JPS63287944A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having satisfactory developability for aq. alkaline developing soln. and high durability for printing by incorporating a water-insoluble and aq. alkali-soluble poly(urethane-amide) resin having carboxyl groups into the compsn. CONSTITUTION:The title photosensitive compsn. contains a water-insoluble, aq. alkali soluble poly(urethane-amide) resin having carboxyl groups. A photosensitive compsn. consisting of a mixture of o-quinonediazide, as a photosensitive compd. in combination with a negatively acting diazonium compd., a polymerizable monomer, and a photopolymn. initiator, or a mixture consisting of a negatively acting diazonium compd. in combination with a polymerizable monomer, and a photopolymn. initiator, etc. may be used also. Therefore, either a positive photosensitive compsn. or a negative photosensitive compsn. is obtainable. Such photosensitive compsn. has high coatability when it is coated on a base and high developability wen it is coated, dried, and image-exposed, and developed with aq. alkali developing soln. Moreover, 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.

Description

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

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

[Conventional technology]

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

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

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Although the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 did have improved film properties, it had the drawback of poor abrasion resistance. Further, 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, but such a polymer compound cannot be used under appropriate development conditions. There were problems such as a narrow range and insufficient wear resistance.

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

Furthermore, 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 resins include diazo resins represented by formaldehyde condensates of p-diazodiphenylamine.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin may be a diazo resin alone, i.e. without a binder, as described, for example, in U.S. Pat. No. 2,714,066. For example, JP-A-50-3060
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years many photosensitive 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. 50-30604, 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 an organic solvent-based developer. The so-called solvent-developed type is known, but from the viewpoint of occupational safety and health, the alkali-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkaline developability to the binder is to copolymerize a carboxylic acid-containing hexamer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861,058. There is a method of introducing carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride, as described in Therefore, only lithographic printing plates with low stiffness resistance could be obtained from photosensitive lithographic printing plates containing such a binder in the photosensitive layer. 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 polycondensed metal and a branched polyurethane resin, respectively. . However, as mentioned above, none of these polyurethane resins has an alkali-soluble group, and their solubility in an aqueous alkaline developer is essentially insufficient.
It was very difficult to carry out development without leaving a residual film. Furthermore, since it does not have a site that causes a photoreaction with the combined diazonium compound during exposure and crosslinks efficiently, it has the disadvantage that it does not form images with sufficient strength.

On the other hand, there have been many attempts to use photopolymerizable compositions as photosensitive image forming layers of negative-working photosensitive lithographic printing plates.
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 new photopolymerization initiators, such as those disclosed in British Patent No. 1,388,492, are known, and some of them are in practical use. Photosensitive compositions also have drawbacks in that their sensitivity is greatly affected by the surface temperature of the photosensitive lithographic printing plate during image exposure, and polymerization is strongly inhibited by oxygen during image exposure.

[Problem that the invention seeks to solve]

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

[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 photosensitive composition containing a poly(urethane-amide) resin having a carboxyl group and being insoluble in water and soluble in alkaline water.

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

(ii) Negative-acting diazonium compounds.

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

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

Photosensitive compounds selected from can be used.

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

(1) Poly (urethane-amide) resin The poly (urethane-amide) resin suitably used in the present invention comprises a diisocyanate compound represented by the following general formula (1), and -
A structure represented by a reaction product of at least one diol compound starting point of formula (■), (III), or (IV) and -m at least one diol compound starting point of formula (V) or (Vl). The basic skeleton is poly(urethane-amide) resin.

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

0OH HO-R2-A r -Rs -OH ■ R6 (m) C00I+ HO-Ri-N R40H ■ Rs (IV
)0OH HO-Ri-NH-CO-Rt-CO-NH-R, -0
11(V)HO-Rt C0-N11 Ri O
In the R(VI) formula, R1 is a substituent (e.g., alkyl,
represents a divalent aliphatic or aromatic hydrocarbon which may have aralkyl, aryl, alkoxy or halogen groups, optionally containing other functional groups which do not react with isocyanate groups in R1. For example, it may contain ester, urethane, amide, or ureido groups.

R2 is a hydrogen atom, a substituent (for example, cyano, nitro, halogen atom (-F, -C7!, -Br, -1), C0N
Hz, COORa, -0R*.

N HCON HRs -, N HCOORs, -NH
COR I10CONHRI, -CON HR.

(Here, R6 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms). ), preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 6 to 15 carbon atoms.
represents an aryl group. R3, R, and R2 may be the same or different, and may include a single bond, a substituent (for example,
Alkyl, aralkyl, aryl, alkoxy, and halogeno groups are preferred. ) represents a divalent aliphatic or aromatic hydrocarbon, preferably having 1 to 2 carbon atoms.
0 alkylene group, an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and, if necessary, R2, R, and R5 which do not react with the isocyanate group. functional groups such as carbonyl, ester, urethane, amide, ureido, and ether groups. Note that 2 of R1, R3, R4, and R1
Alternatively, three may form a ring.

Rh and Rq may be the same or different.<[t
l[(e.g., alkyl, aralkyl, aryl, alkoxy, halogen atom (-F, -CI,
-Br, -■), and other groups are included. ) represents a divalent aliphatic hydrocarbon, aromatic hydrocarbon, or heterocyclic group that may contain. If necessary, Ri may contain other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido groups, etc. Ri, R? may form a ring.

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

Specifically, the diisocyanate compound represented by the general formula (1) includes those shown below.

That is, 2,4-tolylene diisocyanate, a dimer of 2゜4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3°3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; isophorone diisocyanate, 4.4
'-methylenebis(cyclohexyl isocyanate),
Alicyclic diisocyanate compounds such as methylcyclohexane-2,4 (or 2.6) diisocyanate, 1°3-(isocyanatomethyl)cyclohexane, etc.; 1,3
Examples include diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of butylene glycol and 2 mols of tolylene diisocyanate.

Specific examples of the diol compound having a carboxyl group represented by the general formula (n), (I[I) or (IV) include those shown below.

That is, 3,5-dihydroxybenzoic acid, 2,2-bis(
hydroxymethyl)propionic acid, 2゜2-bis(2-
hydroxyethyl)propionic acid, 2,2-bis(3-
hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid,
4,4-bis(4-hydroxyphenyl)pentanoic acid,
Tartaric i1, N, N-dihydroxyethylglycine, N,
N-bis(2-hydroxyethyl)-3-carboxy-
Examples include propionamide.

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

(Hidden 1) (Magnetic 2) CONtl-CHzCL 01 ((II&L3) IO-CIlzCHz NH-COCl1=CII-
CO-Ntl CHzCHz OR (Floor 4) flo CIIzCIIz N)I Co-CM
IC-CO-NHCHtCHz-011 (patient 5) HO-CHzcIl! NHCO→CH2←jcO
-NH-CIl□co, -011 (earth 6) Rib-CHzCHz-Nll-Co→C1hhCO-NH
-CHICH! -0H (隘7) 110-CLCHt-811CO→C)l Tsuji7CO-N
HCHgC)l OH (inhibition 8) 110-CIhCHt NHCO+CL
tl-CLCL-01 ((patient 9) CHl ■ C11゜ (inhibition 10) Co-NH-4CH!←r-OH (patient 12) CO-NH-CLCHz-0-CHtCII□-011
(Floor 19) (Double 20) CH.

t(OC1l! C-Co N)I GHzCL
-OffC11° When the above poly(urethane-amide) resin is used in combination with a negative-acting diazonium compound, hydroxyl groups and/or nitrile groups may be added to the poly( Introduction of hydroxyl groups and/or nitrile groups, which may be introduced into the poly(urethane-amide) resin, can be carried out, for example, by adding a halogen compound having a hydroxyl group and/or nitrile group to the poly(urethane-amide) resin in the presence of a base. This can be achieved by reacting with a portion of carboxyl groups.

In the case of a nitrile group, poly(urethane-
amide) resins.

The poly(urethane-amide) resin of the present invention is a diisocyanate compound represented by the general formula (1), a diisocyanate compound represented by the general formula (I
It may be formed from any one or two or more of the diol compounds represented by I), (■), or (IV) and the diol compounds represented by the general formula (V) or (VT).

Furthermore, a diol compound that does not have a carboxyl group or an amide 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.

Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1.3-7' ethylene glycol, 1
．． 6-hexanediol, 2-butene-1,4-diol, 2゜2.4-trimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclode Candimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F5 ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, to hydrogenated bisphenol ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxy diethyl 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 poly(urethanuramide) resin used in the present invention includes at least one of the above diisocyanate compounds of general formula (II), (I[[) or (IV) and general formula (V) or (
It is synthesized by adding at least one type of Vl) in an aprotic solvent, adding a known catalyst having an activity depending on the reactivity of each compound, and heating the mixture.

General formula (U) for the diisocyanate compound used
, (III) or (TV) and general formula (V) or (V
The total molar ratio of compounds r) is preferably O, S: 1 to
If the ratio is 1.2:1 and an isocyanate group remains at the end of the polymer, it can be finally synthesized in a form in which no isocyanate group remains by treating with an alcohol or an amine. Further, the preferable amount of the compound of general formula (V) or (Vl) to be used with respect to the diisocyanate compound is 1
It is used in an amount of mol % or more, more preferably in a range of 5 to 60 mol %.

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

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

(2) Positive-type O-quinonediazide compound On the other hand, the positive-acting 0-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 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, Kaikai No. 48-13354, Special Publication No. 4
No. 1-11222, No. 45-9610, No. 1973
-17481 Publication, U.S. Patent No. 2,797,213, U.S. Patent No. 3,454,400, U.S. Patent No. 3,544,323
No. 3,573,917, No. 3,674.49
No. 5, No. 3,785,825, British Patent No. 1,22
No. 7,602, No. 1.251,345, No. 1, 2
No. 67.005, No. 1.329.888, No. 1,
Examples include those described in various specifications such as No. 330.932 and German Patent No. 854,890.

The amount of these positive-acting O-quinonediazide compounds in the photosensitive composition of the present invention is 10 to 50% by weight.
More preferably, it is 20 to 40%.

(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. Examples of such monomers or oligomers, which are monomers or oligomers having two or more addition-polymerizable ethylenically unsaturated groups and a molecular ff of 110.000 or less, include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono( Monofunctional acrylates and methacrylates such as meth)acrylate and phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, polybrobylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate
Acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohol such as glycerin or trimethylolethane, which is converted into (meth)acrylate after adding ethylene oxide or propylene oxide,
Special Publication No. 48-41708, Special Publication No. 50-6034,
Urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-A-49-43191, JP-A-52-30490
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 each publication. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association Magazine νo1.20, 7.300-308 can also be used.

These monomers or oligomers and the poly(
The composition ratio of urethane-amide) resin is 5:95 to 7 by weight.
The range of 0:30 is preferable, and the more preferable range is t
o:qo~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. and α-carbonyl compounds disclosed in U.S. Pat. No. 2,367.670, asiroin ethers disclosed in U.S. Pat. alpha-hydrocarbon-substituted aromatic acyloin compounds disclosed in the Proclamation, multi-branched quinone compounds disclosed in U.S. Pat. Triarylimidazole dimer/p disclosed in Patent No. 3,549,367
-Aminophenylketone combination, U.S. Pat. No. 3,87
Benzothiazole compounds disclosed in U.S. Pat. No. 0,524, 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.

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

In the formula, R1° represents a substituted or unsubstituted aryl group or alkenyl group, and R represents Rho, -CX, or a substituted or unsubstituted alkyl group. X represents a chlorine atom or a bromine atom.

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

i.e. thi, 2-phenyl-4,6-bis(trichloromethyl)-3-1 riazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-3-triazine, 2
-(p-)lyl)-4,6-bis(trichloromethyl>
-S-triazine, 2-(p-methoxyphenyl)-4
,6-bis(trichloromethyl)-3-)riazine, 2
-(2',4'-dichlorophenyl)-4,6-bis(
trichloromethyl)-3-triazine, 2°4.6-)
Lis(trichloromethyl)-3-) riazine, 2-methyl-4,6-bis(trichloromethyl)-3-) riazine, 2-n-nonyl-4°6-bis(trichloromethyl)-3-) riazine , 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-3-triazine, 2-styryl-4,6-bis(trichloromethyl)-S-triazine, 2-(p -methylstyryl)
-4,6-bis(trichloromethyl)-5-)riazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-5-triazine, 2-(4-methoxy-naphtho-1- yl)-4゜6-bis(trichloromethyl)-3-triazine, 2-(4-ethoxy-naphtho-
1-yl)-4゜6-bis(trichloromethyl)-S-
1-Ryazine, 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, 2-(acenaphth-5-yl)-4
, 6-bis(trichloromethyl)-S-triazine, 2
-(4-styrylphenyl)-4,6-bis(trichloromethyl)-3-)riazine and the like.

Further, as the compound represented by the general formula (■), for example, JP-A No. 54-74728, JP-A No. 55-77742
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-Trichloromethyl-1,3゜4-oxadiazole, 2-(4-methylstyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(4-methoxystyryl)-5- Trichloromethyl-1,3,4-oxadiazole, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-
(4-styrylstyryl)-5-trichloromethyl-1
, 3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-(
4-methoxyphenyl)-5-trichloromethyl-1,
3,4-oxadiazole, 2-(3,4-dimethoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(4-styrylphenyl)-5-trichloromethyl-1, 3,4-oxadiazole, 2-
(1-naphthyl)-5-trichloromethyl-1,3,4
-Includes oxadiazole, 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 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-menicbutobenzothiazur, and ethyl N,N'-dimethylaminobenzoate are also effectively used in the present invention.

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

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

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

In addition, when combined with an 0-quinonediazide compound, a cyclic acid anhydride may be added to increase sensitivity. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-tetrahydrofucric 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 blank BY, Oil black BS, Oil black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CT4)
2535), Rhodamine B (CI45170B), Malachite Green (CI42000), 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 the polymerizable monomer is combined with a photopolymerization initiator, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during production or storage of the photosensitive composition. It is desirable to add Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,
Pyrogallol, t-butylcatechol, henzoquinone,
4.4'-thiobis(3-methyl-5-t-butylphenol), 2.2'-methylenebis(4-methyl-6-
(t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine cerous salt, and the like.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Methanol, ethanol, isopropanol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol 7-methyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2 -Propertool, 1-methoxy-2-propyl acetate, methyl lactate, ethyl lactate, N,N-dimethylformamide, N,N-dimethyl 7cetamide, γ-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., or plastic films laminated or vapor-deposited with the above metals, etc. included. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. In addition, the special public
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 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. This is carried out by flowing Ti or 'lPt in an electrolytic solution using an aluminum plate as an anode.

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 U.S. 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 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.

16.1 g (0.12 mol) of 2,2-bis(hydroxymethyl)propionic acid, N, was added to a 500 nJ three-day round bottom flask equipped with a bottom flame condenser and a stirrer.

N-bis(2-hydroxyethyl)adipic acid amide 1
Add B, 6 g (0,080 mol), N, N-
Dissolved in dimethylacetamide 120Il11. Add to this 4.4'-diphenylmethane diisocyanate and 50.
1 g (0.20 mol) was added and heated at 100°C for 6 hours.
The mixture was heated and stirred. Then N,N-dimethylformamide 2
00m1! and 50 mj of acetic acid! The diluted 0 reaction solution was poured into water 41 with stirring to precipitate a white polymer. This polymer was filtered, washed with water, and dried under vacuum to obtain 81 g of polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 32,000.

Further, the carboxyl group content (acid value) was measured by titration and found to be 1.36 +weq/g (poly(urethane-amide) resin (a) of the present invention).

In the same manner as in Synthesis Example 1, the poly(urethane-amide) resin of the present invention was synthesized 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 20,000 to 53,000.

1" 1L 2 feet Thickness 0.3. The surface of an OLlm aluminum plate was grained using a nylon brush and a 400 mesh pumice stone suspension in water, and then thoroughly washed with water. 10%
After etching in sodium hydroxide at 70°C for 60 seconds, the film was washed with running water, neutralized with 20% nitric acid, and washed with water. This was carried out at 160 clones/l in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of VA = 12.7■.
Electrolytic surface roughening treatment was performed using a special anode electricity amount of h2. When the surface roughness was measured, it was 0.6.1z (expressed in Ra).

Subsequently, it was immersed in a 30% g-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/da2 to a thickness of 2.7 g/M.

Next, five types of photosensitive liquids (A) were prepared by changing the type of poly(urethane-amide) resin used in the present invention in photosensitive liquid [8] below.
-1 to (A)-5 were prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried at 00°C for 2 minutes to obtain each photosensitive lithographic printing plate (A]-1 to (A)
-5 was produced.

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

The poly(urethane-amide) resins used in the present invention for photosensitive solutions (A)-1 to [8]-5 are shown in Table 2.

Photosensitive liquid (A) Next, as a comparative example, the following photosensitive liquid (] 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/n.

Positive transparent originals of line drawings and halftone dot images were brought into close contact with the photosensitive layers of photosensitive lithographic printing plates (A)-1 to -5 and (B), and exposure was performed from a distance of 70 G using a 30 ampere carbon arc lamp.

Exposed photosensitive lithographic printing plates (A)-1 to (B)
was immersed and developed in an 8-fold diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film 01) at 25° C. for 60 seconds.

The obtained lithographic printing plates CA] 1 to 5 and CB) were printed 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 C
The final number of printed sheets of B) was as shown in Table 2.

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

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

The surface of an aluminum plate having a thickness of 0.24n+w was sanded using a nylon brush and an aqueous suspension of 400 mesoyu of pumice stone, and then thoroughly washed with water. This is 10
976 Sodium hydroxide aqueous solution at 70°C for 60 seconds for etching, washing with running water, neutralization washing with 20% nitric acid, electrochemical surface roughening method described in JP-A-53-67507, That is, vA=12.7V, VC=9. 160°C in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current of IV.
Electrolytic surface roughening treatment was performed using the positive electricity amount of clone/dllllz. Continue to immerse in 30% sulfuric acid aqueous solution.
After desmutting at 5° C. for 2 minutes, anodization treatment was performed in a 7% aqueous sulfuric acid solution so that the V and weight of aluminum oxide was 2.0 g/H. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70° C. for 1 minute, washed with water and dried.

Photosensitive solutions [C)-1 to (C)-5 shown below were applied to the aluminum plate obtained as described above using a wheeler, and dried at 80° C. for 2 minutes. The dry weight is 2. It was Qg/m.

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

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

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

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

Each of the photosensitive lithographic printing plates (C)-1 to 5 and CD) obtained using the photosensitive solutions (C)-1 to 5 and (D) was coated with a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m. After exposing the image to light for 1 minute and infiltrating it with the developer shown below at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area. CD)
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.

Table 3 As can be seen from Table 3, lithographic printing plates (C)-1 to 5 (Examples 6 to 10) using the photosensitive composition of the present invention were superior to Comparative Example (D). It can be printed in large numbers and has excellent rigidity.

Aluminum obtained in Example 6 The following photosensitive solution (B)
-1 to (E)-4 were applied using a wheeler and dried at 80°C for 2 minutes. Dry weight was 2.0 g/rtf.

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

Photosensitive solution (E) Next, as a comparative example, benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer (
A photosensitive solution (F) using a weight average molecular weight of 145.000 (polystyrene standard) was similarly coated and dried. The dry weight was 2.0g1rd.

Each of the photosensitive lithographic printing plates (E)-1 to 4 and CF) obtained using the photosensitive solutions (E)-1 to 4 and (F) was coated with a PS light from a distance of 1 m from a distance of 1 m using Fuji Photo Film Al. After exposing the image for one minute and immersing it in the developer used in Example 6 at room temperature for one 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 (E)-1. ~4
and (F) were obtained.

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

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

Table 4 As can be seen from Table 4, the number of printed 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 (G) 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. Dry weight was 2.0 g/rd.

The poly(urethane-amide) resins used in the present invention for the photosensitive liquids CG)-1 to CG)-2 are shown in Table 5.

Photosensitive liquid (G) Next, as a comparative example, methyl methacrylate-methacrylic acid (mole ratio 80/20) copolymer (weight average molecular weight 52,000 (polystyrene standard)) was similarly applied and dried. Dry weight was 2.0 g/rd.

The photosensitive lithographic printing plates (G)-1 to 2 and (H) obtained using the photosensitive liquids CG)-1 to 2 and (H) were each coated with a PS light manufactured by Fuji Photo Film ■ from a distance of 1 m for 1 minute. After exposing the image and immersing it in the developer used in Example 6 for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and the planographic printing plates (G)-1 to 1 with bright blue images were prepared. 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 CG)-1 to CG-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 high rigidity resistance.

Claims (1)

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