JPH10292083A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable compsn. which is suitable for alkali developing, is excellent in heat resistance, and has a low permittivity by compounding a copolymer comprising phenylmaleimide deriv. units, styrene deriv. units, and carboxylic acid deriv. units in a specified ratio, a compd. having a plurality of oxazoline rings, and polybutadiene modified with reactive groups. SOLUTION: The copolymer used comprises 5-95 wt.% units represented by formula I, 5-95 wt.% units represented by formula II, and 0-50 wt.% units represented by formula III. In those formulae, R<1> , R<3> , and R<4> are each H or methyl; R<2> is alkylene, cycloalkylene, or arylene; X<1> and X<2> are each H, alkyl, or COOH; X<3> is COOH, CONR<5> R<6> (wherein R<5> and R<6> are each H or alkyl), or COOR<7> (wherein R<7> is alkyl) provided one of X<1> , X<2> , and X<3> is alkyl; and (n) is 0 or 1. The oxazoline compd. is compounded in an amt. of 0.5-1.2 equivalents based on 1 equivalent of the carboxylic acid deriv. units in the copolymer, and the modified polybutadiene is compounded in an amt. of 5-100 wt.% of the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a copolymer of a maleimide and a polymerizable compound having an ethylenically unsaturated bond, wherein the copolymer has a carboxylic acid group, a compound having a polybutadiene structure, The present invention relates to a curable composition comprising an oxazoline compound. For more information,
The present invention relates to an alkali-developable curable composition having a high glass transition temperature (Tg), a volume resistivity, a peel strength, and a low dielectric constant suitable for an insulating material of a laminated circuit board.

[0002]

2. Description of the Related Art Curable compositions are cured by heat or light to form paints, adhesives,
It is used for insulating materials for integrated circuits and for modeling purposes.

In recent years, a full additive method has been receiving attention as a method for increasing the density of printed wiring boards. In the full additive method, the plating resist to be used finally becomes an insulating layer between the wirings, so that it is possible to prevent the wiring from being displaced at the time of multilayering, and the printed wiring board having the wiring with a high aspect ratio. Is suitable for multi-layering.

As a plating resist remaining on the printed wiring board as an insulating layer, an epoxy resin has conventionally been used. However, since epoxy resin has poor heat resistance as a sealing material for a highly integrated laminated board, various polyimide resins have been developed.

In addition, the insulating layer is thinner in the full additive method than in a prepreg in which a resin is impregnated in glass fiber or the like, so that the insulating layer has a high degree of electrical insulation and a low dielectric constant that can withstand higher frequencies. Is required. In addition, a resin which can be alkali-developed is required for a developer from environmental issues, and a demand for an insulating material is diversified.

Although a polyimide resin has a lower dielectric constant than an epoxy resin, it has been insufficient to cope with a recent increase in frequency. Also, Japanese Patent Application Laid-Open No. 6-273930 proposes a curable composition comprising a specific polymaleimide. However, although this composition is excellent in heat resistance and has a low dielectric constant, it requires development with an organic solvent, and thus can be used for alkali development.

In order to meet such a demand, Japanese Patent Application Laid-Open No. 2-169602 discloses that an oxazoline compound is added to a photopolymerizable composition having a carboxylic acid, and the carboxylic acid is cured by heat after development. A curable composition that can be alkali-developed and is suitable for a solder resist by reducing the amount has been proposed. JP-A-6-256684 discloses a method of improving heat resistance by using a copolymer of acrylic acid and a polymerizable compound having an epoxy group, and thermally curing the epoxy group and a carboxylic acid after development. It has been proposed. Also, Japanese Patent Application Laid-Open No. 58-21926 proposes polybutadiene as a low dielectric constant insulating material although it is used as a resin for prepreg. But,
The curable compositions described in any of the publications are not practically satisfactory, and are not satisfactory in any of heat resistance, dielectric constant, alkali developability, and mechanical strength.

Accordingly, an object of the present invention is to provide a curable composition which is suitable for alkali development, has excellent heat resistance, and has a low dielectric constant.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a copolymer of a maleimide compound and an ethylenically unsaturated polymerizable compound and having a carboxylic acid group. Coalescence, a compound having a polybutadiene structure, and a curable composition comprising an oxazoline compound,
It has been found that the above object can be achieved.

The present invention has been made based on the above-mentioned findings, and (A) at least one kind of a repeating unit represented by the following general formula (I) represented by the following formula [4] (same as [formula 1]). 9
5% by weight of at least one kind of a repeating unit represented by the following general formula (II) of the following [Chemical formula 5] (the same as the above [Chemical formula 2]).
95% by weight and the following [formula 6] (same as the above [formula 3])
At least one of the repeating units represented by the general formula (III)
A curable composition containing a copolymer having 50% by weight, (B) a compound having two or more oxazoline rings, and (C) polybutadiene modified with a reactive functional group. .

[0011]

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[0012]

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[0013]

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[In the above general formulas (I) to (III), R ¹ , R
³ and R ⁴ represent a hydrogen atom or a methyl group; R ² represents an alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or an arylene group; X ¹ and X ² represent a hydrogen atom and 1 to 4 carbon atoms. X ³ represents COOH, CONR ⁵ R ⁶ (R ⁵ and R ⁶
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Or COOR ⁷ (R ⁷ is carbon atom 1)
Represents an alkyl group of 4 to 4. ), And any one of X ¹ , X ² and X ³ represents COOH, and n is 0 or 1.
Represents ]

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the curable composition of the present invention will be described in detail.

First, the copolymer (A) used in the present invention will be described. In the general formula (II), examples of the alkylene group represented by R ² include methylene, ethylene, propylene, isopropylene, butylene, second butylene, tertiary butylene, pentylene, hexylene, heptylene, octylene, tertiary octylene, and nonylene. , Isononylene, decylene, isodecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene and the like.Examples of the cycloalkylene group include cyclopentylene, cyclohexylene and the like. , Xylylene, naphthylene and the like. In particular, among R ² , an arylene group is preferable from the viewpoint of improving the effect.

In the above general formulas (I), (II) and (III), the number of carbon atoms represented by X ¹ , X ² and R ⁷ is 1
Examples of the alkyl group of (4) to (4) include methyl, ethyl, propyl, butyl, sec-butyl and tert-butyl.

In the above general formula (III), R ⁵ and R ⁶ when X ³ represents an amide group (—CONR ⁵ R ⁶ )
As an alkyl group having 1 to 8 carbon atoms represented by, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, Isooctyl, tertiary octyl and the like.

The repeating unit represented by the above general formula (I) more specifically includes the following repeating units I-1 to I-6 shown in [Chemical Formula 7] to [Chemical Formula 12].

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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When the repeating unit represented by the above formula (I) has a carboxylic acid group, the carboxylic acid group may be an amine salt. Examples of the amine compound used for forming the amine salt include trialkylamines such as trimethylamine and triethylamine, and esters of diethylethanolamine and (meth) acrylic acid.

The repeating unit represented by the above general formula (II) includes, for example, the following [Chemical Formula 13] to [Chemical Formula 18]
And the repeating units II-1 to II-6 shown below.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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When the repeating unit represented by the general formula (II) has a carboxylic acid group, the carboxylic acid group may be an amine salt. Examples of the amine compound used for forming the amine salt include the same amine compounds as those used in the general formula (I).

The copolymer [component (A)] used in the present invention is represented by the above general formula (III) as another component of the repeating units represented by the above general formulas (I) and (II). As the reactive monomer serving as a raw material, various known (meth) acrylic acids and their ester compounds or amide compounds can be used.

The composition of the copolymer used in the present invention is such that at least one kind of the repeating unit represented by the general formula (I) is 5 to 95% by weight, preferably 10 to 90% by weight, At least one of the repeating units represented by II), preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and at least one kind of the repeating units represented by the above general formula (III) 0 to 50% It is. Further, the repeating unit represented by the general formula (I) and the general formula (II)
Is preferably 50% by weight or more, and the carboxylic acid equivalent is preferably 2000 g / eq or less. When the repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (II) are out of the above range, the glass transition temperature and peel strength of the obtained curable composition after curing are reduced. It becomes impractical. If the carboxylic acid equivalent is more than 2000 g / eq, it may not be suitable for alkali development.

The content of the copolymer as the component (A) in the composition is preferably 30 to 90% by weight. If the ratio is out of this range, the mechanical strength may be insufficient, or the electrical characteristics may be reduced, which may be impractical.

Next, the compound (B) used in the present invention, which is a compound having two or more oxoline rings (hereinafter, also referred to as "oxazoline compound") will be described. The oxazoline compound is not particularly limited, for example, 2,2′-bis (2-oxazoline), 2,2′-
Bis (4-methyl-2-oxazoline), 2,2'-bis (5-methyl-2-oxazoline), 2,2'-bis (5,5'-dimethyloxazoline), 2,2'-bis ( 4,4,4 ', 4'-tetramethyl-2
-Oxazoline), 1,2-bis (2-oxazolin-2-yl)
Ethane, 1,4-bis (2-oxazolin-2-yl) butane, 1,6-bis (2-oxazolin-2-yl) hexane,
8-bis (2-oxazolin-2-yl), 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-bis (2-oxazolin-2-yl)
Yl) benzene, 1,2-bis (5-methyl-2-oxazoline
-2-yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,4-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,4 -Bis (4,4'-dimethyl
2-oxazolin-2-yl) bisoxazoline compound such as benzene, and 2 chemical equivalents of oxazoline group of the bisoxazoline compound, and a polybasic carboxylic acid (for example, maleic acid, succinic acid, itaconic acid, phthalic acid, Compounds having a terminal oxazoline group obtained by reacting with 1 chemical equivalent of a carboxyl group of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, chlorendic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc. And the like.

The oxazoline compound as the component (B) is used in an amount of preferably 0.1 to 1.2 chemical equivalents, more preferably 0 to 1 chemical equivalent of the carboxylic acid contained in the copolymer as the component (A). Preferably, it is used in an amount of 0.5 to 1.1 equivalents. When the oxazoline compound is used outside this range, the resulting cured product has chemical resistance, heat resistance,
Plating resistance, electrical insulation, adhesion, etc. may be reduced.

The content of the oxazoline compound (B) in the composition is preferably 3 to 50% by weight. If the ratio is out of this range, the mechanical strength may be insufficient, or the electrical characteristics may be reduced, which may be impractical.

Next, the polybutadiene modified with a reactive functional group, which is the component (C) used in the present invention, will be described. Examples of the polybutadiene include carboxylic acid modified, acrylic modified, epoxy modified, maleated modified, modified polybutadiene such as epoxy resin modified,
More specifically, compounds Nos. IV-1 to IV-6 shown in the following [Chemical Formula 19] to [Chemical Formula 24] are exemplified. However, the present invention is not limited by the following examples.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The butadiene as the component (C) is used in an amount of 5 to 1 based on 100 parts by weight of the copolymer [component (A)].
It is preferably contained in an amount of 00 parts by weight. If the butadiene is less than 5 parts by weight with respect to 100 parts by weight of the copolymer, the effect of improving the dielectric constant is small, and if it exceeds 100 parts by weight, the thermal stability and mechanical strength of the obtained cured product are insufficient. Sometimes.

The content of butadiene as the component (C) in the composition is preferably 3 to 50% by weight. If the ratio is out of this range, the mechanical strength may be insufficient, or the electrical characteristics may be reduced, which may be impractical.

Next, specific examples of the synthesis of the copolymer [component (A)] used in the curable composition of the present invention will be shown. However, the present invention is not limited at all by the following synthesis examples.

Synthesis Example 1 (Synthesis of Polymer 1 [Copolymer of N- (p-carboxyphenyl) maleimide and styrene]) 6.86 g (0.04 mol) of N- (p-carboxyphenyl) maleimide and 4.16 g of styrene (0.04 mol) was dissolved in 200 g of methyl ethyl ketone, and azobisisobutyronitrile (hereinafter, referred to as azobisisobutyronitrile) was dissolved.
2 g (0.012 mol) at 75 ° C
Reacted for 2 hours. The precipitated white precipitate was separated by filtration and washed with toluene to obtain 10.5 g (yield 95%) of white powdery polymer 1. The obtained polymer 1 had an acid value of 174 mgKOH / g and an average molecular weight of 47,800 according to gel permeation chromatography (GPC).

Synthesis Example-2 (Synthesis of Polymer 2 [Copolymer of N-phenylmaleimide and 4-vinylbenzyl-2-carboxyphenyl ether]) 6.92 g (0.04 mol) of N-phenylmaleimide and 4-vinylbenzyl 2-carboxyphenyl ether (10.16 g, 0.04 mol) was dissolved in methyl ethyl ketone (250 g), and AIBN2.
65 g (0.014 mol) was added and reacted at 75 ° C. for 2 hours. The precipitated white precipitate was separated by filtration and washed with toluene to obtain 15.7 g (yield: 92%) of white powdery polymer 2. The obtained polymer 2
Has an acid value of 131 mgKOH / g and an average molecular weight of 51200 from GPC.
Met.

Synthesis Example-3 (Synthesis of Polymer 3 [copolymer of N- (p-carboxyphenyl) maleimide, styrene and methyl acrylate]) 6.86 g (0.04 mol) of N- (p-carboxyphenyl) maleimide And styrene 4.16 g (0.04 mol) and methyl methacrylate
6.88 g (0.08 mol) was dissolved in 300 g of methyl ethyl ketone, 3.23 g (0.020 mol) of AIBN was added, and the mixture was reacted at 75 ° C. for 2 hours. The precipitated white precipitate was separated by filtration and washed with toluene to obtain 16.1 g (yield 90%) of a white powdery polymer 3. The obtained polymer 3 had an acid value of 125 mgKOH / g and an average molecular weight of 38,000 by GPC.

Synthesis Example 4 (Synthesis of triethylamine salt of polymer 1) 110 g of polymer (0.031 mol in terms of carboxylic acid) was dissolved in 90 g of cyclohexanone, and 3.1 g of triethylamine was stirred.
(0.031 mol) was added dropwise, and the precipitated white precipitate was filtered off and washed with cyclohexanone to give a white powdery polymer 4; 1
2.7 g (97% yield) was obtained.

Synthesis Example 5 (Synthesis of acrylate ester of diethylethanolamine of polymer 1) 110 g of polymer (0.031 mol in terms of carboxylic acid) was dissolved in 90 g of cyclohexanone, and 5.3 g of 2-acryloyloxyethyl-diethylamine was stirred. (0.031 mol)
The precipitated white precipitate was separated by filtration and washed with cyclohexanone to obtain 14.7 g (yield: 96%) of a white powdery polymer 5.

Comparative Synthesis Example-1 (Synthesis of Comparative Polymer 1 [Copolymer of Acrylic Acid and Styrene]) Acrylic acid (2.88 g, 0.04 mol) and styrene 4.16 g (0.04 mol) were dissolved in methyl ethyl ketone (100 g). AIBN3.
23 g (0.020 mol) was added and reacted at 75 ° C. for 2 hours. The precipitated white precipitate was separated by filtration and washed with methanol to obtain 6.9 g (yield: 98%) of Comparative Polymer 1 as a white powder. The obtained comparative polymer 1 had an acid value of 318 mgKOH / g and an average molecular weight of 33,100 by GPC.

The curable composition of the present invention may optionally contain an ester compound of (meth) acrylic acid and a polyhydric alcohol in order to adjust mechanical properties such as hardness of the obtained cured product. Good.

Examples of the ester compound of (meth) acrylic acid and polyhydric alcohol include, for example, ethylene glycol di (meth) acrylate and those having 2 to 2 ethylene groups.
14, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate Obtained by esterifying polyhydric alcohol such as dipentaerythritol hexa (meth) acrylate with α, β-unsaturated carboxylic acid; trimethylolpropane triglycidyl ether acrylic acid adduct (1/3), bisphenol A diamine A compound obtained by adding (meth) acrylic acid to a glycidyl group-containing compound such as glycidyl ether acrylic acid adduct (1/2); β
An ester compound or a polyisocyanate of a compound having a hydroxyl group and an ethylenically unsaturated bond such as a phthalic acid diester of -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate with a polycarboxylic acid; Adducts of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, and the like. The ester compound is preferably contained in the curable composition of the present invention in an amount of 3 to 50% by weight. If the content of the ester compound is less than 3% by weight, the effect of addition may not be observed. If the content is more than 50% by weight, the obtained cured product may have reduced mechanical strength or a high dielectric constant, which is not practical. There is.

The curable composition of the present invention can be cured by heat and light, and when it is cured by light, any photopolymerization initiator can be used.

As the photopolymerization initiator that can be used in combination with the composition of the present invention, a conventionally known compound can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, Benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-
Methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4'-methyldiphenylsulfide, benzoin butyl ether, 2-
Hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4
-Butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate,
1,7-bis (9′-acridinyl) heptane, 9-n
-Butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 9-n-octyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2
-Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2- (N-n
-Butyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (N- (2 "-)
Methoxy-1 "-methylethoxycarbonylmethyl)-
3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine and the like. These photopolymerization initiators may be used in combination with one or more known photopolymerization accelerators such as benzoic acid or tertiary amine. The photopolymerization initiator is used in the curable composition in an amount of 0.1.
It is preferably added at 1 to 30% by weight. If the amount is less than 0.1% by weight, the effect of the addition may not be observed.

The properties of the cured product can be improved by using a thermoplastic organic polymer together with the copolymer as the component (A) in the composition of the present invention. Examples of the thermoplastic organic polymer include (meth)
Copolymer of acrylic ester compound and (meth) acrylic acid, (meth) acrylic ester compound, (meth)
Copolymers with acrylic acid and other vinyl monomers copolymerizable therewith are exemplified.

Examples of the (meth) acrylic ester compound include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate tetrahydrofurfuryl (meth) acrylate, tert-butyl (meth)
Acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and the like.
Examples of the other vinyl monomers include diacetone acrylamide, styrene, and vinyl toluene.

The curable composition of the present invention may be subjected to a roughening step performed after curing in order to improve the adhesion.

The curable composition of the present invention may contain, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; a plasticizer; a functional silane coupling. Agents such as silica, alumina, talc, bentonite, zirconium silicate, powdered glass, fillers such as calcium carbonate, pigments, dyes, and coating and defoaming properties.
Conventional additives such as surfactants for improving the leveling property can be added.

The preferred composition of the composition of the present invention is 30 to 90 parts by weight of the copolymer (component (A)), 3 to 50% by weight of the oxazoline compound (component (B)) and polybutadiene [(C ) Ingredient] is a composition containing 3 to 50% by weight. Further, a more preferable composition of the composition of the present invention is 30 to 90 parts by weight of the copolymer [(A) component], 3 to 50% by weight of the oxazoline compound [(B) component], and 3 to 50% by weight of the polybutadiene [(C Component) 3 to 50% by weight, 3 to 50% by weight of an ester compound of (meth) acrylic acid and a polyhydric alcohol, and 0.1 to 30% by weight of a photopolymerization initiator.

The curable composition of the present invention usually contains a solvent capable of dissolving or dispersing the above-mentioned components as necessary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyloselosolve, ethyl cellosolve, N, N
-Dimethylformamide, N, N'-dimethylacetamide, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene,
It is used as a solution composition to which xylene, methanol, ethanol, and isopropanol are added.

The curable composition of the present invention is prepared by a generally known method, and may be a roll coater, a curtain coater,
Spin coater, various printing, by known means such as immersion,
It is applied on a supporting substrate such as metal, paper, plastic, and film. Also, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and there is no limitation on the application method.

The curable composition of the present invention comprises a paint, an ink,
It can be used for various applications such as an adhesive, a printing plate, and a photoresist for a printed wiring board, and the application is not particularly limited.

When the curable composition of the present invention is cured with light, various light sources usually used for photocuring can be used, and examples thereof include an argon laser, a mercury vapor arc, a carbon arc, and a xenon arc. A conventionally known light source can be used.

【Example】

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

Example 1 After the following compositions (composition units; parts by weight) shown in Table 1 were thoroughly mixed, the solution was dried on a surface-treated aluminum plate using a knife coater to obtain a film thickness. Is 30 μm
Was applied. After heating and drying at 80 ° C for 5 minutes,
Ultraviolet curing was performed by irradiation with a xenon lamp (20 mw / cm ² × 10 seconds). Further baking was performed at 150 ° C. for 30 minutes to obtain a cured product.

[0072]

[Table 1]

For the obtained cured product, the glass transition temperature (Tg) based on JIS K7198, the peel strength based on JIS C6481, the volume resistance based on JIS K6911 and the JIS
The relative dielectric constant at 1 MHz was measured based on K6911. The results are shown in Table 2 below.

The resolution was determined as follows. The composition was applied on a SiO ₂ glass substrate using a spinner, and then precured at 80 ° C. for 5 minutes to form a coating film having a thickness of 30 μm. Next, through a negative mask for test (line width 30 μm), a high-pressure mercury lamp was used for 300 mJ.
/ Cm ² . This was developed with a 0.5% by weight aqueous solution of tetramethylammonium hydroxide, washed with running water, and then blown with nitrogen to obtain a residual pattern. The resolution of the obtained pattern was observed with an optical microscope. When the pattern was developed correctly, it was evaluated as ○, when there was a partial defect, as Δ, and when the entire pattern was defective, as ×. The results are shown in Table 2 below.

[0075]

[Table 2]

From the above results, the curable composition of the present invention (Examples 1-1 to 1-5) was compared with Comparative Examples (1-1 to 1-5).
It is understood that a cured product having excellent performance can be provided as compared with the composition of 3).

[0077]

The curable composition of the present invention is not only suitable for alkali development, but also exhibits excellent peel strength and volume resistance, and particularly has a low dielectric constant. It is suitable.

Claims (4)

[Claims] (A) at least one kind of a repeating unit represented by the following general formula (I) represented by the following general formula (I): 5 to 95% by weight,
5 to 95% by weight of at least one of the repeating units represented by the following general formula (II) and one or more of the repeating units represented by the following general formula (III): 50
% By weight of a copolymer comprising (B) an oxazoline ring
A curable composition containing a compound having at least one polybutadiene and (C) a polybutadiene modified with a reactive functional group. Embedded image Embedded image Embedded image [In the above general formulas (I) to (III), R ¹ , R ³ and R ⁴
Represents a hydrogen atom or a methyl group, and R ² has 1 carbon atom.
X ^{1 to} X ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or COOH, and X ³ represents
OOH, CONR ⁵ R ⁶ (R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or COOR ⁷ (R ⁷ represents an alkyl group having 1 to 4 carbon atoms) ), And any one of X ¹ , X ² and X ³ represents COOH, and n represents 0 or 1. ] 2. The curable composition according to claim 1, wherein R ² in the general formula (I) is an arylene group. 3. The curable composition according to claim 1, further comprising an ester compound of acrylic acid or methacrylic acid and a polyhydric alcohol. 4. The curable composition according to claim 2, further comprising a photopolymerization initiator.