TW202337961A - Polymer compound and resin composition containing the polymer compound - Google Patents

Abstract

The present invention provides a polymer compound represented by the following formula (1), which has excellent solubility towards solvents with low boiling point such as toluene. A cured product can be provided by using the polymer compound represented by formula (1), and such cured product has sufficient flexibility for film formation, high adhesiveness to copper foils with low-roughness, low dielectric constant and dielectric loss tangent, and low linear expansion rate;

In formula (1), R₁, R₂, R₃ and R₄ each independently represent a methyl group, an ethyl group, an isopropyl group or a tertiary butyl group. X each independently represents an acetyl group or a partial structure represented by the following formula (2), where 5% or more of the multiple Xs are a structure represented by formula (2). Y represents a residue obtained by removing two amino groups from a diamino compound. n is the average value of the number of repeating units and ranges from 1 to 100;

(In formula (2), R₅ represents a hydrogen atom or a methyl group)

Description

Polymer compound and resin composition containing the same

The present invention relates to a polymer compound that can be easily formed into a thin film (flim) by casting a solution into a base material, and can be cured by heat or light by using it together with a free radical initiator. reaction, and the cured product has excellent dielectric properties, adhesion, and heat resistance.

Phenoxy resin is a polymer compound with a very large molecular weight obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenolic compound. By adding this phenoxy resin, general epoxy resin compositions or radically polymerizable compositions can be formed into a film shape, so it is used as an important component of film-like adhesives in a wide range of fields, especially in electric power/ In the electronic field, it is used in interlayer insulating layers of printed circuit boards and resin-coated copper foil.

Although the cured product of the resin composition containing phenoxy resin has excellent adhesion and film-forming ability, it has low heat resistance and high dielectric constant and dielectric loss tangent (dielectric constant 3.5 and dielectric loss tangent at a frequency of 1 GHz). Loss tangent is about 0.03), so it cannot actually be used in electronic devices where signal response speeds have become faster in recent years. Resins with excellent dielectric properties are generally High-molecular fluorine compounds such as polytetrafluoroethylene (PTFE) (Patent Document 1) and liquid crystal polymers (Patent Document 2) are known. However, the compatibility of these resins with other resins is extremely low, and the adhesion is insufficient.

Although aromatic bismaleimide is known to be a compound with excellent heat resistance and dielectric properties, it generally has poor solubility in solvents and is only soluble in high-boiling aprotic polar solvents such as NMP or DMF, making it difficult to use. In the field of electronic materials using low boiling point solvents such as toluene or methyl ethyl ketone. In addition, the hardened product is generally rigid and lacks flexibility, making it difficult to use it for film applications. Patent Document 3 discloses a method of performing a Michael Addition reaction (Michael Addition) between an aromatic bismaleimide and an aliphatic diamine to increase the molecular weight and thereby improve the solvent solubility. However, this method The polymer compound composed of a maleimine compound and a diamine compound has poor stability and is prone to gelation because the secondary amine remaining in its structure has reactivity with the maleimine group at the end of the molecule. problem. Patent Documents 4 and 5 disclose a method of improving stability by reacting a secondary amine contained in the addition reaction product of bismaleimide and diamine with acetic anhydride to perform acetylation. However, the resin obtained by this method has an extremely high linear expansion rate of the cured product and is not suitable for applications such as electronic devices that require reliability.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2005-001274

[Patent Document 2] Japanese Patent Application Publication No. 2014-060449

[Patent Document 3] Japanese Patent Application Publication No. 2006-241300

[Patent Document 4] Japanese Patent No. 6948907

[Patent Document 5] United States Publication No. 8,637,611

The present invention was developed in view of the above problems, and its object is to provide a polymer compound having excellent solubility in a low-boiling point solvent such as toluene, and a cured product of the polymer compound. The cured product of the polymer compound is It has sufficient flexibility for thin film formation, high adhesion to low-roughness copper foil, low dielectric constant and dielectric loss tangent, and low linear expansion rate.

The present inventors conducted in-depth studies and found that the above-mentioned problems can be solved by using a resin composition containing a polymer compound with a specific structure, and thus completed the present invention.

That is, the present invention relates to the following:

(1) A polymer compound represented by the following formula (1);

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group, an ethyl group, an isopropyl group or a tert-butyl group. X each independently represents an acetyl group or a partial structure represented by the following formula (2), provided that at least one of the plurality of ) shows the structure. Y represents the residue after removing 2 amine groups from the diamine compound; n is the average number of repeating units and ranges from 1 to 100;

(In formula (2), R ₅ represents a hydrogen atom or a methyl group).

(2) A resin composition containing the polymer compound described in the preceding paragraph (1) and a free radical initiator.

(3) The resin composition as described in the preceding item (2), which further contains a radical reactive monomer, and the radical reactive monomer system has a radical reactive functional group.

(4) The resin composition as described in the preceding paragraph (2), which further contains a radical reactive polymer having two or more radical reactive functional groups in one molecule.

(5) A film-like adhesive composed of the resin composition described in any one of the preceding paragraphs (2) to (4).

(6) A cured product of the resin composition described in any one of the preceding paragraphs (2) to (4).

(7) A cured product of the film-like adhesive described in the preceding paragraph (5).

According to the present invention, a polymer compound and a resin composition containing the polymer compound can be provided. The polymer compound and the resin composition containing the polymer compound can be produced by combining a radical initiator and applying heat or light energy. A cured product is formed, and the cured product of the resin composition is excellent in dielectric properties, adhesion, and heat resistance.

Embodiments of the present invention will be described below.

The polymer compound represented by formula (1) of the present invention is a reactant obtained by the following method:

(1) A diamine compound (A) (hereinafter simply referred to as "compound (A)") and a bismaleimide compound (B) with a specific structure in excess molar relative to compound (A) are synthesized. ) (hereinafter simply referred to as "compound (B)") copolymer (C),

(2) The compound (D) having an isocyanate group and a (meth)acrylic acid group (hereinafter simply referred to as "compound (D)") accounts for more than 5% but less than 100% of the secondary amine groups in the copolymer (C). ") react with the isocyanate group,

(3) React the secondary amine group remaining in the reactant of the copolymer (C) and the compound (D) with acetic anhydride.

First, the copolymer (C) which is an intermediate raw material of the polymer compound of the present invention will be described.

Copolymer (C) is a copolymerization reaction product (Michael addition reaction product) of compound (A) and compound (B) in molar excess relative to compound (A).

The compound (A) as the raw material of the copolymer (C) is not particularly limited as long as it has two amine groups in one molecule. Specific examples thereof include: 1,2-diaminoethane, 1,3 -Diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminodecane Dodecane, 4,4'-methylenedicyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis( Aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophorone diamine, norbornene diamine, dimer diamine, 3,3 '-Diamino-N-methyldipropylamine, diamine maleonitrile (diaminomaleonitrile), 1,3-diaminopentane, 9,10-diaminophenanthrene, 4,4'- Diaminooctafluorobiphenyl, 3,5-diaminobenzoic acid, 3,7-diamino-2-methoxyfluorobenzene, 4,4'-diaminodiphenylketone, 3,4- Diaminodiphenyl ketone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diamine Aminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2 -Diaminoanthraquinone, 2,4-isopropylphenylenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-bis Aminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2' -Bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3) ,5-diethylphenyl)methane, 2,3-diaminonaphthalene, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl) Methane, 4,4'-diaminophenyl terine, 3,3'-diaminophenyl terine, 2,2-bis(4,(4aminophenoxy)phenyl) terine, 2,2 -Bis(4-(3-aminophenoxy)phenyl)terine, 4,4'-diaminodiphenyl ether (4,4'-oxydianiline), 4,4'-diaminodiphenyl Sulfide, 3,4'-diaminodiphenyl ether, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy) )benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino- 3,3'-dimethoxybiphenyl, 9,9-bis(4-aminophenyl)quinone, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane , 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane , 2,3,5,6-tetramethyl-1,4-phenylenediamine; 3,3',5,5'-tetramethyl benzidine (3,3',5,5'-tetramethyl benzidine) , 2,2-bis(4-aminophenyl)hexafluoropropane, m-xylylendiamin, p-phenylenediamine, bis(4-amino-3-methylcyclohexyl)methane , 1,2-bis(2-aminoethoxy)ethane, etc.

In addition, the residue (bivalent linking group) after removing the two amine groups of compound (A) is equivalent to Y in formula (1).

Compound (A) is preferably an aliphatic diamine compound having 2 or more carbon atoms. Specific examples thereof include: 1,2-diaminoethane, 1,3-diaminopropane, and 1,4-diaminopropane. Butane, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenebiscyclohexanediamine , 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(amine Methyl) cyclohexane, isophorone diamine, norbornene diamine and dimer diamine, etc.

Y in the formula (1) is preferably a residue (bivalent linking group) obtained by removing two amine groups from the aliphatic diamine compound having 2 or more carbon atoms.

Compound (B) uses a bismaleimide compound, which is ring-closed by condensation of a bis-3,5-dialkyl-4-aminophenylmethane compound and maleic acid. Obtained from the reaction, and the four alkyl groups in the compound are independently methyl, ethyl, isopropyl or tertiary butyl.

Specific examples of compound (B) include: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3',5 ,5'-tetramethyl-4,4'-diphenylmethane bismaleimide, 3,3',5,5'-tetraisopropyl-4,4'-diphenylmethane bismaleimide Leimide, etc.

The alkyl group possessed by the above-mentioned compound (B) corresponds to R ₁ to R ₄ in the formula (1) described below. The alkyl group of compound (B) is preferably methyl or ethyl.

In compound (B), the "bismaleimide compound in which the ortho-position of the carbon atom on the benzene ring bonded to the maleimide group is a hydrogen atom" has high reactivity with the secondary amine group. In the copolymerization reaction used to synthesize copolymer (C), it is easy to gel due to the reaction between the hydrogen atoms in the ortho position and the amine group of the compound (A). However, by using the compound (B) in which the ortho positions are all alkyl groups, it is easy to gel. ), can prevent gelation during copolymerization reaction with compound (A).

When synthesizing copolymer (C), the usage amounts of compound (A) and compound (B) are usually smaller molar amounts compared to compound (B), and 1 molar amount relative to compound (B). Ear, the compound (A) is preferably 0.4 to 0.98 mol, more preferably 0.5 to 0.96 mol.

The reaction temperature during synthesis is usually 50 to 150°C, preferably 60 to 140°C, and the reaction time is usually 0.5 to 30 hours, preferably 1 to 20 hours. A reaction catalyst can also be used. The reaction only requires that the molecular weight obtained by GPC (gel permeation chromatography) cannot be increased from a certain value. Just set the intermediate point as the end point. The solvent used in the reaction may be distilled off under heating and reduced pressure, or may be directly used in the resin composition in a state containing the solvent.

It is preferable to use a solvent in the copolymerization reaction of compound (A) and compound (B). Examples of solvents that can be used include: toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclopentanone. Hexanone and propylene glycol monomethyl ether acetate, etc. The usage amount of the solvent is preferably 10 to 300% by mass, more preferably 20 to 200% by mass relative to the solid content of the raw material used for the copolymerization reaction.

The number average molecular weight of the copolymer (C) is usually 1,000 to 100,000, preferably 1,500 to 80,000. In order to obtain a copolymer (C) with a number average molecular weight within the aforementioned range, the raw material components may be added at the aforementioned ratio. By measuring the number average molecular weight, the value of n in the formula (1) can be calculated. n is the average number of repeating units and is in the range of 1 to 100. If it is within the range, the effect obtained by the polymer compound of the present invention can be exerted.

In addition, the molecular weight in this specification means the value calculated in polystyrene conversion based on the measurement result of GPC.

Next, the polymer compound of the present invention will be described.

The polymer compound of the present invention is a polymer compound in which 5% or more but less than 100% of the secondary amine groups present in the copolymer (C) react with the isocyanate group in the compound (D) represented by the following formula (3). After the reaction, the residual secondary amine group in the reactant obtained above is reacted with acetic anhydride to obtain acetylation.

In addition, R ₅ in the formula (3) has the same meaning as R ₅ in the formula (2). That is, R ₅ in formula (2) is derived from a hydrogen atom or a methyl group possessed by compound (D).

Specific examples of the compound (D) include: 2-isocyanatoethyl methacrylate (product name: Karenz MOI, manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (product name: Karenz AOI, Showa Denko Co., Ltd.) joint stock limited company), etc.

Regarding the usage amounts of copolymer (C) and compound (D) when synthesizing the polymer compound of the present invention, compound (D) is preferred relative to 1 mole equivalent of the secondary amine group in copolymer (C). It is 0.05 to 0.9 mol, more preferably 0.1 to 0.8 mol. The reaction temperature is preferably 10 to 90°C, and the reaction time is preferably 30 minutes to 5 hours.

By adding acetic anhydride to the reaction product of the copolymer (C) and the compound (D) obtained above, the remaining secondary amine groups can be acetylated. A preferred aspect of the synthesis method of the polymer compound of the present invention is as follows: performing a copolymerization reaction of compound (A) and compound (B) in a solvent, and adding compound (D) to the obtained copolymer (C) solution. reaction, and then acetic anhydride is further added to the obtained reaction solution to perform acetylation. .

The amount of acetic anhydride used when synthesizing the polymer compound of the present invention is as long as it is the same or more than the molar number of the secondary amine remaining in the reaction product of the copolymer (C) and the compound (D). Can. The reaction temperature is preferably 10 to 90°C, and the reaction time is preferably 30 minutes to 5 hours. The acetic acid and excess acetic anhydride generated after the reaction can be removed by separation by washing with water.

The resin composition of the present invention contains the polymer compound of the present invention and a free radical initiator.

Preferred thermal radical initiators include, for example: benzyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5- Dimethyl-2,5-bis(tert-butylperoxy)- 3-hexyne, di-tert-butylperoxide, tert-butylperoxycumyl peroxide, α,α-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5- Dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, di(tert-butylperoxy)isophthalate, benzoic acid peroxide Tributyl ester, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5- Peroxides such as bis(benzoylperoxy)hexane, bis(trimethylsilyl)peroxide and trimethylsilyltriphenylsilyl peroxide.

Examples of preferred photoradical initiators include: benzoin, benzoin methyl ether, benzoin ethyl ether and other benzoin and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone Class; Thiaxantrones such as 2,4-dimethylthiaxantrone, 2,4-diisopropylthiaxanthone, and 2-chlorothiaxanthone; acetophenone dimethyl ketal, Ketals such as benzyldimethyl ketal; diphenyl ketones such as diphenyl ketone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane -1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1; acylphosphine oxides and xanthones (xanthone) class, etc.

The content of the radical initiator in the resin composition of the present invention is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the total resin components such as the polymer compound and the radical reactive monomer described below as an optional component. Preferably, it is 0.1 to 8 parts by mass.

The resin composition of the present invention may further contain free radical reactive monomers. By further containing a radical reactive monomer, the reactivity of the resin composition of the present invention and the heat resistance of the cured product can be improved. In addition, the radical reactive monosystem in the present invention means having more than one radical reactive functional group in one molecule, and its number average molecular weight is 500 or less (the lower limit of the number average molecular weight is approximately 100) of compounds.

Specific examples of the radical reactive monomer include: acenaphthylene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glyceryl dimethyl Acrylate, 2-hydroxy-3-propenyloxypropyl methacrylate, alkylene oxide adduct of bisphenol A methacrylate, trimethylolpropane trimethacrylate, tricyclodecane Dimethanol dimethacrylate, glycerol dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated tripolysocyanate triacrylate, ε-caprolactone modified ginseng-(2-propene Ethyloxyethyl)tripolyisocyanate, neopentylerythritol triacrylate, di(trimethylolpropane)tetraacrylate, ethoxylated neopentylerythritol tetraacrylate, neopentylerythritol tetraacrylate, dioxin Pentaerythritol polyacrylate, dipenterythritol hexaacrylate, triallyl isocyanate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-benzene Base-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide, N-p-chlorophenyl-maleimide, N-p-methyl Oxyphenyl-maleimide, N-p-methylphenyl-maleimide, N-p-nitrophenyl-maleimide, N-p-phenoxyphenyl-maleimide Imide, N-p-phenylaminophenyl-maleimide, N-p-phenoxycarbonylphenyl-maleimide, 1-maleimide-4-ethyloxy Succinimide-benzene (1-maleimide-4-acetoxysuccinimide-benzene), 4-maleimide-4'-acetoxysuccinimide-diphenylmethane, 4-maleimide -4'-acetyloxysuccinimide-diphenyl ether, 4-maleimide-4'-acetylamine-diphenyl ether, 2-maleimide-6-acetyl ether Amine-pyridine, 4-maleimide-4'-acetamide-diphenylmethane and N-p-phenylcarbonylphenyl-maleimide N-ethylmaleimide, N- 2.6-Dimethylphenylmaleimide, N-cyclohexylmaleimide, N-2,3-dimethylphenylmaleimide, xylmethane Leimide, 2,6-xylenemaleimide, 4,4'-bismaleimide, diphenylmethane, etc., but those having a maleimide group as a functional group are preferred. .

Only one type of these radical reactive monomers may be used, or two or more types may be mixed and used.

The resin composition of the present invention may further contain a free radical reactive polymer. By further containing a radical reactive polymer, the adhesiveness of the resin composition of the present invention and the heat resistance of the cured product can be improved. In addition, the free radical reactive polymer in the present invention means one having more than one free radical reactive functional group (preferably more than two) in one molecule, and its number average molecular weight is more than 500. compound.

Specific examples of the radical reactive polymer include a copolymer of styrene and butadiene, modified polyphenylene ether resin, bismaleimide extended with amide imide, or the following formula (4) The indicated polymer compounds, etc. In addition, m in the formula (4) is the average value of the number of repeating units and is a real number expressed in the range of 1 to 20.

The copolymer of styrene and butadiene, which is a free radical reactive polymer, can be a random copolymer (commonly known as SBR) or a block copolymer. Alternatively, a double bond derived from butadiene in the block copolymer can be hydrogenated to form a saturated hydrocarbon (commonly known as SEBS resin). The ratio of styrene to butadiene in the polymer is usually 10:90 to 90:10, and its number average molecular weight is usually is 1,000 to 100,000. Specific product examples of SBR include CRAY VALLEY's Ricon100, Ricon181, and Ricon184. Specific product examples of SEBS resin include Asahi Kasei Co., Ltd.'s Tuftec series, Kraton's G polymer series, etc.

The modified polyphenylene ether resin, which is a free radical reactive polymer, is preferably a compound having methacrylyl groups, acrylyl groups or vinyl groups at both ends of the molecule and a number average molecular weight of 1,000 to 10,000. Specific examples thereof include a compound represented by the following formula (5) (product name: SA9000 manufactured by SABIC Japan Contract Co., Ltd.) having a methacryl group at both ends and a number average molecular weight of approximately 1,700, or a compound having a vinyl group at both ends. And a compound represented by the following formula (6) with a number average molecular weight of approximately 1,200 or 2,200 (product name: OPE-2St 1200 or OPE-2St 2200, manufactured by Mitsubishi Gas Chemical Co., Ltd.).

The imine-extended bismaleimide resin, which is a radical reactive polymer, can be obtained by a known method described in Japanese Patent Publication No. 5,328,006 and the like. Specifically, an aliphatic diamine and an aromatic or aliphatic tetracarboxylic dianhydride can be dehydrated and condensed in an organic solvent using an acid catalyst so that the aliphatic diamine becomes an excess molar ratio. It is obtained by subjecting the amine group present at the end of the polymer to dehydration condensation with maleic anhydride, and then removing the catalyst by washing with water.

Specific examples of aliphatic diamines include: 1,10-diaminodecane; 1,12-diaminododecane; dimer diamine; 1,2-diamino-2-methylpropane ;1,2-diaminocyclohexane;1,2-diaminopropane;1,3-diaminopropane;1,4-diaminobutane;1,5-diaminopentane;1 ,7-diaminoheptane; 1,8-diaminomenthane; 1,8-diaminooctane; 1,9-diaminononane; 3,3'-diamino-N- Methyldipropylamine; diaminomaleonitrile; 1,3-diaminopentane; 9,10-diaminophenanthrene, etc., but dimer diamine is particularly preferred.

Specific examples of aromatic or aliphatic tetracarboxylic dianhydride include: pyromellitic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. Carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, diethylene trianhydride Aminopentaacetic dianhydride, ethylenediaminetetraacetic dianhydride, 3,3',4,4'-diphenylketonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic Acid dianhydride, 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride), 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2 '-Bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-bisphenol A diphthalic anhydride, 5-(2,5-dioxytetrahydro)-3- Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, ethylene glycol bis(trimellitic anhydride), hydroquinone diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride (CBDA), 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,1'- Bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,4: 3',4'-dianhydride, 4-(2,5-dilateral oxytetrahydrofuran-3-yl)-1 ,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-bis-oxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6 -Tricarboxy-2-norbornane acetic dianhydride, etc., but particularly preferred ones are pyromellitic anhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride. Specific product names include Designer Molecules Inc.'s BMI-3000.

The resin composition of the present invention may further contain an organic solvent. Specific examples of organic solvents include aromatic solvents such as toluene and xylene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether mono. Ether solvents such as acetate and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; γ-butyrolactone and γ-valerolactone Lactones such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide and N,N-dimethylimidazolidone, etc. Amide solvents; tetramethylene and other solvents; etc. The content of the organic solvent in the resin composition of the present invention is usually 90 mass% or less in the resin composition, preferably 30 to 80 mass%.

The resin composition of the present invention may further contain a polymerization inhibitor to improve storage stability. The polymerization inhibitor that can be used together is not particularly limited as long as it is generally known, and examples thereof include benzoquinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil, and trimethylbenzoquinone; Or aromatic diols, di-tert-butylhydroxytoluene, etc.

The resin composition of the present invention can be used by blending an amount of fillers or additives within a range that does not impair the original performance for the purpose of imparting desired performance according to its intended use. The filler can be in fiber or powder form, and can include: silicon oxide, carbon black, alumina, talc, mica, glass beads, glass hollow spheres, etc.

The resin composition of the present invention may further contain flame retardant compounds, additives, etc. There are no special restrictions if these are generally used. For example, flame retardant compounds include: bromine compounds such as 4,4-dibromobiphenyl; nitrogen compounds such as phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, melamine, and benzoguanamine; Azine ring compounds, silicon compounds, etc. As additives, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent Optical whitening agents, photosensitizers, dyes, pigments, tackifiers, lubricants, defoaming agents, dispersants, leveling agents, gloss agents, etc. are used in appropriate combinations.

The resin composition of the present invention can be coated or impregnated on various substrates and used. For example, when a thermal radical initiator is used, it can be used as an interlayer insulating layer of a multilayer printed circuit board by coating on a PET film, and can be used as a cover layer by coating on a polyimide film. It is used as a resin-attached copper foil by coating it on copper foil and drying it. In addition, by impregnating glass cloth, cellophane, carbon fiber, various non-woven fabrics, etc., it can be used as a prepreg for printed circuit boards or CFRP. Furthermore, it can also be used as various resistors by using photoradical initiators.

The interlayer insulating layer or covering layer, resin-coated copper foil, prepreg, etc. of the present invention can be heated and pressed by a hot press or the like to form a hardened product.

(Example)

The present invention will be described in more detail below through Examples and Comparative Examples. In addition, the present invention is not limited to these examples.

Example 1 (Synthesis of polymer compound of the present invention)

Add 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleamide into a flask equipped with a thermometer, cooling tube, nitrogen introduction tube, and stirrer. Amine (product name: BMI-70, manufactured by K.I Chemical Industry Co., Ltd.) 22.10 parts (0.05 mol), dimer diamine (product name: Priamine 074, manufactured by Croda Co., Ltd.) 20.18 parts (0.0375 mol), 20 parts of toluene was reacted at 100°C for 8 hours in a nitrogen environment to obtain copolymer 1 (copolymer (C) corresponding to the intermediate raw material of the polymer compound of the present invention) represented by the following formula (7) copolymer, Y in formula (7) represents the toluene solution of the residue after removing two amine groups from the dimer diamine). The number average molecular weight of Copolymer 1 is 2,700 and the weight average molecular weight is 15,100. Calculated from number average molecular weight The value of n in formula (7) is 2.5. 1.16 parts (0.0075 moles) of Karenz MOI (manufactured by Showa Denko Co., Ltd.) was added to the toluene solution of the copolymer, and the reaction was carried out at 60° C. for 1 hour. Then, 6.12 parts (0.0675 moles) of acetic anhydride was added, and the reaction was continued. It reacted at 60°C for 1 hour. After adding 100 parts of toluene to the reaction solution for dilution, 50 parts of pure water was added, and the by-produced acetic acid was removed by stirring and washing with water. After washing with water repeatedly until the water layer becomes neutral, the toluene solution is concentrated to obtain a 25 mass % toluene solution of the polymer compound of the present invention. It is speculated that in the obtained polymer compound, 10% of X in the formula (1) is a part derived from Karenz MOI, and the remainder is an acetyl group.

Comparative Example 1 (Synthesis of Comparative Polymer Compound)

The polymer compound for comparison was obtained according to the method of Example 1, except that the step of adding Karenz MOI and reacting at 60°C for 1 hour was not performed, and the amount of acetic anhydride was changed to 7.65 parts (0.075 mol). 25 mass% toluene solution. It is speculated that in the obtained polymer compound, all X's in the formula (1) are acetyl groups.

Example 2, Comparative Example 2 (Preparation of Resin Composition)

Add 0.05 part of dicumyl peroxide as a free radical initiator to 10 parts of the polymer compound solution obtained in Example 1 and Comparative Example 1, and mix them uniformly to obtain the resin composition and resin composition of the present invention respectively. Resin compositions used for comparison.

(Evaluation of dielectric properties, glass transition temperature, and linear expansion coefficient (α1) of cured resin compositions)

Using an applicator, apply the resin compositions obtained in Example 2 and Comparative Example 2 to a thickness of 280 μm on the mirror surface of a copper foil with a thickness of 18 μm, and heat at 90°C for 10 minutes to dry the solvent to obtain a film. Adhesive. The film-like adhesive on the copper foil obtained above was heated and hardened at 180° C. for 1 hour using a vacuum oven, and then immersed in an etching liquid to remove the copper foil. Since both the film-like adhesive of the present invention and the comparative film-like adhesive were used to obtain cured products with a thickness of 70 μm that could be used as films, the dielectric properties of the cured products obtained were evaluated. The dielectric properties were measured using a network analyzer 8719ET (manufactured by Agilent Technologies) using the cavity resonance method to measure the dielectric constant and dielectric loss tangent at 10 GHz. Furthermore, the glass transition temperature and the linear expansion coefficient (α1) of the cured product of the film-like adhesive were determined using a TMA (thermomechanical measuring device). The results are shown in Table 1.

(Evaluation of bonding strength and heat resistance of cured resin compositions)

Using an applicator, the resin compositions obtained in Example 2 and Comparative Example 2 were each coated to a thickness of 50 μm on a low-roughness copper foil for high frequency with a thickness of 12 μm (CF-T4X-SV: Fukuda Metal Foil Powder Co., Ltd. Co., Ltd.), the solvent was dried by heating at 90° C. for 10 minutes, thereby obtaining a copper foil having a film-like adhesive composed of the resin composition of the present invention. The matte surface of another copper foil (the copper foil used is the same type of copper foil) is overlapped on the adhesive surface of the copper foil obtained above, and heated and hardened under vacuum pressure at a pressure of 3MPa for 1 hour. The 90° peel strength (adhesion strength) between copper foils was measured using a universal testing machine AGX-50 (manufactured by Shimadzu Corporation). Furthermore, the bonded copper foil was cut into 3 cm squares, floated in a 288° C. solder bath, and the time until abnormalities such as expansion and peeling occurred on the copper foil was measured. The results are shown in Table 1.

[Table 1] Evaluation results of cured products of resin compositions

Example 3 (Preparation of the resin composition of the present invention)

To 10 parts of the polymer compound solution of the present invention obtained in Example 1, 0.05 part of dicumyl peroxide as a free radical initiator and Ricon 100 (manufactured by CRAY VALLEY Co., Ltd., a copolymer of butadiene and styrene) were added. 0.5 parts and mix uniformly to obtain the resin composition of the present invention.

Example 4 (Preparation of the resin composition of the present invention)

To 10 parts of the polymer compound solution of the present invention obtained in Example 1, 0.05 part of dicumyl peroxide as a free radical initiator and 0.5 part of modified polyphenylene ether resin SA-9000 (manufactured by SABIC Contract Company) were added. parts and mix them uniformly to obtain the resin composition of the present invention.

Example 5 (Preparation of the resin composition of the present invention)

To 10 parts of the polymer compound solution of the present invention obtained in Example 1, 0.05 part of dicumyl peroxide as a free radical initiator and bismaleimide resin BMI-3000 ( Designer Molecules Inc.) and mix them uniformly to obtain the resin composition of the present invention.

(Evaluation of hardened products of resin compositions)

Evaluation was carried out in the same manner as the above "Evaluation of dielectric properties, glass transition temperature and linear expansion coefficient (α1) of cured products of resin compositions" and "Evaluation of bonding strength and heat resistance of cured products of resin compositions" Various characteristics of the resin compositions obtained in Examples 3 to 5. The results are shown in Table 2.

[Table 2] Evaluation results of cured products of resin compositions

As described above, the polymer compound of the present invention can be cured by using a radical initiator together to form a flexible film, and the cured product exhibits excellent dielectric properties, adhesion and heat resistance.

Claims (7)

A polymer compound represented by the following formula (1),

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group, an ethyl group, an isopropyl group or a tert-butyl group; X each independently represents an acetyl group or the following formula (2 ), only one of the plurality of Xs present is an acetyl group, and more than 5% of the plurality of Xs present is a structure represented by formula (2); The residue after excluding 2 amine groups; n is the average number of repeating units and ranges from 1 to 100

In formula (2), R ₅ represents a hydrogen atom or a methyl group. A resin composition comprising the polymer compound described in claim 1 and a free radical initiator. The resin composition according to claim 2 further contains a free radical reactive monomer, and the free radical reactive monomer system has a free radical reactive functional group. The resin composition as described in claim 2 further contains a free radical reactive polymer, and the free radical reactive polymer has two or more free radical reactive functional groups in one molecule. A film-like adhesive composed of the resin composition described in any one of claims 2 to 4. A cured product is a cured product of the resin composition described in any one of claims 2 to 4. A cured product is a cured product of the film-like adhesive according to claim 5.