko Showa 4
No. 1-11222, No. 45-9610, No. 1-11222, No. 45-9610, No. 49
-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
7.602, 1,251,345, 1 and 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 these positive-acting O-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, 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 monomer or oligomer having two or more addition-polymerizable ethylenically unsaturated groups, tio, ooo or less. Such polymers 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 , polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohols such as glycerin and trimethylolethane, and ethylene. Urethane acrylates, which are obtained by adding oxide or propylene oxide and then turning into (meth)acrylates, as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 6034-1982, and Japanese Patent Application Laid-Open No. 51-37193. , JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, polyester acrylates, epoxy acrylates prepared by reacting epoxy resin with (meth)acrylic acid, etc. Examples include polyfunctional acrylates and methacrylates. In addition, Japan Adhesive Association Magazine Vol.
．． 20, Arashi 7, pages 300 to 308, those introduced as photocurable polymers and oligomers 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, more preferably 10:90 to 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 and U.S. Pat. No. 2,367.661. α-carbonyl compounds disclosed in U.S. Pat. α-hydrocarbon-substituted aromatic acyloinated metal compounds disclosed in the specification, multi-branched quinone compounds disclosed in U.S. Pat. Triarylimidazole dimer/p- disclosed in Patent No. 3,549.367
Combination of Aminophenyl Ketones, U.S. Patent No. 3.870
．． benzothiazole compounds disclosed in U.S. Pat. No. 524, acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751,259, and acridine and phenazine compounds disclosed in U.S. Pat. This includes oxadiazole compounds, etc.

Preferred examples include trihalomethyl-3-triazine compounds and trihalomethyloxadiazole compounds represented by the following general formula (■) or (■).

Back.

In the formula, R9 is a substituted or unsubstituted aryl group,
Alkenyl group, R8 is R*, CX! Alternatively, X represents a substituted or unsubstituted alkyl group, and X represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (■) include Wakabu et al., Bull, Che+w, 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.

Namely, 2-phenyl-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-3-triazine, 2
-(p-)lyl)-4,6-bis(trichloromethyl)
-S-) riazine, 2-(p-methoxyphenyl)-4
,6-bis(trichloromethyl)-S-)riazine, 2
-(2',4'-dichlorophenyl)-4,6-bis(
trichloromethyl)-3-triazine, 2゜4.6-tris(trichloromethyl)-3-1-riazine, 2-methyl-4,6-bis(trichloromethyl)-3-triazine, 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-methoxystyryl)-4,6-bis(trichloromethyl) )-3-triazine, 2-(4-methoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4-ethoxy-naphth-■-yl)-4゜6-bis(trichloromethyl)-3
-triazine, 2- (4-(2-ethoxyethyl)-
Naphth-1-yl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4,7-dimethoxy-naphth-1-yl)-4,6-bis(trichloromethyl)
-3-triazine, Z-(acenaphth-5-yl)-4
,6-bis(trichloromethyl)-3-)riazine, 2
- (4-styrylphenyl)-4,6-bis(trichloromethyl)-3-)riazine, etc. are included.

Further, as the compound represented by the general formula (Vl), 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)-5-1-lichloromethyl-1,3,4-oxadiazole, 2-(4-methoxystyryl) -5-trichloromethyl-1,3,4-oxacyapur, 2-(4-butoxystyryl)-5-
Trichloromethyl-1,3,4-oxadiazole, 2
-(4-styrylstyryl)-5-)lichloromethyl-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
-(l-naphthyl)-5-trichloromethyl-1,3,
Includes 4-oxadiazole and the like.

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 biryllium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, ketocoumarins, etc. Can be mentioned. Furthermore, systems in which these are combined with hydrogen donors such as N-phenylglycine, 2-menicabutobenzothiazole, 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
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 polyurethane resin mentioned above, 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 accounts for 70% by weight of the total composition.
It is used in the following amounts.

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. .

In addition, when combined with an O-quinonediazide compound, a cyclic acid anhydride may be added to increase sensitivity. As a cyclic acid anhydride, as described in U.S. Pat. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride There are acids, pyromellitic anhydride, etc. 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 #101, oil yellow #130, oil pink #312, oil green BG, oil blue BO3, oil blue #60.
3. Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Vinia Blue, Crystal Violet (CI42555), Methyl Bioleft (CI4)
2535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (
C152015).

Furthermore, when combined with a diazonium compound, stabilizers include phosphoric acid, phosphorous acid, Cheryl 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. Suitable thermal polymerization inhibitors that are preferably added include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,
Pyrogallol, t-butylcatechol, benzoquinone,
4.41-thiobis(3-methyl-6-t-butylphenol), 2.2'-methylenebis(4-methyl-6-
(=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, [-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, 1-methoxy-2-propylacetate, methyl lactate, ethyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, T-butyrolactone, N-methylpyrrolidone, tetramethylurea, tetrahydrofuran, dioxane, dimethyl sulfoxide , sulfolane, toluene, ethyl acetate, etc., and these solvents may be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight. Further, 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/d. As the coating amount 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 (also includes aluminum alloys).

), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate,
Plastic films such as cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, bopropylene, polycarbonate, polyvinyl acetal, etc., and plastic films laminated or vapor-deposited with the above metals are included. It will be done. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive;
Also preferred are composite sheets in which an aluminum sheet is bonded onto a polyethylene terephthalate film, as described in Japanese Patent No. 8-18327.

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 Also, 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 pores are sealed after graining and anodizing.
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.

500mj with top condenser and agitator on the bottom of the car! 13.4 g (0.10 mol) of 2,2-bis(hydroxymethyl)propionic acid and 11.0 g of resorcinol were placed in a round bottom flask.
Add 0 g (0.10 mol) and 120 mj of N,N-dimethyl-l-reacetamide! dissolved in.

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 20 On+A of N,N-dimethylformamide and 50 IIll of acetic acid. The reaction solution was poured into water 41 with stirring to precipitate a white polymer. The polymer was filtered off, washed with water, and dried under vacuum to obtain 71 g of polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 43,000.

Further, the carboxyl group content (acid value) was measured by titration and found to be 1.31 meq/g.

The polyurethane resin of the present invention was synthesized in the same manner as in Synthesis Example 1 using the diisocyanate compounds and diol compounds shown in Table 1.

Furthermore, the molecular weight was measured by GPC, and the acid value was measured by titration. The measured acid values are shown in Table 1.

Moreover, the weight average molecular weight (polystyrene standard) of each was 18,000 to 55,000.

After the surface of a 0.30 m thick aluminum plate was grained using a nylon brush and a 400 mesh water suspension of pumice stone, it was thoroughly washed with water. After etching by crushing in 10% sodium hydroxide at 70°C for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and washing with water. This was electrolytically roughened in a 1% nitric acid aqueous solution using an alternating sinusoidal waveform current under the condition of Va-12.7V with an anode special electric charge of 160 clones/da''.The surface roughness When measured, it was 0.6μ (indicated by 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% aqueous sulfuric acid solution at a current density of 2 A/ds'' to a thickness of 2.7 g/d.

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

The coating amount at this time was 2.5 g/rd in terms of dry weight.

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

Photosensitive liquid (A) Next, as a comparative example, the following photosensitive liquid (B) was applied in the same manner as photosensitive liquid (A) to prepare a photosensitive lithographic printing plate (B). The coating weight after drying was 2.5 g/rrr. Photosensitive liquid CB) Positive transparent originals of line drawings and halftone dot images were placed on the photosensitive layer of photosensitive lithographic printing plates (A)-1 to -5 and (B). In close contact, exposure was performed from a distance of 70 with a 30 ampere carbon arc lamp.

Exposed photosensitive lithographic printing plates (A)-1 to (B)
was imaged with an 8-fold diluted aqueous solution of DP-4 (product name: Fuji Photo Film ■) at 25° C. for 60 seconds.

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

Lithographic printing plates (A)-1 to 5 using materials (Examples 1 to 5)
) has a larger number of prints than Comparative Example (B) and has excellent printing durability.

In addition, in place of the resin of the present invention in the photosensitive liquid (A), Estane #5715 (Estane 15715, B,
When coating, exposing, and developing were carried out in the same manner using the same method as F, manufactured by Goodlynch Co., Ltd., the development was defective 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 having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh 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 surface is roughened using the electrochemical surface roughening method described in JP-A-53-67507, that is, V ^-12.7V, Vc””9. Using an IV sinusoidal alternating waveform current, electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution with an anode specific electricity amount of 160 chrome/dm''.Subsequently, it was immersed in a 30% sulfuric acid aqueous solution at 55°C. So 2
After desmanting for a minute, anodic oxidation treatment was performed in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g/rrr. Its t & 3 of sodium silicate at 70℃
The following photosensitive solution (C
)-1 to (C)-5 using a wheeler and heated at 80°C.
and dried for 2 minutes. Dry weight was 2.0 g/rd.

The polyurethane resins used in the present invention for photosensitive solutions (C)-1 to (C)-5 are shown in Table 3.

Photosensitive liquid [C] Next, as a comparative example, a photosensitive liquid (C) was prepared using the following polymer instead of the polyurethane resin used in the present invention in the above photosensitive liquid.
D) was applied and dried in the same manner. Dry weight is 2.0g/-
Met.

(Polymer used in comparative example) A polymer with H structure, a / b / c /
The molar ratio of d was 9/2415 B/9.

Moreover, the molecular weight is 55.
It was 000.

Each photosensitive lithographic printing plate (C)-1 to (C)-5 and (D) obtained using the photosensitive solution (C)-1 to CD) was coated with 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 (D)
I got it.

(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.

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 were as follows:
Compared to the comparative example (D), the number of prints was larger (and the rigidity resistance was very excellent).

The following photosensitive solution (E) was applied to the aluminum plate obtained in Example 6.
-1 to (E)-4 were applied using a wheeler and dried at 80°C for 2 minutes. The dry amount was 2.0g1rd.

The polyurethane 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 (weight average molecular weight 45,000 (polystyrene) was used instead of the polyurethane resin used in the present invention in the photosensitive solution. standard)) using a photosensitive solution (
F) was applied in the same manner and dried. Dry weight is 2.0g/r
It was d.

Each photosensitive lithographic printing plate (E)-1 to (E)-4 and (F) obtained using photosensitive liquids (E)-1 to 4 and (F) was coated with a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m. 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 image was obtained. 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 CF) was examined and was as shown in Table 4.

Table 4 As can be seen from Table 4, the number of printed sheets of lithographic printing plates (E)-1 to 4 (Examples 11 to 14) using the photosensitive composition of the present invention was lower than that of Comparative Example CF). Many of them have excellent printing durability.

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

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

Photosensitive liquid CG) Next, as a comparative example, methyl methacrylate-methacrylic acid (molar ratio 80/20) copolymer (weight average molecular weight 5) was used instead of the polyurethane resin used in the present invention in the photosensitive liquid.
2.000 (polystyrene standard))
) was applied and dried in the same manner. Dry weight is 2.0g/nl
Met.

The photosensitive lithographic printing plates (G)-1 to 2 and (H) obtained using the photosensitive solutions (G)-1 to 2 and (H) were coated with a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m. 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 bright blue image was formed on the lithographic printing plate (G)-1. ~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 (Gl-1 to Gl-2 and (H)) was examined and was as shown in Table 5.

Table 5 As can be seen from Table 5, the lithographic printing plates (G)-1 and -2 (Examples 15 and 16) using the photosensitive composition of the present invention had better printing performance than the comparative example (H). It has a large number of sheets and has excellent rigidity.

〔Effect of the invention〕

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

Claims (1)

[Claims] A polyurethane resin that is insoluble in water and soluble in alkaline water and has a carboxyl group, the resin having at least 1 mol% of urethane bonds derived from a reaction between a phenolic hydroxyl group and an isocyanate group based on the total urethane bonds. A photosensitive composition comprising a resin.