JP2000010280A - Photosensitive resin composition and photosensitive resin laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. which prevents oxidation deterioration and polymn. due to heat and light during production and preservation and has high sensitivity, high resolution and high elasticity. SOLUTION: The photosensitive resin compsn. contains at least a compd. having a conjugated diene chain and a mixture of a compd. having a phenol structure and a compd. contg. at least one selected from P, S, N and B and/or a compd. contg. a phenol structure and at least one selected from P, S, N and B in one molecule. A photosensitive layer contg. the photosensitive resin compsn. is laminated to obtain the objective photosensitive resin laminated body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition containing a compound having a conjugated diene chain, and more particularly to a photosensitive resin composition useful for flexographic printing and a photosensitive resin laminate using the composition. About the body.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive resin composition for flexographic printing, rubber elasticity has been required, and as a constituent material thereof, a composition containing an oligomer or a polymer having a conjugated diene chain has been known. I have. Further, among these, those which can be developed with an aqueous developer for toxicity, flammability, human body and environmental safety have been proposed.

As such a photosensitive resin composition, for example, JP-A-52-134655 and JP-A-53-10
648, JP-A-61-22339, JP-A-60-221451, JP-A-60-173055
JP, JP-A-2-175702, JP-A-3-2
28060, JP-A-4-293907, JP-A-4-293909, JP-A-4-294353
JP, JP-A-4-340968, JP-A-5-3
No. 2,743, JP-A-5-150451, JP-A-5-204139, and the like.

[0004] However, oligomers and polymers having a conjugated diene chain are disclosed in The Rubber Society of Japan, Vol.
Page (1959), Rubber Chem. Technol., 28: 74
6 (1955), Rubber Chem. Technol. 41, 18
2 (1968), Ind. Eng. Chem. Prod Res. Debelo
p.2, p.273 (1963), Journal of the Rubber Society of Japan, volume 40, 8
As described on page 81 (1967) and the like, it is known that deterioration is caused by oxygen, peroxide, ozone, radical components, and the like. For this reason, the photosensitive resin composition containing the oligomer or polymer having a conjugated diene chain,
Heat applied at the time of manufacture, deterioration due to the above factors during storage and storage and deterioration easily occur, as a photosensitive resin composition and printing plate, cracks, reduction in rubber elasticity,
Problems such as the inability to maintain sufficient quality due to the decrease in strength occur.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and its object is to provide high sensitivity, high resolution, high elasticity, and storage stability. An object of the present invention is to provide a photosensitive resin composition having excellent properties.

[0006]

Means for Solving the Problems The present inventors have intensively studied and studied to solve the above-mentioned problems, and as a result, they have found that a compound having a phenol structure and at least one of phosphorus, sulfur, nitrogen and boron are contained. The inventors have found that the above problems can be solved by using a hetero compound in combination with a compound having a conjugated diene chain, and have finally completed the present invention.
That is, the present invention relates to a photosensitive resin composition containing at least a compound having a conjugated diene chain, wherein (A) a compound having a phenol structure and (B) a compound containing at least one of phosphorus, sulfur, nitrogen, and boron. Mixture and / or
Or (C) a phenolic structure and phosphorus, sulfur,
A photosensitive resin composition containing a compound containing at least one of nitrogen and boron, and a photosensitive resin laminate using the composition.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As the compound having a conjugated diene chain contained in the present invention, an oligomer having a conjugated diene chain or /
And a polymer, an ethylenically unsaturated compound having a conjugated diene chain, and the oligomer or polymer having a conjugated diene chain is an oligomer or polymer obtained by polymerizing a conjugated diene-based hydrocarbon; a conjugated diene-based hydrocarbon and a monoolefin Examples include a random copolymer and a block copolymer obtained by polymerizing a system unsaturated compound,
It has a molecular weight of about 500 or more.

Specific examples of the conjugated diene hydrocarbon include 1,3-butadiene, isoprene, and chloroprene. These compounds are used alone or in combination of two or more. As the monoolefinically unsaturated compound, specifically, for example, styrene, α-methylstyrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl methacrylamide acetate, acrylate, methacrylate and the like.

The polymer obtained by polymerizing the conjugated diene hydrocarbon or the copolymer obtained by polymerizing a conjugated diene hydrocarbon and a monoolefinic unsaturated compound is specifically exemplified by butadiene. Polymer, isoprene polymer, chloroprene polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene copolymer Polymer, acrylate-butadiene copolymer, methacrylate-butadiene copolymer, acrylate-chloroprene copolymer, methacrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile - isoprene - styrene copolymers, acrylonitrile - chloroprene - styrene copolymer, and the like.

The oligomer or / and polymer having a conjugated diene chain in the present invention is an oligomer or / and polymer having a conjugated diene chain and having a number average molecular weight of 500 or more, and a terminal or side chain of the oligomer or / polymer. Functional groups such as hydroxyl group, carboxyl group, amino group, acrylate group, methacrylate group, etc. ester group, acrylamide group, methacrylamide group, urethane acrylate group, urethane methacrylate group, maleic ester group, maleic imide group, fumaric ester group, etc. It may include those having a group.

The ethylenically unsaturated compound having a conjugated diene chain is a compound having a conjugated diene chain and an ethylenically unsaturated group and having a number average molecular weight of 500 or more, and having an acrylate group or a methacrylate group at a terminal or a side chain. Isoester group, acrylamide group, methacrylamide group,
Urethane acrylate group, urethane methacrylate group,
It contains an ethylenically unsaturated group such as a maleic ester group, a maleic imide group and a fumaric ester group.
In the present invention, unsaturated acid esters of polyols having a conjugated diene chain are preferred. Specifically, polybutadiene polyol (di) (meth) (urethane) acrylate, polynitrile butadiene polyol (di) (meth)
(Urethane) acrylate, polyisoprene polyol (di) (meth) (urethane) acrylate, polyconjugated diene polyol (di) (meth) (urethane) acrylate such as polystyrene butadiene polyol (di) (meth) (urethane) acrylate, etc. Is mentioned. These include, but are not limited to, those in which a part of the conjugated diene chain is reduced, maleic esters of the above polyols, and the like. These compounds may be used alone or in combination of two or more.

The compound (A) having a phenol structure in the present invention includes all compounds having a phenol skeleton. Representative compounds include phenol and phenol.
o-cresol, 2,6-xylinol, 2,4,6-
Trimethylphenol, β-naphthol, tert-butylphenol, 2,6-di-tert-butylphenol,
2,6-di-t-butyl-4-methylphenol, 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-
Butylphenol), hydroquinone, catechol, p
-T-butylcatechol, 2,6-di-t-butyl-p
-Non-hetero compound composed of carbon, oxygen and hydrogen elements such as cresol, and 2,4-bis (n-octylthio)-
Hetero compounds containing nitrogen and sulfur, such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, and other hetero compounds to which elements such as phosphorus and boron are bonded. Can be mentioned.

In the present invention, the compound (B) containing at least one of phosphorus, sulfur, nitrogen and boron includes:
Triphenylphosphine, triphenylphosphite,
Tris nonylphenyl phosphite, trilauryl trithiophosphite, trimethyl phosphate, hexamethyl phosphoramide, triphenyl borate, 2,6-
Di-t-butyl-4-methylphenyldibutyl borate, dibutyl dicarbato zinc complex, distearyl dibutyl dithiocarbamate, 2-mercaptobenzimidazole, 2,4-bis- (n-octylthio) -6
(4-hydroxy-3,5-di-t-butylanilino)
-1,3,5-triazine and the like.

The mixing of (A) the compound having a phenol structure and (B) the compound containing at least one of phosphorus, sulfur, nitrogen and boron in the present invention is described in The Rubber Society of Japan, Vol. 42, No. 9, page 661. As described in Industrial Chemistry Magazine Vol. 71, No. 11, p. 1919, a compound having a phenol structure as a radical-accepting antioxidant and at least one of phosphorus, sulfur, nitrogen and boron as hydroperoxide-inactivating antioxidants are used. It is known that the antioxidant ability is remarkably improved by a synergistic effect with a compound containing the compound, but it is not known to stabilize a compound having a conjugated diene chain as in the present invention.

Next, the compound (C) contained in the present invention and containing at least one phenol structure and at least one of phosphorus, sulfur, nitrogen and boron in one molecule includes phosphorus, sulfur and nitrogen at a site having a phenol structure. And a heterostructure site having at least one boron is chemically bonded, for example, represented by the following general formula (1), but is not limited thereto.

[0016]

Embedded image R ¹ and R ² are an alkyl group having 1 to 30 carbon atoms and a hydroxyl group, which may be the same or different. X: heterostructure site containing at least one of phosphorus, sulfur, nitrogen and boron

In the general formula (1), R¹, R^TwoIs
An alkyl group having 1 to 30 carbon atoms or a hydroxyl group,
The kill group may have a linear or branched structure,
R¹, R ^TwoMay be the same or different. The present invention
And preferably a hydroxyl group, a methyl group, a t-butyl group, etc.
Can be mentioned.

In the general formula (1), X is N, S,
A heterostructure site containing at least one of P and B, specifically, triphenylphosphine, triphenylphosphite, trinonylphenylphosphite, trilauryltrithiophosphite, trimethylphosphate, hexamethylphosphoramide, Triphenyl borate, 2,6-di-t-butyl-4-methylphenyl dibutyl borate, dibutyl diocarbato zinc complex,
Distearyldibutyldithiocarbamate, 2-mercaptobenzimidazole, thiodipropionic acid, and o-cresol, 2,6, bonded via a compound containing at least one of nitrogen, sulfur, phosphorus, and boron.
-Xylinol, 2,4,6-trimethylphenol,
β-naphthol, t-butylphenol, 2,6-di-
t-butylphenol, 2,6-di-t-butyl-4-
Methylphenol and 2,2'-methylenebis (4-methyl-6-t-butylphenol) are exemplified.

Further, as specific examples of the general formula (1), 2,4
-Bis (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 2,4-bis [(octylthio) Methyl] -o-cresol, 2-
[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamamide), 2- (3,5
-Di-t-butyl-2-hydroxyphenyl) benzotriazole, 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], tris- (3,5-di-tert-butyl-4-hydroxylbenzyl) -isocyanurate, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (5-methyl-2-hydroxylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5 -Di-butyl-4
-Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N'-bis [3,5-di-t-butyl-4 −
Hydroxyphenyl) propionyl] hydrazine, 3,
5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2- (2'-hydroxyl-
5′-t-octylphenyl) benzotriazole,
4,4'-thiobis (3-methyl-6-t-butylphenol) and the like.

A mixture of (A) a compound having a phenol structure, which is a feature of the present invention, and (B) a compound containing at least one of phosphorus, sulfur, nitrogen and boron, and / or (C) a phenol structure in one molecule. And a compound containing at least one of phosphorus, sulfur, nitrogen, and boron are used to prevent a cross-linking reaction, oxidative deterioration, and deterioration of a compound having a conjugated diene chain without suppressing a photopolymerization reaction. 0.001 to 100 parts by weight of the product
Parts by weight to 10 parts by weight, more preferably 0.01 parts by weight to
It is compounded at a ratio of 5 parts by weight, and the compounding ratio of each compound is arbitrary.

Various polymers can be used as the base polymer in the photosensitive resin composition of the present invention.
These include hydrophobic polymers used as general-purpose elastomers, and specifically include non-conjugated diene-based elastomers and conjugated diene-based elastomers. Examples of the non-conjugated diene-based elastomer include a polyolefin-based elastomer having a chlorine atom and a polyolefin-based elastomer having no chlorine atom. Examples of the polyolefin elastomer having a chlorine atom include an elastomer obtained by chlorinating a polyolefin elastomer, an elastomer obtained by polymerizing a monomer having a chlorine atom, and a monomer having a chlorine atom and a chlorine atom. Elastomers obtained by copolymerization with a non-chlorinated monomer or an elastomer obtained by reacting chlorine or an active substance having a chlorine atom with a polymer having no chlorine atom. Specific examples of such a polyolefin-based elastomer having a chlorine atom include, for example, chlorinated polyethylene (Eraslen manufactured by Showa Denko KK, Daisorak manufactured by Daiso, HOLTALIZ manufactured by Hoechst, and Dow Chemical Co., Ltd.). DOW-CPE), chlorinated ethylene-propylene rubber (Eraslen manufactured by Showa Denko KK), butyl rubber, chlorinated polypropylene, vinyl chloride copolymer, polyvinylidene chloride, epichlorohydrin rubber, epichlorohydrin and ethylene oxide Copolymer of epichlorohydrin and propylene oxide, copolymer of epichlorohydrin and acrylic glycidyl ether (Epichromer manufactured by Daiso Co., Ltd., Goodrich Co., Ltd.)
And chlorinated polyethylene and chlorinated ethylene propylene rubber. These polymers are used alone or in combination of two or more.

The viscosity of the above-mentioned polyolefin elastomer having a chlorine atom may be, for example, ML _{1 + 4} (121) in consideration of the phase separation from an ethylenically unsaturated compound as described later. C) is preferably from 10 to 150. The chlorine content of the polyolefin-based elastomer having a chlorine atom is preferably 5 to 60% by weight, more preferably 10 to 60% by weight.
If the chlorine content is outside this range, the flexibility may be impaired or the thermal stability may be impaired, and the photosensitive resin composition may be hardened or colored.

Examples of the polyolefin elastomer having no chlorine atom include ethylene-propylene rubber, isobutylene rubber, ethylene-propylene-butadiene terpolymer, acrylic rubber, ethylene-acryl rubber, ethylene-vinyl acetate copolymer, and butyl rubber. Butyl rubber, hydrogen reduced styrene-isoprene rubber, and the like. Considering the point of phase separation with an ethylenically unsaturated compound as described later, for example, the Mooney viscosity of ethylene-propylene rubber is ML.
_{1 + 4} (100 ° C.) is preferably 20 to 150.

Other conjugated diene-based elastomers include polymers obtained by polymerizing conjugated diene-based hydrocarbons and copolymers obtained by polymerizing conjugated diene-based hydrocarbons with monoolefinic unsaturated compounds. Is mentioned.
Specific examples of the conjugated diene-based hydrocarbon include 1,3-butadiene, isoprene, and chloroprene. These compounds are used alone or in combination of two or more. Specific examples of the above monoolefinically unsaturated compound include, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, and chloride. Examples include vinylidene, acrylamide, methacrylamide, methacrylamide vinyl acetate, acrylate, and methacrylate.

The polymer obtained by polymerizing the conjugated diene-based hydrocarbon or the copolymer obtained by polymerizing a conjugated diene-based hydrocarbon and a monoolefinic unsaturated compound is specifically described as follows. Butadiene polymer, isoprene polymer, chloroprene polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-
Chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene copolymer, acrylate-butadiene copolymer, methacrylate-
Butadiene copolymer, acrylate-isoprene copolymer, methacrylate-isoprene copolymer, acrylate-chloroprene copolymer, methacrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer, An acrylonitrile-isoprene-styrene copolymer, an acrylonitrile-chloroprene-styrene copolymer and the like can be mentioned.

Considering the phase separation of the conjugated diene elastomer from the ethylenically unsaturated compound as described later, for example, the Mooney viscosity of acrylonitrile-butadiene rubber is 25 as ML _{1 + 4} (100 ° C.). ~ 95, Mooney viscosity of polybutadiene rubber is ML
_{1 + 4} (100 ° C.) is 25 to 65, and the Mooney viscosity of polyisoprene rubber is 30 to ML _{1 + 4} (100 ° C.).
Preferably it is 100.

In addition to the above, a hydrophilic polymer can be selected as the base polymer in the photosensitive resin composition of the present invention when development is carried out with an aqueous developer. The hydrophilic polymer used in the present invention is a polymer that is soluble or swells in water or a developer containing water as a main component (hereinafter, also referred to as a shell phase-forming hydrophilic polymer). Such a hydrophilic polymer is selected depending on the type of the core phase-forming hydrophobic polymer or the ethylenically unsaturated compound, and has a higher affinity with the core phase-forming hydrophobic polymer, but the ethylenically unsaturated polymer described later. It is said that a compound having a structure exhibiting lower affinity (for example, a compound having a common structure in a molecule, a compound having a similar solubility parameter (SP value), a compound having a similar viscosity, and an affinity based on empirical rules are referred to as compounds. Etc.) are selected. Examples of such a hydrophilic polymer include a —COOM ¹ group, a —SO ₃ M ² group,
-CONH ₂ group, -NH ₂ group, -OH group, and a polymer having a hydrophilic group such as -PO ₃ M group, crosslinked polymers and uncrosslinked linear polymers are also included.

Specifically, polyvinyl alcohol (PV
A), a general-purpose resin such as carboxymethyl cellulose, a diene rubber obtained by copolymerizing (meth) acrylic acid and a diene compound, a liquid polybutadiene modified with maleic anhydride, a liquid polyacrylonitrile-butadiene, and a monomer having a phosphate group. Examples thereof include a polymer obtained by copolymerizing a diene compound and a (meth) acrylate, and it is preferable to use a hydrophilic polymer having the above-mentioned hydrophilic group of 50 to 50,000 equivalent / 10 ⁶ g. If these groups are less than 50 equivalents / 10 ⁶ g, the affinity for water is poor, and it may be difficult to develop with neutral water. Conversely, if these groups exceed 50000 equivalents / 10 ⁶ g, the ink resistance may be poor. May be inferior.

The above M¹, M^TwoAre hydrogen ions
Monovalent metal ions (eg, Li ⁺, Na⁺, K⁺
Etc.) divalent metal ions (eg, Ca²⁺, Mg
²⁺Etc.) trivalent metal ions (eg, Al³⁺Etc.) or
Either a substituted or unsubstituted ammonium ion
U.

[0030] Representative polymers with ¹ group -COOM, polyurethanes with ¹ group -COOM, -C
Polyureaurethane having OOM ¹ group, —COOM ¹
Epoxy compounds having a polyester, a ¹ group -COOM having a group, polyamic acid having ¹ group -COOM, -
Acrylonitrile having COOM ¹ group - butadiene copolymer, a styrene having ¹ group -COOM - butadiene copolymer, polybutadiene having a ¹ group -COOM, polyisoprene having ¹ group -COOM, -COO
Polychloroprene having an M ¹ group, polyolefin having a —COOM ¹ group, sodium polyacrylate, polyacrylamide, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and derivatives thereof. However, the present invention is not limited to these.

The above -COOM ¹ group is in an acid or salt form. The polymer in which the —COOM ¹ group is in the form of a salt is obtained by neutralizing the polymer having the —COOH group. Compounds used in the neutralization include hydroxides of alkali metals such as lithium hydroxide, potassium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; potassium-t. -Alkoxides of alkali metals such as butoxide and sodium methoxide, hydroxides of polyvalent metals such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, polyvalent metal alkoxides such as aluminum isopropoxide, triethylamine and tri-n- Tertiary amines such as propylamine; secondary amines such as diethylamine and di-n-propylamine; cyclic amines such as morpholine; amino group-containing (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate; Ammonium such as ammonium salts , Magnesium acetate, Arushiumu, acetic acid metal salts such as aluminum acetate and the like. These may be used alone or in combination of two or more.

The above hydrophilic polymer may further have a polyoxyalkylene moiety as a hydrophilic group.
Further, it may have an ethylenically unsaturated group at a molecular terminal or a molecular inner chain so as to act as a crosslinking agent. The hydrophilic polymer is blended in an amount of preferably 3 to 100 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the hydrophobic polymer. If the amount is less than 3 parts by weight, the water developability of a photosensitive resin printing plate prepared from the resulting photosensitive resin composition may be insufficient, which is not preferred.

The photosensitive resin composition of the present invention contains an ethylenically unsaturated compound, for example, cetyl alcohol,
And unsaturated esters of aliphatic alcohols such as stearyl alcohol. Other examples include unsaturated esters of polyols. For example, ethylene glycol (di) (meth) acrylate, diethylene glycol (di) (meth) acrylate, glycerol (di) (meth) acrylate, 1,3-propanediol (di)
(Meth) acrylate, 1,4-butanediol (di)
(Meth) acrylate, 1,2,4-butanetriol (di) (meth) acrylate, 1,2,4-butanetriol (tri) (meth) acrylate, 1,4-cyclohexanediol (di) (meth) acrylate , 1,6
-Cyclohexanediol (di) (meth) acrylate, trimethylolpropane (di) (meth) acrylate, diallyl phthalate, trimethylolpropane (tri) (meth) acrylate, diallyl phthalate, diethyl fumarate, dibutyl maleate, 1,9 -Nonanediol (di) (meth) acrylate, N-substituted maleamide compounds (eg, N-methylmaleamide, N-ethylmaleamide, N-laurylmaleamide, etc.).

The other ethylenically unsaturated compounds include unsaturated esters of polyol oligomers. Examples of such materials include polyethylene glycol (di) (meth) (urethane) acrylate, polypropylene glycol (di) (meth) (urethane) acrylate, and polytetramethylene glycol (di) (meth) (urethane) acrylate. Polyester polyol obtained by condensation reaction of polyol such as polyether polyol (di) (meth) (urethane) acrylate and polyethylene glycol with polycarboxylic acid such as terephthalic acid and adibic acid, and polyester polyol obtained by introducing unsaturated ester ( Di) (meth) (urethane) acrylate, polyethylene polyol (di) (meth) (urethane) acrylate, polypropylene polyol (di)
Examples thereof include polyolefin polyols (di) (meth) (urethane) acrylates such as (meth) (urethane) acrylate and polyethylene propylene polyol (di) (meth) (urethane) acrylate, and maleic esters of the above-mentioned high molecular weight polyols.

The ethylenically unsaturated compound in the present invention may have a conjugated diene chain. In this case, the effect of stability during production and storage as a photosensitive resin composition which is a feature of the present invention is obtained. Appears. Specific examples include the aforementioned ethylenically unsaturated compounds having a conjugated diene chain.

Examples of the photopolymerization initiator to be added to the photosensitive resin composition of the present invention include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzylalkyl ketals, anthraquinones, thioxanthones and the like. Specifically, benzophenone, chlorobenzophenone, benzoin, acetophenone, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin dibutyl ether, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl isopropyl ketal, anthraquinone, Examples thereof include 2-chloroanthraquinone, 2-ethylanthraquinone, thioxanthone, 2-chlorothioxanthone, and methylnaphthoquinone. Also, benzyl dimethyl ketal,
Methylnaphthoquinone and 2-ethylanthraquinone are preferred.

In the present invention, a plasticizer other than those described above as a composition can be blended. Examples of the plasticizer used in the present invention include, for example, liquid polybutadiene rubber, liquid polyacrylonitrile butadiene rubber, liquid polystyrene butadiene rubber, liquid rubber such as liquid isoprene rubber, etc., dioctyl phthalate, aliphatic carbonized diphenyl phthalate and the like. Plasticizers such as phthalic acid ester of hydrogen, trimellitic acid ester such as trioctyl trimellitate, and adipic acid ester such as 2-ethylhexyl adipate, having a molecular weight of 400 to 3000
Nearby plasticizers such as adipic acid-based polyester or polyetherester may be used, and these may be used alone or in combination of two or more.

Examples of the method for preparing the photosensitive resin composition of the present invention include a method in which the above-mentioned components are mixed or mixed together in an arbitrary order, and a method in which the components are swelled and dispersed in an arbitrary solvent to form a uniform mixture. After that, a method of removing the solvent and the like are included. The photosensitive resin composition thus obtained is usually molded into a desired shape.

The photosensitive resin laminate of the present invention obtained by using the photosensitive resin composition of the present invention having the above-mentioned structure, that is, the printing original plate, comprises a photosensitive layer comprising the photosensitive resin composition on at least a support. May be provided, but preferably,
It comprises an adhesive layer, a photosensitive layer comprising the above-mentioned photosensitive resin composition, an anti-adhesion layer and a cover film on a support. As a method for producing the same, a support having an adhesive layer,
A photosensitive resin composition is sandwiched between a cover film having an anti-adhesive layer and a sandwich (with both the adhesive layer and the anti-adhesive layer inside) and heated and pressed to produce a photosensitive resin plate. . The anti-adhesion layer contains polyvinyl alcohol, polyacrylamide, cellulose, polyamide and the like. As the support, a polyester film, a polyethylene film, a polypropylene film, or the like is used, and a polyester film is preferably used.

When such a photosensitive resin printing plate is irradiated with ultraviolet rays, at least the ethylenically unsaturated compound is polymerized and cured. The UV light applied during curing is
Those having a wavelength of 150 to 500 nm, particularly 300 to 450 nm are preferable. Examples of such ultraviolet light sources include a low-thickness mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp,
A zirconium lamp or the like is desirable. The photosensitive resin composition of the present invention obtains an image by utilizing a difference in solubility in a developer before and after a photoreaction or a change in viscosity through a photoreaction with a negative film having an image and a developing process by a developer or peeling. Is what you can do.

The developer used as the developer may be any of commonly used organic solvents such as hexane, heptane, orange oil, olive oil, gasoline, kerosene, toluene, xylene and other hydrocarbon solvents, tetrahydrofuran, dioxane and ethyl ether. The first ether solvent, acetate ester, propyl acetate, and other ester solvents, such as methyl ethyl ketone, methyl butyl ketone, acetone and other ketone organic solvents, ethyl cellosolve, butyl cellosolve and other cellulosolve organic solvents, Ethanol, methanol, isopropanol, propanol, butanol and other alcoholic organic solvents, trichloroethane,
Examples thereof include halogen-based organic solvents such as trichloroethane, trichloroethylene, and chloroform.

Further, from the viewpoints of safety for the working environment, protection of human health, and protection of the global environment, an aqueous developer which is easily available as a developer can be used. As an aqueous developer, a surfactant can be added in addition to pure water and tap water. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Activators and the like can be widely used.
The addition amount of the surfactant is preferably 0.01 to 10% by weight in the developer. Further, a plurality of the above surfactants may be used in combination so as to perform optimum development.

The developer is preferably an aqueous developer in consideration of worker safety and environmental considerations. If necessary, a water-based developer such as ethanol, isopropanol, cellosolve, glycerin, polyethylene glycol, dimethylformamide, dimethylacetamide, or acetone may be used. And an organic solvent miscible with water.

In the developing solution, neutral carbonates, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium sulfate, sodium borate, sodium acetate, magnesium acetate, sodium citrate, sodium succinate, etc. Acidic or alkaline inorganic or organic salts; polymeric additives such as carboxymethylcellulose and methylcellulose; acids such as sulfuric acid, hydrochloric acid and phosphoric acid for adjusting pH, sodium hydroxide, potassium hydroxide and calcium hydroxide Alkali; other, viscosity modifiers, dispersion stabilizers, flocculants,
Various additives such as zeolite may be added as necessary.

For development, the photosensitive resin printing plate is immersed in a developer, and if necessary, the photosensitive resin layer is rubbed with a brush.
This is performed by removing uncured portions. The temperature during development is 20-50
C is preferred.

[0046]

EXAMPLES The present invention will be described specifically with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight", which are measured by the following methods of each physical property value or evaluation. (1) Mn and Mw / Mn of an ethylenically unsaturated compound
Measurement conditions: Equipment used: GPC LC-4A manufactured by Shimadzu Corporation Sample used: 1% by weight THF solution Flow rate: 1 ml / min Column: Shodex KF-805L Measurement temperature: 20 ° C UV wavelength: 220 nm (2) Ethylene unsaturated compound Viscosity measurement method: JIS K using a rotor Brookfield viscometer
It measured at 20 degreeC according to -6726. (3) Relief depth: For a photosensitive resin printing plate, the difference between the height of the developed image area and the height of the non-image area was determined by OG- manufactured by ONO SOKKI.
911. (4) Hardness: JIS-K6 for photosensitive resin printing plate
Spring-type hardness test according to 301 (Method A)
It was measured at 0 ° C. (5) Rebound resilience: For photosensitive resin printing plate, diameter 10
mm (weight 4.16 g) steel ball was dropped from a height of 20 cm, the height (a) at which the steel ball rebounded was read, and (a / 2
0) × 100% was set as a display value. (6) Water swelling ratio: the photosensitive layer resin composition was 0.1 cm thick,
The sheet was formed into a sheet having a length of 2.0 cm and a width of 5.0 cm, and was exposed at a dose of 4000 mJ / cm ² . The sheet was dried at 60 ° C. in a vacuum drier for 24 hours. This weight was weighed (a (g)). This was immersed in ion exchanged water at 20 ° C. for 24 hours and weighed (b (g)). The indicated value was (ba) / a × 100% as the water swelling ratio. (7) Shape stability: cylindrical detection terminal (detection terminal diameter: 1
Thickness gauge (DG-Ono Sokki Co., Ltd.)
The detection terminal of 911) was placed on the photosensitive layer side of the support (total thickness 2800 mm) on which the photosensitive layer made of the photosensitive resin composition was formed, and the change (amm) was read.
(A / 2800) × 100% was set as a display value.

Reference Example 1 Synthesis of ethylenically unsaturated compounds a to e Liquid polybutadiene having a hydroxyl group terminal (Idemitsu Petrochemical Co., Ltd .: Poly-bd R45HT, number average molecular weight 2)
800), acrylic acid, a compound having a phenolic structure, and a system containing no compound containing at least one compound containing at least one of phosphorus, sulfur, nitrogen, and boron at 80 to 90 ° C.
The esterification reaction was carried out for about 4 hours, and the properties of the obtained ethylenically unsaturated compound are shown in Table 1.

Reference Example 2 Synthesis of ethylenically unsaturated compounds f and g Liquid polybutadiene having a hydroxyl group terminal (Idemitsu Petrochemical Co., Ltd., Poly-bd R45HT, number average molecular weight 2)
800), a compound not containing a compound containing at least one compound containing at least one of phosphorus, sulfur, nitrogen and boron, and a compound not containing a compound having at least one of phosphorus, sulfur, nitrogen and methyl acrylate.
The transesterification reaction was carried out at 0 ° C. for about 4 hours, and the properties of the obtained ethylenically unsaturated compound are shown in Table 1.

Reference Example 3 Synthesis of ethylenically unsaturated compounds h and i A liquid polyisoprene having a hydroxyl group terminal (PIP number average molecular weight 2800, manufactured by Idemitsu Petrochemical Co., Ltd.), acrylic acid, a phenol structure, nitrogen and sulfur were prepared. The esterification reaction was carried out at 80 to 90 ° C. for about 4 hours in a system containing the compound and a compound not containing the compound, and the properties of the obtained ethylenically unsaturated compound are shown in Table 1.

Reference Example 4 Synthesis of ethylenically unsaturated compounds j and k 2,4-bis (n-octylthio) -6- (4) was added to 100 parts by weight of an acrylated polybutadiene (BAC-45: manufactured by Osaka Organic Co., Ltd.). Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (Irg. 56)
By mixing 1 part by weight of 5), an ethylenically unsaturated compound j was obtained. On the other hand, methacrylated nitrile butadiene rubber (VTBNX33: Ube Industries, Ltd.-BF-Go)
od ricn) 100 parts by weight of Irg. By mixing 1 part by weight of 565, an ethylenically unsaturated compound j was obtained.

[0051]

[Table 1] Table 1 Irg. 565: 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine WXR: 4,4'-thiobis (3-methyl- 6-t-butylphenol) TNP: trisnonylphenylphosphoite TPB: triphenylborate HMPA: hexamethylphosphoramide

Reference Example 5 Synthesis of hydrophilic polymer I 276 parts of hexamethylene diisocyanate, 145 parts of dimethylolpropionic acid, polyoxytetramethylene glycol (PTMG-850, manufactured by Hodogaya Chemical Co., Ltd.) 17
A polymer obtained by reacting 5 parts, 60 parts of hydroxyethyl methacrylate, and 343 parts of an acrylonitributadiene oligomer having a terminal amino group (HYCAR-ATBN1300 × 16, manufactured by Ube Industries, Ltd.) was obtained. Number average molecular weight (Mn) 1 of this polymer
The ratio Mw / Mn to the number average molecular weight (Mn) and the weight average molecular weight (Mn) was 4.5. The -COOH group in this polymer was neutralized with lithium hydroxide and magnesium acetate in the same amount to obtain a hydrophilic polymer I.

Examples 1-37 An oligomer or polymer having a conjugated diene chain, an ethylenically unsaturated compound and a photopolymerization initiator, benzine dimethyl ketal, as shown in Tables 2 to 4, were respectively added to all photosensitive resin compositions. 1% by weight and a compound containing at least one phenolic structure, phosphorus, nitrogen, sulfur, boron,
As necessary, a photosensitive resin composition containing the hydrophilic polymer I obtained in Reference Example 5 was obtained. Tables 2 to 4 show the respective initial performances and aging performances. In addition, Examples 1-4, Examples 8-25, Examples 30, 31, 33,
35 and 37 are aliphatic soap water (40 ° C.), Examples 6, 7, Examples 26 to 29, and Examples 32, 34, and 36 are trichloroethane 30 / isopropanol = 80/20.
(25 ° C.).

Comparative Examples 1 to 9 Photosensitive resin products were obtained in the same manner as in Example 1 except that a compound containing at least one of a phenol structure, phosphorus, nitrogen, sulfur and boron was not blended. Table 5 shows the evaluation results. In addition, as a developing solution, Comparative Examples 1-3, Comparative Examples 5-9
Is aliphatic soap water (40 ° C.), and Comparative Examples 4 and 9 are trichloroethane 30 / isopropanol = 80/20 (2
5 ° C.).

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

In Tables 2 to 5, NBR: nitrile butadiene rubber BR: polybutadiene rubber IR: isoprene rubber SIS: styrene isoprene styrene block polymer SBS: styrene butadiene styrene block polymer 1,9NDH: 1,9-nonanediol dimethacrylate 1, 6HX-1,6 hexanediol dimethacrylate SEMA: stearyl acrylate CPE: chlorinated polyethylene Irg. 1520L: 2,4-bis [(octylthio)
Methyl] -o-cresol Irg. 1222: 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester WXR, TNP, TPB, HMPA, Irg. 565 are the same as in Table 1, respectively. Addition method X: Not added during synthesis of ethylenically unsaturated compound, but added during production of photosensitive composition. Y: Compounded at the time of synthesis of the ethylenically unsaturated compound. Z: Compounded with an already synthesized ethylenically unsaturated compound.

[0060]

As is clear from Tables 2 to 5, outside of the present invention, the time required for forming the relief is as follows:
The initial value and the one-month aging value at 50 ° C. are longer than those obtained in the examples containing the compound having a phenolic structure and at least one of phosphorus, nitrogen, sulfur and boron, and change with time is poor. In each case, the ability to form a halftone dot of 1150 lines / inch 3% changes with time and is poor in performance. That is, the photosensitive resin composition of the present invention has a surprising effect of not only preventing oxidative deterioration when the photosensitive resin composition is stored, but also preventing polymerization by heat and light during production and storage. It is possible to provide a photosensitive resin composition having high resolution, high elasticity and excellent storage stability, which greatly contributes to the industry.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA02 AA11 AB02 AC01 AD01 BC55 BC81 BJ07 CB11 CC01 CC20 2H096 AA02 BA06 EA02 4F100 AH01A AH02A AH03A AH04A AK01A AK02A AK28A AL05A AT00B00 J02

Claims (4)

[Claims] 1. A photosensitive resin composition containing at least a compound having a conjugated diene chain, wherein (A) a compound having a phenol structure and (B) a compound containing at least one of phosphorus, sulfur, nitrogen and boron. A photosensitive resin composition comprising a mixture and / or (C) a compound containing a phenol structure and at least one of phosphorus, sulfur, nitrogen and boron in one molecule. 2. The photosensitive resin composition according to claim 1, wherein the compound having a conjugated diene chain is an oligomer and / or a polymer having a conjugated diene chain. 3. The photosensitive resin composition according to claim 1, wherein the compound having a conjugated diene chain is an ethylenically unsaturated compound having a conjugated diene chain. 4. A photosensitive resin laminate comprising at least a support and a photosensitive layer containing the photosensitive resin composition according to claim 1.