JP3240781B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin composition having water developability.

[0002]

2. Description of the Related Art Hitherto, various photosensitive resin compositions have been widely used in the fields of photoresists, printing inks, plate making and the like. Examples of the photosensitive resin composition include a composition containing a cyclized rubber and a bisazide compound, a thermoplastic elastomer, a composition containing an acrylic monomer and a photopolymerization initiator, polyester acrylate, epoxy acrylate, polyvinyl cinnamate, Compositions based on photosensitive resins such as chloromethylated polystyrene and aromatic azide group-containing resins are known, but all of these photosensitive resin compositions are water-insoluble and require an organic solvent during development. You are using However, in recent years, in addition to safety and health problems at the time of work, the influence of an organic solvent on the environment has become a problem. As a solution to the above problem, a novolak resin or an alkali-developable photosensitive resin composition comprising a poly (vinylphenol) and a quinonediazide compound is known. However, safer and easier development with neutral water is possible. A photosensitive resin composition is desired. Such a water-developable photosensitive resin composition includes, for example, a composition comprising a water-soluble resin such as polyvinyl alcohol, gelatin, casein and a dichromate, a diazonium salt or a bisazide compound, a water-soluble resin, a water-soluble acryl. A composition based on a water-soluble resin such as a composition comprising a system monomer and a photopolymerization initiator has been proposed. However, the conventional water-developable photosensitive resin composition has a too high affinity for water for the base resin, and swells during development to cause a decrease in strength and dimensional change. As a result, for example, the dimensional accuracy of the resist And the printing durability and printing quality of the printing plate are reduced. In order to solve the problems of such a water-developable photosensitive resin composition, the present applicant has already
(I) a copolymer of a conjugated diene compound or an acrylic ester compound, an α, β-ethylenically unsaturated carboxylic acid and a polyfunctional vinyl compound is soluble in an aqueous alkaline solution, and the (i) copolymer By mixing (ii) a photopolymerizable unsaturated monomer, (iii) a photopolymerization initiator and (iv) an amino group-containing compound, a photosensitive resin composition having water developability can be obtained. (For example, JP-A-60-179411, JP-A-60-21920)
No. 8, JP-A-61-181811).
However, for these water-developable photosensitive resin compositions, it is desired to further improve the strength of the resin plate after exposure and development. And (i) an aliphatic conjugated diene,
a partially crosslinked copolymer obtained by emulsion polymerization of an α, β-ethylenically unsaturated carboxylic acid and a compound having at least two groups capable of undergoing addition polymerization, (ii) an aliphatic conjugated diene polymer,
ii) a water-developable composition which contains a photopolymerizable unsaturated monomer, (iv) a compound containing a basic nitrogen atom and (v) a photopolymerization initiator and can form a printing plate having good dimensional stability and water resistance. Light-sensitive resin compositions are also known (for example, see JP-A-1-300246).
This composition does not solve the problems such as the strength of the resin plate after exposure.

[0003]

Accordingly, the present invention provides a method for reducing swelling during water development and reducing strength reduction and dimensional change.
An object of the present invention is to provide a novel water-developable photosensitive resin composition having an excellent property balance.

[0004]

According to the present invention, the above object is achieved by (1) a carboxyl group-containing diene polymer,
(2) a hydrogenated diene-based polymer containing a repeating unit composed of an aliphatic conjugated diene and having at least 80% of the double bonds of the repeating unit hydrogenated, (3) a photopolymerizable unsaturated monomer, (4) a photosensitive resin composition comprising: an amino group-containing compound; and (5) a photopolymerization initiator.
Is achieved by

Hereinafter, the present invention will be described in detail, which will clarify the objects, configurations and effects of the present invention. Component (1) First, (1) a carboxyl group-containing diene polymer (hereinafter, referred to as “component (1)”) is a carboxyl group-containing diene polymer having a repeating unit having an aliphatic conjugated diene bond as an essential component. It consists of at least one kind of coalescence. The carboxyl group in the polymer may be, for example, a method of copolymerizing a monomer mixture containing an aliphatic conjugated diene and a carboxyl group-containing unsaturated compound, and a polymer containing a repeating unit composed of an aliphatic conjugated diene. Can be introduced by a carboxylation treatment such as a maleic acid addition reaction. Component (1) can be morphologically linear or branched.

As the component (1), a carboxyl group-containing copolymer (hereinafter, referred to as an aliphatic conjugated diene, an α, β-ethylenically unsaturated carboxylic acid and a compound having at least two unsaturated groups) is used as a copolymerization component. Simply referred to as “carboxyl group-containing diene copolymer”). Thus, by using a compound having at least two unsaturated groups as a copolymer component, a crosslinked structure is introduced into the produced copolymer. The copolymer may further contain at least one of other monomer components in an amount of 70 mol% or less of all copolymer components, if necessary.

In the carboxyl group-containing diene-based copolymer, the content of each of the aliphatic conjugated diene, the α, β-ethylenically unsaturated carboxylic acid and the compound having at least two unsaturated groups is determined by their monomeric values. Based on the total amount of the body components, the aliphatic conjugated diene is 10-95.
Mol%, preferably 30 to 80 mol%, α, β
-0.1 to 30 mol% of an ethylenically unsaturated carboxylic acid,
Preferably it is 0.1 to 20 mol%, at least 2
The compound having one unsaturated group is 0.1 to 20 mol%, preferably 0.5 to 10 mol%.

[0008] In this case, if the content of the aliphatic conjugated diene is less than 10 mol%, the strength of the composition after exposure tends to decrease, while if it exceeds 95 mol%, the water developability of the composition becomes poor. It may be insufficient. Α, β
-When the content of the ethylenically unsaturated carboxylic acid is less than 0.1 mol%, the water developability of the composition may be insufficient, while when it exceeds 30 mol%, the composition after exposure becomes hard. Tends to be brittle. Further, if the content of the compound having at least two unsaturated groups is less than 0.1 mol%, the water developability of the composition may be insufficient, while if it exceeds 20 mol%, the component ( In some cases, the compatibility between 1) and (3) the photopolymerizable unsaturated monomer is deteriorated and the processability is reduced, and the strength of the composition after exposure may be insufficient.

As the aliphatic conjugated diene, for example, butadiene, isoprene, 1,3-pentadiene, 1,1,
3-hexadiene, 2,3-dimethylbutadiene, 4,
5-diethyl-1,3-octadiene, 3-butyl-
Examples thereof include 1,3-octadiene, chloroprene, 2,3-dichlorobutadiene, and 1,3-cyclopentadiene. These aliphatic conjugated dienes can be used alone or in combination of two or more.

The α, β-ethylenically unsaturated carboxylic acids include, for example, (meth) acrylic acid, itaconic acid,
Α, β-ethylene such as itaconic anhydride, maleic anhydride, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, cinnamic acid, etc. Examples thereof include free carboxyl group-containing esters such as monomethyl esters, monoethyl esters, and monopropyl esters of unsaturated polycarboxylic acids. These α, β-
The ethylenically unsaturated carboxylic acids can be used alone or in combination of two or more.

Examples of the compound having at least two unsaturated groups include dialkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. (Meth) acrylates;

Di (meth) acrylates of polyalkylene glycol (alkylene glycol units = 2 to 23) such as polyethylene glycol and polypropylene glycol;

Di (meth) acrylates of polymers having hydroxyl groups at both ends, such as hydroxy-butadiene at both ends, hydroxy-polyisoprene at both ends, hydroxybutadiene-acrylonitrile copolymer at both ends, hydroxy-polycaprolactone at both ends;

Trivalent such as glycerin, 1,2,4-butanetriol, trimethylolalkane (alkane has 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon atoms) and pentaerythritol Oligo (meth) acrylates of the above polyhydric alcohols;

Oligo (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols;

1,4-cyclohexanediol, 1,4
-Di (meth) acrylates of cyclic polyols such as benzenediol;

Oligo (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate ;

Bis (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide;

Polyvinyl aromatic compounds such as divinylbenzene, diisopropenylbenzene and trivinylbenzene;

Unsaturated alcohol esters of polycarboxylic acids such as divinyl phthalate and diallyl phthalate;

Examples include polyfunctional unsaturated ethers such as divinyl ether and diallyl ether.
These compounds having at least two unsaturated groups can be used alone or in combination of two or more.

Further, other monomer components other than the following are not particularly limited, but specific examples thereof include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Methylstyrene, pt
-Butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, N, N-dimethyl-p-aminostyrene, N, N
-Diethyl-p-aminostyrene, vinylpyridine, vinylpiperidine, vinylpyrrolidone, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic nitrile, cinnamic acid Nitrile, dinitrile itaconic acid, dinitrile maleate, dinitrile fumarate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxy Ethyl) (meta)
Acrylamide, crotonic amide, cinnamamide,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t- Butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methyl crotonate, ethyl crotonate, Propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate, fuma Diethyl, vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate and the like.

The component (1) such as a carboxyl group-containing diene copolymer is preferably in the form of particles. Such a particulate component (1) can be directly produced by, for example, emulsion polymerization, suspension polymerization, precipitation polymerization, or the like using a radical polymerization initiator. Alternatively, for example, a previously produced bulk polymer is granulated, Alternatively, it can be obtained by obtaining a polymer in a particle form from a polymer solution. The particulate component (1) is preferably produced by emulsion polymerization or suspension polymerization, and particularly preferably produced by emulsion polymerization from the viewpoints of particle size and particle diameter uniformity.

Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, paramenthane hydroperoxide, and di-tert-butyl peroxide; and 2,2'-azobisisobutyro. Nitrile, 2, 2 '
Azo compounds such as -azobisisovaleronitrile and 2,2'-azobisisocapronitrile; inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide; the above-mentioned organic peroxides and inorganic peroxides And a redox catalyst comprising an organic amine, a reducing agent such as organic amine, ferrous sulfate, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, L-ascorbic acid, and sulfinic acid.

As the emulsifier used in the emulsion polymerization, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used. Agents and nonionic surfactants are preferred. These surfactants can be fluorinated surfactants. In the emulsion polymerization, a suspension stabilizer or a thickening agent as described below can be used together with the emulsifier in order to adjust the viscosity, the particle size and the like of the reaction system.

The suspension stabilizer used in the suspension polymerization includes polyvinyl alcohol, sodium polyacrylate, methyl vinyl ether-maleic anhydride copolymer, water-soluble polyether, hydroxyethyl cellulose, carboxymethyl cellulose, starch, gelatin. , Casein, alginate and the like.

In the above polymerization, the reaction components such as a monomer and a radical polymerization initiator may be added in their entirety before the start of the reaction, or a part or all of them may be divided or continuously divided after the start of the reaction. May be added. The polymerization reaction is
Usually, the reaction is performed at 0 to 60 ° C. in an atmosphere from which oxygen has been removed (for example, nitrogen). However, operating conditions such as temperature and stirring speed can be appropriately changed during the reaction. The polymerization reaction can be carried out in any of a continuous system and a batch system.

Component (2) also contains (2) a repeating unit consisting of an aliphatic conjugated diene and at least 80% of the double bonds in the repeating unit
Is hydrogenated diene polymer (hereinafter, referred to as “component (2)”), the diene polymer before hydrogenation is a polymer consisting of only one or more aliphatic conjugated dienes or It comprises at least one of a random copolymer or a block copolymer of one or more aliphatic conjugated dienes and one or more other monomers. These polymers or copolymers can be morphologically linear or branched.

As the component (2), in particular, the following (2-
At least one of the hydrogenated diene copolymers (1), (2-2) and (2-3) is preferred. (2-1) AB block copolymer comprising a polymer block A of a vinyl aromatic compound and an aliphatic conjugated diene polymer block or a random copolymer block B of a vinyl aromatic compound and an aliphatic conjugated diene An ABC block copolymer further comprising a taper block C comprising a copolymer block of a vinyl aromatic compound and an aliphatic conjugated diene, wherein the content of the vinyl aromatic compound is gradually increased or decreased, or An ABA block copolymer further containing a polymer block A of a compound, wherein (a) the weight ratio of the vinyl aromatic compound to the aliphatic conjugated diene is 5 to 60/95 to 40, ) Block A
And the total binding content of vinyl aromatic compounds in C is 3-50% by weight of all monomers and the content of vinyl aromatic compounds in block A is at least 3% by weight of all monomers;
And (c) a block copolymer having a vinyl bond content of an aliphatic conjugated diene moiety in the block B of more than 40 mol% (hereinafter, referred to as “block copolymer (2-1a)”);
And the block copolymer (2-1a) unit has at least one of the above A, B or C via a coupling agent residue.
Selected from the group consisting of block copolymers having a polymer molecular chain extended or branched by bonding to a polymer unit consisting of two blocks (hereinafter, referred to as “block copolymer (2-1b)”). Hydrogenation of at least one type of block copolymer has saturated at least 80% of the double bonds of the aliphatic conjugated diene portion, and has a number average molecular weight (hereinafter, referred to as “Mn”) of 50,000 to 60. 10,000 hydrogenated diene copolymers,

(2-2) Vinyl aromatic compounds 90 to 10
A polymer block D comprising 0% by weight and 10 to 0% by weight of an aliphatic conjugated diene, and having a vinyl bond content of 30 to 90% by mole.
Has at least one aliphatic conjugated diene polymer block E and at least one polybutadiene polymer block F having a vinyl bond content of less than 30 mol%, the total content of block D is 10 to 50% by weight, and the total content of block E is Is 30 to 80
Block copolymer (hereinafter referred to as “block copolymer (2)
-2a))) and the block copolymer (2-
2a) a block copolymer in which a polymer molecular chain is extended or branched by bonding a unit to a polymer unit comprising at least one block of D, E or F via a coupling agent residue (hereinafter, referred to as a block copolymer) Hydrogenation of at least one block copolymer selected from the group consisting of "block copolymer (2-2b)") to form at least 80 of the double bonds of the aliphatic conjugated diene moiety.
% Of saturated hydrogenated diene copolymer having Mn of 40,000 to 700,000,

(2-3) A polybutadiene polymer block G having a vinyl bond content of 20 mol% or less, and an aliphatic conjugated diene polymer block or a random copolymer block of a vinyl aromatic compound and an aliphatic conjugated diene. The vinyl bond content of the aliphatic conjugated diene moiety is 25 to 9;
It consists of 5 mol% of block H, and the block structure is [G-
HG] p or [GH] q (where p is an integer of 1 or more;
q is an integer of 2 or more. )) (Hereinafter, referred to as “block copolymer (2-3a)”), and the block copolymer (2-3a) unit is formed of the above-described G or From the group consisting of block copolymers in which the polymer molecular chain is extended or branched by bonding to a polymer unit consisting of at least one block of H (hereinafter, referred to as “block copolymer (2-3b)”) Mn in which at least 80% of the double bonds of the aliphatic conjugated diene portion are saturated by hydrogenating at least one selected block copolymer.
Is a hydrogenated diene copolymer of 50,000 to 600,000.

These block copolymers (2-1),
Examples of the vinyl aromatic compound used in (2-2) and (2-3) include, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butyl Styrene, divinylbenzene, diisopropenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1
-Diphenylethylene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, vinylpyridine and the like. Particularly preferred vinyl aromatic compounds are styrene and α-methylstyrene.

Further, the block copolymers (2-1) and (2)
Examples of the aliphatic conjugated diene used in -2) and (2-3) include butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and 4,5-diethyl- Examples thereof include 1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, 2,3-dichlorobutadiene, and 1,3-cyclopentadiene. Of these, butadiene, isoprene, 1,1, and 2 are required to obtain a hydrogenated diene copolymer which is industrially easy to use and excellent in physical properties.
3-pentadiene is preferred, and butadiene is particularly preferred.

Hereinafter, (2-1), (2-2) and (2)
Each hydrogenated diene copolymer of -3) will be further described. First, in (2-1) hydrogenated diene copolymer,
The weight ratio of (a) the vinyl aromatic compound to the aliphatic conjugated diene in the block copolymer (2-1a) is 5 to 60/95.
-40% by weight, preferably 7-50 / 93-50.
% By weight. 5% by weight of vinyl aromatic compound
If it is less than 7, the molded appearance of the composition may be impaired, which is not preferable. On the other hand, when the content of the vinyl aromatic compound is 60
If the content is more than 1% by weight, the (2-1) hydrogenated diene copolymer becomes resinous, and the impact resistance of the composition after exposure, particularly the low-temperature impact resistance, becomes insufficient.

In the block copolymer (2-1a), the total bond content of the vinyl aromatic compounds in the (b) blocks A and C is 3 to 50% by weight of the total monomers, preferably 5 to 50% by weight. 40% by weight, more preferably 5 to 25% by weight, and the binding content of the vinyl aromatic compound in the block A is at least 3% by weight of all monomers, preferably 5 to 5% by weight.
15% by weight. If the total binding content is less than 3% by weight, the molded appearance of the composition may be impaired, which is not preferred. If it exceeds 50% by weight, the (2-1) hydrogenated diene-based copolymer becomes resinous, The impact resistance, especially low-temperature impact resistance, of the composition after exposure becomes insufficient.

As the coupling agent used for producing the block copolymer (2-1b), for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, Dimethyldichlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4-di (chloromethyl) benzene, bis (trichlorosilyl)
Examples thereof include ethane, epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-vencentriisocyanate.

The block copolymer (2-1a) or (2a)
In the hydrogenation of -1b), at least 80% of the double bonds of the aliphatic conjugated diene portion must be saturated, preferably 90% or more, more preferably 95 to 1%.
Desirably, 00% is saturated. If the proportion of double bonds saturated by hydrogenation is less than 80%, heat resistance, weather resistance, ozone resistance, etc. may be insufficient depending on the purpose of use of the composition.

Mn of each of the block copolymer (2-1a), the block copolymer (2-1b) and the (2-1) hydrogenated diene copolymer is 50,000 to 600,000, preferably They are 80,000 to 500,000, respectively. If the Mn is less than 50,000, the strength, heat resistance and the like of the composition decrease, while
If it exceeds 10,000, fluidity and processability will decrease, and the molded appearance of the composition will also be impaired.

The method for producing the block copolymer (2-1a), the block copolymer (2-1b) and the (2-1) hydrogenated diene copolymer is described in, for example, JP-A-3-72512.
No., published in Japanese Unexamined Patent Publication No.

Next, in the (2-2) hydrogenated diene copolymer, the block D constituting the block copolymer (2-2a) is composed of 90 to 100% by weight of a vinyl aromatic compound and an aliphatic conjugated diene. 10 to 0% by weight. Block D
When the content of the vinyl aromatic compound is less than 90% by weight, the weather resistance and the ozone resistance of the composition deteriorate.

The vinyl conjugate content of the aliphatic conjugated diene portion in the block E constituting the block copolymer (2-2a) is 30 to 90 mol%, preferably 40 to 70 mol%. The block E is a polymer block having a structure similar to that of a rubber-like ethylene / butene-1 random copolymer block when, for example, the double bond of the aliphatic conjugated diene portion is hydrogenated by 100%. If the bond content is less than 30 mol%, the proportion of polyethylene chains after hydrogenation is too large, while if it exceeds 90 mol%, the glass transition point after hydrogenation increases, and in each case, the rubbery properties are lost, The effect of imparting flexibility to the composition becomes insufficient.

The vinyl conjugate content of the aliphatic conjugated diene portion in the block F constituting the block copolymer (2-2a) is less than 30 mol%, preferably 3 to 20 mol%. Block F has a vinyl bond content of 30 mol%
Above, the workability after hydrogenation decreases.

As the coupling agent used for producing the block copolymer (2-2b), the same as those for the block copolymer (2-1b) can be used.

The block copolymer (2-2a) or (2a)
In the hydrogenation of -2b), at least 80% of the double bonds of the aliphatic conjugated diene portion must be saturated, preferably 90% or more, more preferably 95 to 1%.
Desirably, 00% is saturated. If the proportion of double bonds saturated by hydrogenation is less than 80%, heat resistance, weather resistance, ozone resistance, etc. may be insufficient depending on the purpose of use of the composition.

Mn of each of the block copolymer (2-2a), the block copolymer (2-2b) and the (2-2) hydrogenated diene copolymer is 40,000 to 700,000, preferably Each is 50,000 to 500,000. If the Mn is less than 40,000, the strength of the composition after exposure is reduced, while if it exceeds 700,000, the fluidity and processability of the composition are reduced, and the appearance of the molded article is impaired.

The method for producing the block copolymer (2-2a), the block copolymer (2-2b) and the (2-2) hydrogenated diene copolymer is described in, for example, JP-A-2-13340.
No. 6 is described.

Further, in the (2-3) hydrogenated diene copolymer, the vinyl bond content in the block G constituting the block copolymer (2-3a) is 20 mol% or less;
It is preferably at most 18 mol%, more preferably at most 15 mol%. When the double bond of the aliphatic conjugated diene portion is hydrogenated at 100%, the block G is a crystalline polymer block having a structure similar to that of low density polyethylene (LDPE). %
If it exceeds 300, the drop of the crystal melting point after hydrogenation becomes large, and the strength of the composition after exposure is reduced.

The content of the vinyl bond in the block H constituting the block copolymer (2-3a) is 25 to 95 mol%, preferably 25 to 75 mol%, more preferably 25 to 55 mol%. is there. The block H is composed of an aliphatic conjugated diene polymer block or a random copolymer block of a vinyl aromatic compound and an aliphatic conjugated diene. When the bond is 100% hydrogenated, a rubbery ethylene / butene-1 random copolymer or ethylene / butene-1 / vinyl aromatic compound random copolymer, or a polymer block having a structure similar to a derivative thereof Where the vinyl bond content is 25
If it is less than 95 mol% or more than 95 mol%, after hydrogenation, it will have a crystal structure similar to that of polyethylene chains or polybutene-1 chains, etc., exhibit resinous properties, and thus the strength of the composition after exposure. Decrease.

The content of the vinyl aromatic compound in the block H is usually 35% by weight or less, preferably 3% by weight.
0 wt% or less, more preferably 25 wt% or less. As the content of the vinyl aromatic compound increases, the glass transition point of the block H increases accordingly, and the strength of the composition after exposure tends to decrease.

The content of the polymer blocks G and H in the (2-3) hydrogenated diene copolymer is such that the content of the block G is usually 5 to 90% by weight, preferably 10 to 85% by weight. H is usually 95 to 10% by weight, preferably 90 to 15% by weight. When the content of the block G is less than 5% by weight and the content of the block H exceeds 95% by weight, the crystalline polymer block component in the (2-3) hydrogenated diene copolymer becomes insufficient, The strength of the composition after exposure may be insufficient. If the content of the block G exceeds 90% by weight and the content of the block H is less than 10% by weight, the hardness of the composition after exposure may be too high.

As the coupling agent used in the production of the block copolymer (2-3b), the same coupling agents as in the case of the block copolymer (2-1b) can be used.

The block copolymer (2-3a) or (2
In the hydrogenation of -3b), at least 80% of the double bonds of the aliphatic conjugated diene portion must be saturated, preferably 90% or more, and more preferably 95 to 1%.
Desirably, 00% is saturated. If the proportion of double bonds saturated by hydrogenation is less than 80%, heat resistance, weather resistance, ozone resistance, etc. may be insufficient depending on the purpose of use of the composition.

Mn of each of the block copolymer (2-3a), the block copolymer (2-3b) and the (2-3) hydrogenated diene copolymer is 50,000 to 600,000, preferably They are 100,000 to 500,000, respectively. When these Mn are 5
If it is less than 10,000 or more than 600,000, the fluidity and processability of the composition are reduced, and the appearance of the molded product is also impaired.

The method for producing the block copolymer (2-3a), the block copolymer (2-3b) and the (2-3) hydrogenated diene copolymer is described in, for example, JP-A-2-11047.
No. 7 is described.

The above (2-1), (2-2), (2-3)
The amount of component (2) to be added can be appropriately selected according to the intended use of the composition, but is preferably 0.1 to 100 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of component (1). Is from 1 to 90 parts by weight, particularly preferably from 2 to 70 parts by weight. When the amount of the component (2) is less than 0.1 part by weight, the strength of the composition after exposure may be insufficient,
If it exceeds 100 parts by weight, the water developability of the composition tends to decrease.

Component (3) Next, (3) a photopolymerizable unsaturated monomer (hereinafter referred to as "component (3)") is irradiated with light in the presence of (5) a photopolymerization initiator described later. Is a compound having an unsaturated bond that can be polymerized by

As the component (3), for example, styrene, α
-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, divinylbenzene, diisopropenylbenzene, o
-Chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N,
Vinyl aromatic compounds such as N-diethyl-p-aminostyrene and vinylpyridine;

(Meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile,
unsaturated nitriles such as α-methoxyacrylonitrile, α-ethoxyacrylonitrile, nitrile crotonic acid, nitrile cinnamate, dinitrile itaconate, dinitrile maleate and dinitrile fumarate;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate And alkyl (meth) such as t-butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate Acrylates, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate,
Methyl cinnamate, ethyl cinnamate, propyl cinnamate,
Unsaturated carboxylic esters such as butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate and heptafluorobutyl (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate;

Mono (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, Ethoxypropyl (meth)
Alkoxyalkyl (meth) acrylates such as acrylate;

Cyanoalkyl (meth) acrylates such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate;

2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, 3
Aryloxyalkyl (meth) acrylates such as phenoxypropyl (meth) acrylate;

Mono (meth) acrylates of alkoxypolyalkylene glycols such as methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropyleneglycol and ethoxypolypropyleneglycol;

Mono (meth) acrylates of aryloxy polyalkylene glycols such as phenoxy polyethylene glycol and phenoxy polypropylene glycol;

Di (meth) acrylates of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol;

Di (meth) acrylates of polyalkylene glycols (alkylene glycol units = 2 to 23) such as polyethylene glycol and polypropylene glycol; hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, and hydroxybutadiene-acrylonitrile at both ends Polymerized di (meth) acrylates having hydroxyl groups at both ends, such as coalesced, hydroxypolycaprolactone at both ends;

Glycerin, 1,2,4-butanetriol, trimethylolalkane (carbon number of alkane = 1 to 1)
3), tetramethylolalkane (carbon number of alkane =
1-3), tri (meth) acrylate, tetra (meth) acrylate of trihydric or higher polyhydric alcohol such as pentaerythritol
Oligo (meth) acrylates such as acrylates;

Oligo (meth) acrylates such as tri (meth) acrylate and tetra (meth) acrylate of a polyalkylene glycol adduct of a trihydric or higher polyhydric alcohol;

1,4-cyclohexanediol, 1,4
-Di (meth) acrylates of cyclic polyols such as benzenediol and 1,4-dihydroxyethylbenzene;

Oligo (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid and mesaconic acid;

Monomethyl esters, monoethyl esters, monopropyl esters, monobutyl esters, monohexyl esters of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid;
Free carboxyl group-containing esters such as monooctyl ester;

Esters such as dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester and dioctyl ester of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid;

(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-
(Hydroxyethyl) (meth) acrylamide, N, N ′
Unsaturated amides such as -methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide;

Vinyl halide compounds such as vinyl chloride and vinylidene chloride; unsaturated alcohol esters such as vinyl acetate, allyl acetate, divinyl phthalate and diallyl phthalate; cyclopentene, dicyclopentadiene,
Examples thereof include cycloolefins such as ethylidene norbornene and norbornadiene.

These components (3) can be used alone or in combination of two or more. In the present invention, desired properties can be imparted to the composition after exposure by appropriately selecting the component (3) or a combination thereof.

The fluidity of the composition of the present invention can be freely changed from waxy or rubbery to low-viscosity liquid depending on the amount of component (3). The amount can be appropriately selected according to the purpose of use of the composition, but is preferably 10 to 100,000 parts by weight, more preferably 50 to 10,000 parts by weight, per 100 parts by weight of the component (1). Department. Ingredient (3)
If the amount is less than 10 parts by weight, the strength of the composition after exposure tends to decrease, and if it exceeds 100,000 parts by weight, the composition shrinks greatly after exposure and the water developability of the composition And water resistance after exposure are difficult to achieve, and the degree of freedom in designing the viscosity of the composition tends to decrease.

Component (4) Next, (4) an amino group-containing compound (hereinafter referred to as "component (4)") is a compound containing at least one of primary to tertiary amino groups. Become.

The component (4) includes, for example, primary amines such as methylamine, ethylamine, propylamine and butylamine:

Secondary amines such as dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine and the like:

As tertiary amines, trimethylamine,
Methyl diethylamine, dimethylethylamine, triethylamine, dimethylpropylamine, methylethylpropylamine, diethylpropylamine, methyldipropylamine, ethyldipropylamine, tripropylamine, dimethylbutylamine, methyldibutylamine,
Methylethylbutylamine, diethylbutylamine, ethyldibutylamine, methylpropylbutylamine, ethylpropylbutylamine, dipropylbutylamine,
Trialkylamines such as propyldibutylamine and tributylamine;

Alkyl alkanol tertiary amines such as dimethylethanolamine, methyldiethanolamine, diethylethanolamine and ethyldiethanolamine;

Trialkanolamines such as triethanolamine, diethanolpropanolamine, ethanoldipropanolamine and tripropanolamine;

N, N-dimethylaminoethoxyethanol, N, N-diethylaminoethoxyethanol, N, N
N, N-dialkylaminoalkoxyalkanols such as N-dimethylaminoethoxypropanol and N, N-diethylaminoethoxypropanol;

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N -Diethylaminopropyl (meth) acrylate, N, N-dipropylaminopropyl (meth)
N, N-dialkylaminoalkyl (meth) acrylates such as acrylate;

N, N-dialkylaminoalkoxyalkyl (meth) acrylates such as N, N-dimethylaminoethoxyethyl (meth) acrylate and N, N-diethylaminoethoxyethyl (meth) acrylate;

N- (N ', N'-dimethylaminoethyl) (meth) acrylamide, N- (N', N'-diethylaminoethyl) (meth) acrylamide, N-
Tertiary amino group-containing (meth) acrylamides such as (N ′, N′-dimethylaminopropyl) (meth) acrylamide and N- (N ′, N′-diethylaminopropyl) (meth) acrylamide;

N, N-dimethylaminoethyl-N'-
Examples thereof include tertiary amino group-containing carbamates such as (meth) acryloyl carbamate and N, N-diethylaminoethyl-N ′-(meth) acryloyl carbamate. These components (4) can be used alone or in combination of two or more.

As the component (4), a tertiary amine having good water developability is preferable. From the viewpoint of the strength of the composition after exposure, tertiary amino group-containing (meth) acrylates,
Α, such as tertiary amino group-containing (meth) acrylamides,
Compounds having a β-ethylenically unsaturated group are preferred.

The amount of component (4) can be appropriately selected according to the intended use of the composition. The content of amino groups is preferably 0.1 to 1 mol of carboxyl group in component (1). It is used in an amount of 5 mol or more, more preferably 0.8 mol or more. The content of the amino group in the component (4) is 0.5% per mole of the carboxyl group in the component (1).
If the amount is less than the mole, the water developability of the composition may be insufficient. However, even if the content of the amino group exceeds 2 mol,
The water developability of the composition is not particularly improved.

In the present invention, the component (3) and the component (4) may be the same compound. In such a case, the compounding amount of the compound with respect to the component (1) may be less than the component (1). It is adjusted so as to satisfy both the above-mentioned preferred ranges as 3) and component (4).

Component (5) Further, (5) a photopolymerization initiator (hereinafter, referred to as “component 5”) is used to polymerize the component (3) by light irradiation, and in a preferred embodiment of the present invention, The polymerization of the compound having an α, β-ethylenically unsaturated group in the component (4) is also a component that initiates or sensitizes.

As the component (5), for example, diacetyl,
Α-diketone compounds such as methylbenzoyl formate and benzyl, and acyloins such as benzoin and pivaloin;
Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; polynuclear quinones such as anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1,4-naphthoquinone;
Acetophenone, 2-hydroxy-2-methyl-propiophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxyphenylacetophenone,
Acetophenones such as 2,2-diethoxyacetophenone and trichloroacetophenone; benzophenones such as benzophenone, methyl-o-benzoylbenzoate and Michler's ketone; xanthones, thioxanthones,
And xanthones such as chlorothioxanthone.

The compounding amount of the component (5) is 100
The amount is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on parts by weight. When the amount of the component (5) is less than 0.1 part by weight, the photocuring of the composition may be insufficient. It is not economical because it does not contribute to curing, and sometimes it is not possible to disperse uniformly because of poor compatibility with component (3) or component (4).

Further, various additives can be added to the composition of the present invention, if necessary. Examples of such additives include thermal addition polymerization inhibitors that act as storage stabilizers. Examples of the thermal addition polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, pt-butyl catechol, p-methoxyphenol, pt-butyl catechol, and 2,6-di- hydroxy aromatic compounds such as t-butyl-p-cresol, 2,6-di-t-butyl-m-cresol, pyrogallol, β-naphthol; benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, quinones such as p-xyloquinone; nitro compounds such as nitrobenzene, m-dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-t-butylnitrone and 5,5-dimethyl-1-pyrroline-1-oxide Or a nitrone compound; chloranyl-amine, diphenylamine, dife Amines such as nilpicrylhydrazine, phenol-α-naphthylamine, pyridine and phenothiazine; sulfides such as dithiobenzoyl sulfide and dibenzyltetrasulfide; unsaturated compounds such as 1,1-diphenylethylene and α-methylthioacrylonitrile; Thiazine dyes such as blue, toluidine blue, and methylene blue;
1-diphenyl-2-picrylhydrazyl, 1,3,5
-Triphenylferdazyl, 4-hydroxy-2,
2,6,6-tetramethylpiperidine-1-oxyl,
2,6-di-t-butyl-α- (3,5-di-t-butyl) -4-oxo-2,5-cyclohexadiene-1-
Stable radicals such as ylidene-p-trioxyl and the like can be mentioned.

The amount of the heat addition polymerization inhibitor is, for example, 0.0 parts by weight based on 100 parts by weight of the entire photosensitive resin composition.
It is about 01 to 2.0 parts by weight.

Further, other additives include an antioxidant, a filler, a reinforcing material, a plasticizer, an antihalation agent, an adhesion aid and the like.

The composition of the present invention comprises component (1), component (2), component (3), component (4) and component (5).
Usually, it can be obtained by sufficiently mixing with various additives optionally blended under heating, for example, using a kneader or an intermixer. The properties of the composition obtained can be freely adjusted from a waxy or rubbery material having no fluidity to a low-viscosity liquid having good fluidity, and the degree of fluidity depends on the intended use of the composition. It is appropriately selected according to the situation. When a low-viscosity composition is particularly preferred, a suitable amount of a solvent can be added.

In processing a photosensitive resin plate from the composition of the present invention, various methods can be employed depending on the degree of fluidity of the composition. For example, when there is no fluidity or the fluidity is low, it is passed between spacers with an appropriate interval, or applied on an appropriate support using a coating device such as a roll coater, or compression molding, extrusion molding, A desired film thickness can be formed by calendering or the like.

The composition having good fluidity can be applied to a support by an appropriate application method such as roll coating, calender coating, doctor blade coating, air knife coating or the like, and processed into a photosensitive resin plate. In addition, it is particularly useful as a resist suitable for spin coating.

These photosensitive resin plates or resists are exposed to a chemical actinic ray such as ultraviolet rays through a negative film or the like having a desired pattern, and the unexposed portions are washed and removed with water, and then dried. A clear relief image can be formed. In this case, if necessary, re-exposure can be performed after drying.

[0105]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. Here, parts are based on weight. Example 1 Component (1) butadiene / methacrylic acid / ethylene glycol dimethacrylate / ethyl acrylate = 84.1 / 2.2 /
A monomer mixture having a composition of 1.2 / 12.5 (mol%)
Emulsion polymerization was performed using sodium lauryl sulfate as an emulsifier and 2,2'-azobisisobutyronitrile as a polymerization initiator. After the polymerization, the obtained emulsion was salted out and coagulated with calcium chloride, washed with water, and dried to produce a component (1) composed of a granular carboxyl group-containing diene copolymer.

Component (2) As the component (2), a hydrogenated diene polymer shown in Table 1 was used.

Photosensitive Resin Composition For 100 parts of the component (1) and 10 parts of the component (2), 15 parts of nonaethylene glycol monomethacrylate and 15 parts of trimethylolpropane trimethacrylate were used as the component (3). ) As N, N-dimethylaminopropylacrylamide, 3 parts of 2,2-dimethoxyphenylacetophenone as component (5),
And pt-butylcatechol as a storage stabilizer.
5 parts were blended and this was adjusted in a kneader controlled at 50 ° C.
The mixture was stirred for 30 minutes to prepare a photosensitive resin composition. The resulting composition was a clear wax.

Evaluation Using the photosensitive resin composition obtained as described above, a resin layer having a thickness of 0.5 mm was formed on a polyester sheet to prepare a photosensitive resin plate. The resin layer of the resin plate,
Using a developing machine (JOW-A-4P) manufactured by JEOL Ltd., the time required for dissolution of the resin layer was measured by brushing in warm water at 30 ° C. In addition, the resin plate,
After exposing for 6 minutes using an exposure machine (JE-A-SS) manufactured by JEOL Ltd., tensile strength, elongation at break and rebound resilience were measured in accordance with JIS K6301. As a result, both the water developability of the composition and the strength of the resin plate after exposure are excellent, the breaking elongation and rebound resilience of the resin plate after exposure are good, the transparency is good, and an excellent property balance is obtained. Was. The above results are shown in Tables 1 and 2.

Examples 2 to 4 As component (1), butadiene / methacrylic acid / divinylbenzene / methyl methacrylate = 84.1 / 2.2 /
A carboxyl group-containing diene copolymer consisting of 1.2 / 12.5 (mol%) was used.
Preparation and evaluation of a photosensitive resin composition were performed in the same manner as in Example 1 except that the hydrogenated diene polymer shown in (1) was used. As a result, the water developability of the composition and the strength of the resin plate after exposure are both excellent, the breaking elongation and rebound resilience of the resin plate after exposure are good, and the transparency is also good,
It had an excellent balance of properties. Table 1 shows the above results.
And Table 2.

Comparative Example 1 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the component (2) was not blended. As a result, although the water developability of the composition was good, the strength and elongation at break of the resin plate after exposure were extremely low. The above results are shown in Tables 1 and 2.

Comparative Example 2 Instead of the component (2) of Example 1, a styrene-butadiene-styrene block copolymer not subjected to hydrogenation (trade name: JSR TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Preparation and evaluation of a photosensitive resin composition were performed in the same manner as in Example 1 except that 30 parts of the photosensitive resin composition were used. as a result,
Although the water developability of the composition was good, the strength of the resin plate after exposure was extremely low, and the elongation at break was insufficient. The above results are shown in Tables 1 and 2.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

The photosensitive resin composition of the present invention has both excellent water developability and strength of the composition after exposure, and
The composition after exposure has good elongation at break and rebound resilience, good transparency, and excellent balance of properties.
In addition, the composition of the present invention can be freely adjusted to properties from a waxy or rubbery state having no fluidity to a low-viscosity liquid state. Therefore, the present composition can be used very suitably as a photosensitive material in the fields of photoresist, plate making, printing ink, and the like, and is also useful as a photosensitive paint, a photosensitive adhesive, a photo molding material, and the like. is there.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G03F 7/00 501 G03F 7/00 501 7/028 7/028 (72) Inventor Noboru Oshima 2-11 Tsukiji, Chuo-ku, Tokyo 24 Japan Synthetic Rubber Co., Ltd. (72) Inventor Takashi Nishioka 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-3-198058 (JP, A) JP JP-A-61-22339 (JP, A) JP-A-61-278845 (JP, A) JP-A-60-195038 (JP, A) JP-B-55-34930 (JP, B1) (58) Fields investigated (Int .Cl. ⁷ , DB name) G03F 7/038 C08L 53/02 C09D 4/00 C09J 4/00 C09J 113/00 G03F 7/00 G03F 7/028

Claims (1)

(57) [Claims] 1. A hydrogenated hydrogen containing a repeating unit consisting of (1) a carboxyl group-containing diene polymer and (2) an aliphatic conjugated diene, wherein at least 80% of the double bonds in the repeating unit are hydrogenated. A diene polymer, (3) a photopolymerizable unsaturated monomer, (4) an amino group-containing compound, and (5)
A photosensitive resin composition comprising a photopolymerization initiator.