JPS63287949A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having superior developability for aq. alkali developing soln. and superior durability for printing by incorporating polyurethane resin having carboxyl groups and specified siloxane bonds into the compsn. CONSTITUTION:The title photosensitive compsn. contains polyurethane resin having carboxyl groups and siloxane bonds expressed by the formula: identicalSi-O- Siidentical. Also a photosensitive compsn consisting of an o-quinonediazide compd. as a photosensitive compd., a negatively acting diazonium compds., a polymerizable monomer, and a photopolymn. initiator, or a compsn. consisting of a negatively acting diazonium compd., polymerizable monomer, and a photopolymn. initiator, etc. may be used. Accordingly, either a positive photosensitive compsn. or a negative photosensitive compsn. is obtainable. Such photosensitive compsn. has superior coatability when it is coated on a base, and superior developability for aq. alkali developing soln. when the compsn. is coated, dried, and image-exposed, and then developed. 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 has limited printing durability when used in lithographic printing plates. There were some points that needed to be improved, such as insufficiency, 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
The polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 certainly had improved film properties, but 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.
Such polymer compounds have problems such as a narrow range of appropriate development conditions and insufficient abrasion 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 diazonium 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, so it cannot be developed to completely remove the photosensitive layer in the non-image area (exposed area). 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 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 lithographic printing plates using diazonium compounds have a high printing durability. It is made of a diazonium compound and a polymer that acts as a binder.

As described in JP-A No. 50-30604, such a photosensitive layer is of the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the photosensitive layer is developed with an organic solvent developer. Although the so-called solvent-developed type is known, from the viewpoint of occupational safety and health, the alkaline-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkaline developability to the binder is to copolymerize a carboxylic acid-containing monomer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861,058. There is a method of introducing carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride, as shown in the figure, but the resulting polymer has poor wear resistance due to its structure. 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 polycondensate and a branched polyurethane resin, respectively. There is. 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, making it difficult to perform development without forming a residual film. It 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-
3' 8403, Japanese Patent Publication No. 53-27605, and compositions using novel photopolymerization initiators as disclosed in British Patent No. 1,388,492, etc. are known. However, the sensitivity of any photosensitive composition is greatly affected by the surface temperature of the photosensitive lithographic printing plate during image exposure, and it is difficult to prevent polymerization inhibition by oxygen during image exposure. It had the disadvantage of being strongly affected.

[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 printing durability.

[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 is a photosensitive composition characterized by containing a polyurethane resin having a carboxyl group and a siloxane bond represented by the following general formula (I).

This provides MiSi0−Siε(I).

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) combination of a polymerizable monomer and a photoinitiator;

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

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.

(I) Polyurethane resin The polyurethane resin suitably used in the present invention is mainly a polyurethane resin containing a group having a carboxyl group and a group having a siloxane bond in the main chain, and is preferably represented by the following general formula (I). It includes a polyurethane resin whose basic skeleton is a reaction product of a diisocyanate compound represented by the formula (n), (I) or (TV) and a diol compound having a carboxyl group represented by the general formula (n), (I) or (TV).

OC'N-R,-N["0
(I) HO-R, -C-R, -0H 1 (■) R3 嘗OH )In -L -Ar -L -OH Rs (m)0OH 80-R, -N-R, -OH ■ Rs ( rV)(:[1
O)1 In the formula, R1 is a divalent aliphatic or aromatic carbonized group which may have a substituent (for example, alkyl, aralquinopearyl, alkoxy, cyano, nitro, and halogeno groups are preferred) Indicates hydrogen. If necessary, R1 may contain other functional groups that do not react with the incyanate group, such as an ethenopeester, urethane, amide, ureido, or carbonyl group.

R2 is a hydrogen atom, a substituent (for example, cyan, nitro, halogen atom (-F, -C1), CONH2, C00Rt
, ORt, NHCONHRq, NHCOOR7
, -NHCORt, -0CONHR? , CONH
R? , -COR, (, -, -, R7 has 1-10 carbon atoms
represents an alkyl group and an aralkyl group having 7 to 15 carbon atoms.

) and other groups are included. ) alkyl, aralkyl, alinopealkoxy, aIJD
It represents an xy 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.
, R-, and Rs may be the same or different, and have a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, cyano, nitro, or halogeno groups are preferred). Indicates a divalent aliphatic or aromatic hydrocarbon. Preferably it is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, R3, R<, and Rs may contain other functional groups that do not react with incyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. Note that 2 of R2, Rs, R4, and Rs
Alternatively, three may form a ring.

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

The diisocyanate compound represented by the general formula (I) specifically includes the following: 2.4
-tolylene diisocyanate, 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. Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl-4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; isophorone diisocyanate, 4.4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate,
■.

Alicyclic diisocyanate compounds such as 3-(isocyanatomethyl)cyclohexane; diisocyanate compounds 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; Can be mentioned.

Further, the diol compound having a carboxy group represented by the general formula (n), (I[I) or (IV)] specifically includes those shown below.

That is, 3,5-dihydroxybenzoic acid, 2,2-bis(
hydroxymethyl)propion L2゜2-bis(2-hydroxyethyl)propionic acid, 2.2-bis(3-
Hydroxypropyl) propionic acid, bis(hydroxymethyl) acetic acid, bis(4-hydroxyphenyl) vinegar L4
, 4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-bis(2-hydroxyethyl)-3-carboxy-propionamide, N,N-bis(2-hydroxyethyl)glycine, etc. .

The siloxane bond in the polyurethane resin of the present invention is a halogen (C
β, Br5I) compound or a sulfonate compound in the presence of a base, it can be incorporated into a polyurethane resin.

Further, a diisocyanate compound having a siloxane bond can also be incorporated into the polyurethane resin by using the diisocyanate compound of general formula (I) together.

Furthermore, a diol compound having a siloxane bond can also be incorporated into the polyurethane resin by using it in combination with a diol compound of general formula (II), (I[) or (IV).

Here, the siloxane bond refers to a 5i-0-3i bond represented by the following general formula (I).

USi OSiE ・ ・ ・ ・ ・ ・ (
I) The siloxane bond represented by the general formula (I) may be independent or continuous, or may have a branch.

Substituents on silicon include substituents (for example, alkyl, aralkyl, aryl, alkoxy, cyano,
Examples include aliphatic or aromatic hydrocarbon groups or siloxy groups which may have nitro groups (preferably nitro groups). Among these, the most preferred aliphatic or aromatic hydrocarbon group is a methyl group or a phenyl group.

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

Furthermore, a diol compound that does not have a carboxyl group and may have other substituents that do not react with incyanate 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, holapropylene glycol, neopentyl glyconope 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, hydrogenated bisphenol A 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 used in the present invention is prepared by adding the above diisocyanate compound and diol compound in a non-butonic solution.
Add a known catalyst with activity according to each reactivity,
Synthesized by heating. The molar ratio of diisocyanate and diol compound used is preferably 0.8
:l to 1.2:1, and if an incyanate group remains at the end of the polymer, it is finally synthesized in a form in which no incyanate group remains by treating with alcohols, amines, etc.

The molecular weight of the polyurethane resin used in the present invention is preferably 1,000 or more on weight average, more preferably 5.
It ranges from OOO to 100,000.

These polyurethane resins may be used alone or in combination. The content of these polyurethane resins contained in the photosensitive composition is about 5 to 90% by weight, preferably about 10 to 60% 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, Domachi No. 48-63802, Domachi No. 48-63803, Domachi No. 48-96575, Domachi No. 4
No. 9-38701 1. No. 48-13354, Special Publication No. 11222-1970, No. 9610-1973, Opening/closing No. 4
Publication No. 9-17481, U.S. Patent No. 2.797.213
No. 3,454,400, No. 3.544,3
No. 23, No. 1573,917, No. 1674.49
No. 5, No. 3,785,825, British Patent No. 1.22
7.602, 1.251.345, 126
No. 7.005, No. 1,329,888, No. 1, 3
Examples include those described in various specifications such as No. 30.932 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 (e.g., p-toluenesulfonates, dodecylbenzenesulfonates, 2-methoxy-4-hydroquine-5-benzoyl Also preferred are benzene sulfonates, etc.), phosphinates (eg, benzene phosphinates), hydroquine group-containing compound salts (eg, 2,4-dihydroxybenzophenone salts, etc.), and organic carboxylates.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4,4
'-bis-methoxymethyl-diphenyl etherte condensed mesitylene sulfonate 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 present in at least one monomer per molecule, more preferably two monomers per molecule. It is a monomer or oligomer having a molecular weight of 000 or less and having an ethylenically unsaturated group capable of addition polymerization. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and phenoxyethyl (meth)acrylate; polyprolene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; Brobylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylate, hexanediol di(meth)
Acrylates, tri(acryloylquinethyl)isoanate, polyhydric alcohols such as glycerin and trimethylolethane that are converted into (meth)acrylates after adding ethylene oxide or propylene oxide;
Special Publication No. 48-41708, Special Publication No. 50-6034,
Urethane acrylates as described in each publication of JP-A-51-37193, JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490
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. Further, those introduced as photocurable monomers and oligomers in Japan Adhesion Society Journal VOI, 20, No. 7, pages 300 to 308 can also be used.

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

Photoinitiators that can be added to the photosensitive composition of the present invention include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367.660 and U.S. Pat. No. 2,367.661. α-carbonyl compounds disclosed in U.S. Pat. Aromatic acyloin compounds substituted with alpha-hydrocarbons as disclosed in the specification, multi-branched quinone compounds as disclosed in U.S. Pat. No. 3.046.127 and U.S. Pat. 3.549.367, triarylimidazole dimer/p-
Combination of Aminophenyl Ketones, U.S. Patent No. 3.870
．． benzothiazole compounds disclosed in US Pat. No. 524; acridine and phenazine compounds disclosed in US Pat. No. 3,751.259; and acridine and phenazine compounds disclosed in US Pat. This includes oxadiazole compounds, etc.

Preferred examples include trihalomethyl-3-)riazine compounds and trihalomethyloxadiazole compounds represented by the following general formula (V) or (VI).

Here, in the formula, R3 is a substituted or unsubstituted aryl group,
The alkenyl group R8 represents R3, -CX3 or a substituted or unsubstituted alkyl group. X represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (V) include Wakabu et al., Bull, Chem, Sac, Japan;
Compounds described in Volume 42, Page 2924 (I969), British Patent No. 1.388.492, West German Patent No. 2.7
18.259, and the compounds described in West German Patent No. 3,337,024. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis(trichloromethyl)-3-triazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-3-triazine, 2
-(p-)lyl)-4,6-bis(trichloromethyl)
-3-) riazine, 2-(p-methoxyphenyl)-4
,6-bis(trichloromethyl)-3-)riazine, 2
-(2',4'-dichlorophenyl)-4,6-bis(
Trichloromethyl)-3-triazine, 2゜4,6-tris(tric60methyl)-3-)riazine, 2-methyl-4,6-bis(trichloromethyl)-3-)riazine, 2-n-nonyl -4゜6-bis(trichloromethyl)-3-)'J azine, 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-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4-methoxy-naphth-1-yl) )-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4-ethoxy-naphtho-
1-yl)-4゜6-bis(trichloromethyl)-3-
to! J Azine, 2-[4-(2-nitoxyethyl)-
Naphth-1-yl: l-4,6-bis(trichloromethyl)-3-) riazine, 2-(4,7-dimethoxy-naphth-1-yl)-4,6-bis(trichloromethyl)
-3-)Ryazine, 2-(acenaphth-5-yl)-
4,6-bis(trichloromethyl)-3-)riazine,
2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-3-)riazine and the like are included.

Further, as the compound represented by the general formula (VI), for example, JP-A No. 54-7472 g, JP-A No. 55-777
Examples thereof include compounds described in JP-A No. 42 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-)lichloromethyl-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-)!J chloromethyl-i, 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-
Included are oxadiazole, 2-(I-naphthyl)-5-trichloromethyl-i, 3,4-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 dye shown in JP-A No. 51024, aromatic Thiobi IJ shown in JP-A No. 58-40302
Examples include IJium salts, aromatic biryllium salts, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, and ketocoumarins. Furthermore, these include N-phenylglycine, 2-menicaptobenzothiazole, N,N
A system in which a hydrogen donor such as ethyl '-dimethylaminobenzoate is combined can also be 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 resins mentioned above, the composition of the present invention includes phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyno\logenated hydroxystyrene, and carboxyl group-containing epoxy resin. Known alkali-soluble polymer compounds such as polyacetal resin, acrylic resin, methacrylic resin, etc. can be contained. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

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

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

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
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 #6.
03, Oil Black BY, Oil Black BS, Oil Blank T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet) (CI42555), Methyl Violet
(C[42535), Rhodamine B (CI45170B
), malachite green (CI42000), methylene blue (CI52015), etc.

Furthermore, when combined with a diazonium compound, stabilizers include phosphoric acid, phosphorous acid, sychoic acid, p-toluenesulfonic acid, dipicoline L'Jnchoic acid, tartaric acid, 2-methoxy-4-hydroxy-5-benzoyl- Examples include benzenesulfonic 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-methoxyphenonopegyt-butyl-p-cresol,
Pyrogallol, t-butylcatechol, pentuquinone,
4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2'-methylenebis(4-methyl-5-
(t-butylphenol), 2-mercaptobenzimidazole, N-nitron phenylhydroxyamine 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, impropatol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2- Examples include propatool, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, toluene, and ethyl acetate, and these solvents may be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight.

The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3.
．． 0 g/m' is preferred. 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,
Films of plastics such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated with or vapor-deposited with the above metals, etc. is included. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.

In addition, in the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable that Further, as described in U.S. Pat. after being anodized 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. Also suitable are aluminum supports. The above-mentioned anodizing treatment may be performed using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination of two or more. It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution.

It is also preferable that the material is grained, anodized, and then sealed. Such pore sealing treatment is performed using a sodium silicate aqueous solution,
This is carried out by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

Also effective is silicate electrodeposition as described in 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 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.

Synthesis Example 1 500-3-tip 1i equipped with condenser and stirrer
ffi flask with 4,4'-diphenylmethane diiso/
125 g (0.50 mol) of anate and 67 g (0.50 mol) of 2°2-bis(hydroxymethyl)propionic acid were added and dissolved in 290 rnl of dioxane. 1 g of N,N-diethylaniline was added as a catalyst, and the mixture was heated under reflux for 6 hours with stirring. Thereafter, the reaction solution was poured into a solution of 4β of water and 40 of acetic acid with stirring to precipitate a white polymer. After filtering this polymer and washing with water,
185 g of polymer was obtained by drying under vacuum.

The molecular weight was measured by gel vermien chromatography (GPC) and found to be 28.000 on a weight average basis (polystyrene standard). Further, the carboxyl group content was measured by titration and found to be 2.47 meq/g.

Furthermore, 40g of this polymer was put into a 300mj machine equipped with a condenser and a stirrer! Place in a three-necked bottom flask and add DMF.
It was dissolved in 200ml. 2.2 g (0,022 mol) of triethylamine was added to this solution, and after heating to 80°C,
10.2 g (0.022 moles) of 3-iodopropyltris(trimethylsiloxy)silane were added. After that 2
Stirring was continued for an hour.

After the reaction is complete, add 4β of water and 200 mj of acetic acid to the reaction solution. was added to the solution while stirring to precipitate a white polymer. This polymer was filtered, washed with water, and then dried under vacuum to obtain 42 g of polymer.

It was confirmed by NMR measurement that a tris(trimethylsiloxy)silyl group had been introduced, and the acid value was further measured by titration and found to be 1.81 meq/g [
Polyurethane [a)] used in the present invention.

Synthesis example 500m7 with condenser and stirrer! 94 g (m-xylylene diisocyanate) in a three-necked round flask (
0,50 mol), 1,3-bis(3-hydroxypropyl)-1,1,3,3,-tetramethyldisiloxane 3
Add 8 g (0.15 mol) and 47 g (0.35 mol) of 2,2-bis(hydroxymethyl)propionic acid,
Dissolved in dioxane 330-. 1 g of N-diethylaniline was added as a catalyst, and the mixture was heated under reflux for 6 hours with stirring.

Thereafter, the reaction solution was poured into a solution of 4β of water and 40 of acetic acid with stirring to precipitate a white polymer. This polymer was filtered, washed with water, and dried under vacuum to obtain 170 g of polymer.

When the molecular weight was measured by GPC, the weight average (polystyrene standard) was 21,000. Furthermore, when the acid value was measured by titration, it was 1.82 (IleQ/g (Polysrene used in the present invention)).

Synthesis Examples 3 to 14 Polyurethane resins used in the present invention were synthesized in the same manner as Synthesis Example 1 or 2 using the diisocyanate and diol compounds shown in Table 1.

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 13,000 to 34,000.

Examples 1 to 5 The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a water suspension of 400 mesh of Bumiston, and then thoroughly washed with water. After etching by immersing it in 10% sodium hydroxide at 70°C for 60 seconds, it was washed with running water, neutralized with 20% nitric acid, and washed with water.

This was carried out in a 1% nitric acid aqueous solution at a rate of 160 chrome/dm' under the condition of VA=12.7■ using a sinusoidal alternating waveform current.
Electrolytic surface roughening treatment was performed using a special anode electricity amount of . When the surface roughness was measured, it was 0.6μ (expressed as Ra).

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

Next, by changing the type of polyurethane resin used in the present invention in the following photosensitive liquid (A), five types of photosensitive liquids [Δ]-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 respective photosensitive lithographic printing plates [A)-1 to [A)-5. .

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

The polyurethane resins used in the present invention for the photosensitive liquids [:Al-1 to [:A)-5] are shown in Table 2.

Photosensitive liquid [Al] Next, as a comparative example, the following photosensitive liquid CB) was applied in the same manner as the photosensitive liquid [Al] to prepare a photosensitive planographic printing plate CBI. The coating weight after drying was 2.5 g/m''.

A positive transparent original of the line drawing and halftone image was brought into close contact with the photosensitive layer of the photosensitive solution [BE photosensitive lithographic printing plates [A)-1 to 5 and CB], and exposed from a distance of 70 cm using a 30 ampere carbon arc lamp. I did it.

Exposed photosensitive lithographic printing plate [Al-1 to 5 and CB]
was immersed and developed in an 8-fold diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film 1m) at 25° C. for 60 seconds.

Heidelberg Co., Ltd. using the obtained lithographic printing plates (A)-1 to -5 and [B]! ! Printed on high-quality paper using commercially available ink on a KOR printer. The final number of printed sheets of lithographic printing plate 1: A)-1 to -5 and [B] was examined and was as shown in Table 2.

Table 2 As can be seen from Table 2, the number of prints for the lithographic printing plates CA)-1 to 5 (Examples 1 to 5) using the photosensitive composition of the present invention was higher than that of the comparative example CB). It has a high rigidity and excellent rigidity.

In addition, instead of the resin of the present invention in the photosensitive liquid (A), a commercially available polyurethane resin having no carboxyl group was used instead of Estane #5715 (Estane 85715, B).
When coating, exposing, and developing were performed in the same manner using the same method (manufactured by F. Gudrich), the 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.

Examples 6 to IO The surface of an aluminum plate having a thickness of 0.24 thts was grained using a nylon brush and an aqueous suspension of 400 mesh bumiston, and then thoroughly washed with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70°C for 60 seconds, then washed with running water, neutralized with 20% nitric acid, and then electrochemically roughened as described in JP-A-53-67507. law, i.e. VA = 12.7V, Vc = 9.
Electrolytic surface roughening treatment was carried out using an IV sinusoidal alternating current in a 1% nitric acid aqueous solution with an anode special electricity amount of 160 chrome/dm'. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55° C. for 2 minutes, and then anodized in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g/m'. Then silicic acid at 70℃) I
It was immersed in a 3% aqueous solution of Jum for 1 minute, washed with water and dried. The following photosensitive solutions [C)-1 to [CD-5] were applied to the aluminum plate obtained as described above using a wheeler and dried at 80°C for 2 minutes. Dry weight is 2.0g/m
"Met.

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, 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, soot weight is 2.0g/
It was rn'.

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

In addition, the weight average molecular weight (polystyrene standard) is 5.5.
．． 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 Fuji Photo Film side-type PS light from a distance of 1 m. 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 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 the lithographic printing plates (C)-1 to -5 and CD) 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 Comparative Example [D], the number of prints was larger and the printing durability was very excellent.

Examples 11 to 14 The following photosensitive liquid (E) was applied to the aluminum plate obtained in Example 6.
-1 to (E]-4 were applied using a wheeler and dried for 2 minutes at 80°C.The dry weight was 2.0 g/m'.

The polyurethane resins used in the present invention for photosensitive solutions [E)-1 to [E)-4 are shown in Table 4.

Photosensitive liquid [E] Next, as a comparative example, a benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer with a weight average molecular weight of 45.000 (polystyrene) was used instead of the polyurethane resin used in the present invention in the photosensitive liquid. standard)) using a photosensitive solution (
F) was applied in the same manner and dried. Dry weight is 2.0g/m
"Met.

Each photosensitive lithographic printing plate (E)-1 to (E)-4 and (Fl) obtained using photosensitive solutions (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 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 CF) 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 1'E)-1 to 4 and CF) was examined and was as shown in Table 4.

Table 4 As can be seen from Table 4, lithographic printing plates (E)-1 to 4 (Examples 11 to 14) using the photosensitive composition of the present invention had a higher number of prints than Comparative Example (F). It has a high printing durability and has excellent printing durability.

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

The polyurethane resins used in the present invention for photosensitive liquids [G)-1 to CG:l-2 are shown in Table 5.

Photosensitive liquid [G] Next, as a comparative example, methyl methacrylate-methacrylic acid (molar ratio 80/20) copolymer (weight average molecular weight 5
2,000 (polystyrene standard))
] was applied and dried in the same manner. Dry weight is 2.0g/m'
Met.

The photosensitive lithographic printing plates [G:]-1 to 2 and [H] obtained using the photosensitive liquids CG)-1 to 2 and [H] were coated with 1 meter from a distance of 1 m using a PS light manufactured by Fuji Photo Film QM, respectively. 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 CG)-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 CG)-1 to 2 and [H] was examined, and the results were as shown in Table 5.

Table 5 As can be seen from Table 5, the number of printed sheets was lower than that of the lithographic printing plates (GE-1 to GE-2 (Examples 15 to 16) were comparative examples of CH) using the photosensitive composition of the present invention. Many of them have excellent printing durability.

〔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)

[Scope of Claims] A photosensitive composition comprising a polyurethane resin having a carboxyl group and a siloxane bond represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I)