WO2023120234A1

WO2023120234A1 - Polymeric compound and resin composition containing said compound

Info

Publication number: WO2023120234A1
Application number: PCT/JP2022/045421
Authority: WO
Inventors: 泰昌赤塚; 成生林本
Original assignee: 日本化薬株式会社
Priority date: 2021-12-21
Filing date: 2022-12-09
Publication date: 2023-06-29
Also published as: TW202337961A; JP2023092046A

Abstract

Provided is a polymeric compound represented by formula (1) (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's each independently represent an acetyl group or a partial structure represented by formula (2) (in formula (2), R5 represents a hydrogen atom or a methyl group), in which each of 5% or more of the plurality of X's represents the structure represented by formula (2); Y represents a residue having such a structure that two amino groups are removed from a diamino compound; and n represents an average number of repeating units and is within the range from 1 to 100).　The polymeric compound represented by formula (1) has excellent solubility in a low-boiling-point solvent such as toluene. By using the polymeric compound represented by formula (1), it is possible to provide a cured article having flexibility sufficient for the formation of a film, having high adhesiveness to a low-roughness copper foil, having a low dielectric constant and a low dielectric loss tangent, and having a low linear expansion coefficient.

Description

Polymer compound and resin composition containing the compound

The present invention can be easily formed into a film by a method of casting a solution into a base material, and by using it together with a radical initiator, a heat or photo-curing reaction is possible, and the cured product has dielectric properties. , to a polymer compound having excellent adhesiveness and heat resistance.

A phenoxy resin is a polymer compound with a very large molecular weight obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenol compound. By adding this phenoxy resin, general epoxy resin compositions and radically polymerizable compositions can be made into films, so it is used in a wide range of fields as an important component of film adhesives. In the electrical and electronic fields, it is used for interlayer insulating layers of printed wiring boards and resin-coated copper foils.

A cured product of a resin composition to which a phenoxy resin is added has excellent adhesiveness and film-forming ability, but has low heat resistance. 03), and it cannot be used for electronic devices with high signal response speed in recent years. Polymer fluorine compounds such as polytetrafluoroethylene (PTFE) (Patent Document 1) and liquid crystal polymers (Patent Document 2) are generally known as resins having excellent dielectric properties, but these resins are different from other resins. compatibility is extremely low, and adhesion is also insufficient.

Aromatic bismaleimides are known as compounds with excellent heat resistance and dielectric properties, but they generally have poor solvent solubility and dissolve only in high-boiling aprotic polar solvents such as NMP and DMF. It is difficult to use in the field of electronic materials that use low boiling point solvents such as methyl ethyl ketone. In addition, the cured product is generally rigid and lacks flexibility, making it difficult to use it for film applications. Patent Document 3 discloses a method for improving solvent solubility by subjecting an aromatic bismaleimide to a Michael addition reaction with an aliphatic diamine to increase the molecular weight of the aromatic bismaleimide. The problem with polymer compounds is that the secondary amines remaining in the structure thereof have reactivity with maleimide groups at the ends of the molecules, resulting in poor stability and a tendency to gel. Patent Documents 4 and 5 disclose a method of improving stability by reacting secondary amines of adducts of bismaleimide and diamines with acetic anhydride to acetylate the secondary amines. However, the resin obtained by such a method has a very high coefficient of linear expansion of the cured product, and is not suitable for applications such as electronic devices that require reliability.

JP 2005-001274 A JP 2014-060449 A Japanese Patent Application Laid-Open No. 2006-241300 Japanese Patent No. 6948907 US Pat. No. 8,637,611

The present invention has been made in view of the above points, and has a polymer compound that has excellent solubility in a low boiling point solvent such as toluene, and has sufficient flexibility to form a film, and has a low roughness. It is an object of the present invention to provide a cured product of the polymer compound having high adhesiveness to copper foil, low dielectric constant and dielectric loss tangent, and low coefficient of linear expansion.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a resin composition containing a polymer compound having a specific structure, and have completed the present invention.
That is, the present invention
(1) Formula (1) below

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a methyl group, ethyl group, isopropyl group or tertiary butyl group. X each independently represents an acetyl group or the following formula (2)

(In formula (2), _R5 represents a hydrogen atom or a methyl group.)
At least one of the multiple X's is an acetyl group, and 5% or more of the multiple X's are structures represented by formula (2). Y represents a residue obtained by removing two amino groups from a diamino compound. n is the average number of repeating units and ranges from 1 to 100; ) polymer compound represented by
(2) a resin composition comprising the polymer compound according to (1) above and a radical initiator;
(3) The resin composition according to (2) above, further comprising a radical-reactive monomer having a radical-reactive functional group;
(4) The resin composition according to the preceding item (2), further comprising a radical-reactive polymer having two or more radical-reactive functional groups in one molecule,
(5) a film-like adhesive comprising the resin composition according to any one of the preceding items (2) to (4); and (6) the resin according to any one of the preceding items (2) to (4). A cured product of the composition.
(7) A cured product of the film adhesive described in (5) above.
Regarding.

The polymer compound and the resin composition containing it according to the present invention can be cured by applying heat or light energy in combination with a radical initiator, and the cured product of the resin composition has dielectric properties, adhesion It is possible to provide a polymer compound having excellent properties and heat resistance.

Embodiments of the present invention are described below.
The polymer compound represented by formula (1) of the present invention is
(1) A diamino compound (A) (hereinafter simply referred to as “compound (A)”) and a bismaleimide compound (B) having a specific structure having an excess number of moles relative to compound (A) (hereinafter simply referred to as “compound ( B)”) to synthesize a copolymer (C) with
(2) A compound (D) having 5% or more and less than 100% of the secondary amino groups in the copolymer (C) and an isocyanate group and a (meth)acrylic group (hereinafter simply referred to as "compound (D)" to react with the isocyanate group in the
(3) A reaction product obtained by reacting a secondary amino group remaining in the reaction product of copolymer (C) and compound (D) with acetic anhydride.
First, the copolymer (C), which is an intermediate raw material for 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 a molar excess over compound (A).
The compound (A), which is a raw material for the copolymer (C), is not particularly limited as long as it is a compound having two amino groups in one molecule, and specific examples thereof include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 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(aminomethyl)cyclohexane, isophoronediamine, norbornenediamine, dimer diamine , 3,3′-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, 9,10-diaminophenanthrene, 4,4′-diaminooctafluorobiphenyl, 3,5-diaminobenzoic acid , 3,7-diamino-2-methoxyfluorene, 4,4′-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2, 3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2 -diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 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'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, 2,2-bis(4,(4aminophenoxy)phenyl)sulfone, 2,2-bis(4-( 3-aminophenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 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)fluorene, 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′-tetramethylbenzidine, 2,2-bis(4-aminophenyl)hexafluoropropane, m-xylylenediamine, p-xylylenediamine, bis(4-amino-3-methyl cyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane and the like.
The residue (divalent linking group) of compound (A) excluding the two amino groups corresponds to Y in formula (1).

The compound (A) is preferably an aliphatic diamino compound having 2 or more carbon atoms, and specific examples thereof include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 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(aminomethyl)cyclohexane, isophorone diamine, norbornene diamine and dimer diamine.
Y in formula (1) is preferably a residue (a divalent linking group) obtained by removing two amino groups from the above aliphatic diamino compound having 2 or more carbon atoms.

The compound (B) is a bismaleimide compound obtained by a condensation ring-closing reaction of a bis-3,5-dialkyl-4-aminophenylmethane compound and maleic acid, wherein the four alkyl groups in the compound are each independently A bismaleimide compound having a methyl group, an ethyl group, an isopropyl group or a tertiary butyl group is used.
Specific examples of compound (B) include 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 3,3′,5,5′-tetramethyl-4,4′- diphenylmethanebismaleimide, 3,3',5,5'-tetraisopropyl-4,4'-diphenylmethanebismaleimide and the like.
The alkyl group of the compound (B) described above corresponds to R ₁ to R ₄ in formula (1) described later. The alkyl group of compound (B) is preferably a methyl group or an ethyl group.

In the compound (B), a bismaleimide compound having a hydrogen atom at the ortho position of the carbon atom on the benzene ring to which the maleimide group is bonded has high reactivity with the secondary amino group. is likely to gel due to the reaction between the ortho-positioned hydrogen atoms and the amino groups of compound (A) during the copolymerization reaction of (A). can prevent gelation during the copolymerization reaction.

The amount of the compound (A) and the compound (B) used when synthesizing the copolymer (C) is usually a molar amount in which the compound (A) is less than the compound (B), preferably the compound (B ) is 0.4 to 0.98 mol, more preferably 0.5 to 0.96 mol, per 1 mol of compound (A).
The reaction temperature during synthesis is usually 50 to 150° C., preferably 60 to 140° C., the reaction time is usually 0.5 to 30 hours, preferably 1 to 20 hours, and a reaction catalyst may be used. . The end point of the reaction may be the time when the molecular weight stops increasing from a certain value by GPC (gel permeation chromatography). The solvent used in the reaction may be distilled off under heating and reduced pressure, or may be used as it is in the solvent-containing resin composition.

It is preferable to use a solvent for the copolymerization reaction of the compound (A) and the compound (B), and usable solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and propylene glycol monomethyl ether. Acetate etc. are mentioned. The amount of the solvent used is preferably 10 to 300% by mass, more preferably 20 to 200% by mass, based on the solid content of the raw materials used in the copolymerization reaction.

The number average molecular weight of the copolymer (C) is generally 1,000 to 100,000, preferably 1,500 to 80,000. In order to obtain a copolymer (C) having a number average molecular weight within the above range, the raw material components should be charged in the above ratio. By measuring this number average molecular weight, the value of n in formula (1) can be calculated. n is the average number of repeating units and ranges from 1 to 100. Within this range, the effect of the polymer compound of the present invention can be exhibited.
In addition, the molecular weight in this specification means the value calculated by polystyrene conversion based on the measurement result of GPC.

Next, the polymer compound of the present invention will be explained.
In the polymer compound of the present invention, 5% or more and less than 100% of the secondary amino groups present in the copolymer (C) are isocyanate groups in the compound (D) represented by the following formula (3). After the reaction, the secondary amino group remaining in the reactant obtained above is acetylated by reacting it with acetic anhydride.
_R5 in formula (3) has the same meaning as _R5 in formula (2). That is, R ₅ in formula (2) is derived from the hydrogen atom or methyl group of compound (D).

Specific examples of the compound (D) include 2-isocyanatoethyl methacrylate (product name Karenz MOI manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (product name Karenz AOI manufactured by Showa Denko K.K.), and the like. .

The amount of the copolymer (C) and the compound (D) to be used when synthesizing the polymer compound of the present invention is such that the amount of the compound (D) per 1 molar equivalent of the secondary amino group in the copolymer (C) is It is preferably 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) obtained above and the compound (D), the remaining secondary amino groups can be acetylated. A copolymerization reaction of the compound (A) and the compound (B) is carried out in a solvent, the compound (D) is added to the obtained copolymer (C) solution and reacted, and acetic anhydride is further added to the obtained reaction solution. In addition, acetylation is a preferred embodiment of the method for synthesizing the polymer compound of the present invention.
The amount of acetic anhydride used when synthesizing the polymer compound of the present invention is equal to or greater than the number of moles of the secondary amine remaining in the reaction product of the copolymer (C) and the compound (D). I wish I had. The reaction temperature is preferably 10 to 90°C, and the reaction time is preferably 30 minutes to 5 hours. Acetic acid produced after the reaction and excess acetic anhydride can be removed by washing with water.

The resin composition of the invention contains the polymer compound of the invention and a radical initiator.
Preferred thermal radical initiators include, for example, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butyl peroxide). oxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di (t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis and peroxides such as (t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide and trimethylsilyltriphenylsilylperoxide.

Examples of preferred photoradical initiators include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides and xanthones;

The content of the radical initiator in the resin composition of the present invention is usually 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of resin components such as a polymer compound and a radical reactive monomer which is an optional component described later. , preferably 0.1 to 8 parts by mass.

The resin composition of the present invention may further contain a radical reactive monomer. 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. The radical-reactive monomer in the present invention is a compound having one or more radical-reactive functional groups in one molecule and having a number-average molecular weight of 500 or less (the lower limit of the number-average molecular weight is approximately 100). means
Specific examples of radical reactive monomers 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, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene oxide adduct methacrylate of bisphenol A, trimethylolpropane trimethacrylate, tricyclodecanedimethanol Dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated penta Erythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide , N-phenyl-chloromaleimide, Np-chlorophenyl-maleimide, Np-methoxyphenyl-maleimide, Np-methylphenyl-maleimide, Np-nitrophenyl-maleimide, Np-phenoxyphenyl- Maleimide, Np-phenylaminophenyl-maleimide, Np-phenoxycarbonylphenyl-maleimide, 1-maleimido-4-acetoxysuccinimide-benzene, 4-maleimido-4′-acetoxysuccinimide-diphenylmethane, 4-maleimide-4 '-acetoxysuccinimide-diphenyl ether, 4-maleimido-4'-acetamido-diphenyl ether, 2-maleimido-6-acetamido-pyridine, 4-maleimido-4'-acetamido-diphenylmethane and Np-phenylcarbonylphenyl-maleimide N- ethylmaleimide, N-2.6-xylylmaleimide, N-cyclohexylmaleimide, N-2,3-xylylmaleimide, xylylmaleimide, 2,6-xylenemaleimide and 4,4′-bismaleimidediphenylmethane; However, those having a maleimide group as a functional group are preferred.
These radical reactive monomers may be used alone or in combination of two or more.

The resin composition of the present invention may further contain a radical reactive polymer. By further containing the radical reactive polymer, the adhesiveness of the resin composition of the present invention and the heat resistance of the cured product can be improved. The term "radical-reactive polymer" as used in the present invention means a compound having one or more, preferably two or more, radical-reactive functional groups in one molecule and having a number average molecular weight of 500 or more.
Specific examples of radical-reactive polymers include copolymers of styrene and butadiene, modified polyphenylene ether resins, imide-extended bismaleimides, and polymeric compounds represented by the following formula (4). Incidentally, m in the formula (4) represents the average value of the number of repeating units and represents a real number in the range of 1 to 20.

The copolymer of styrene and butadiene, which is a radical reactive polymer, may be a random copolymer (commonly known as SBR) or a block copolymer. A block copolymer in which the butadiene-derived double bond is hydrogenated to a saturated hydrocarbon (commonly known as SEBS resin) may also be used. The ratio of styrene to butadiene in the polymer is typically 10:90 to 90:10 and its number average molecular weight is typically 1,000 to 100,000. Specific product examples of SBR include Clay Valley's Ricon 100, Ricon 181, and Ricon 184, and specific product examples of SEBS resin include Asahi Kasei Corporation's Tuftec series and Kraton's G Polymer series.

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

An imide-extended bismaleimide resin, which is a radical-reactive polymer, can be obtained by a known method described in Patent Publication No. 5,328,006. Specifically, an aliphatic diamine and an aromatic or aliphatic tetracarboxylic dianhydride were subjected to a dehydration condensation reaction in an organic solvent at a molar ratio in which the aliphatic diamine was excessive using an acid catalyst. After that, the amino group present at the end of the polymer is dehydrated and condensed with maleic anhydride, and the catalyst is removed 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; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; 1,7-diaminoheptane; 1,8-diaminomenthane; 3′-diamino-N-methyldipropylamine; diaminomaleonitrile; 1,3-diaminopentane;

Specific examples of aromatic or aliphatic tetracarboxylic dianhydrides include pyromellitic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetra Carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride , diethylenetriaminepentaacetic dianhydride, ethylenediaminetetraacetic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride , 4,4′-oxydiphthalix anhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic 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(trimellit acid anhydride), hydroquinone diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride anhydride, 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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3- methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4 ,5-tetrahydrofurantetracarboxylic acid dianhydride, 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, and particularly pyromellitic anhydride and 1,2,4,5-cyclohexanetetracarboxylic acid. Dianhydrides are preferred. A specific product name is BMI-3000 manufactured by Designer Molecules Inc.

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, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, lactones such as γ-butyrolactone and γ-valerolactone, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N, Amide solvents such as N-dimethylacetamide and N,N-dimethylimidazolidinone, sulfones such as tetramethylenesulfone, and the like. The content of the organic solvent in the resin composition of the present invention is usually 90% by mass or less, preferably 30 to 80% by mass.

The resin composition of the present invention may further contain a polymerization inhibitor in order to improve storage stability. The polymerization inhibitor that can be used in combination is not particularly limited as long as it is generally known, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil and trimethylquinone, aromatic diols, and di-t-butyl. Hydroxytoluene and the like can be mentioned.

The resin composition of the present invention can be used by blending fillers and additives in an amount within a range that does not impair the original performance for the purpose of imparting desired performance according to its use. The filler may be fibrous or powdery, and includes silica, carbon black, alumina, talc, mica, glass beads, glass hollow spheres, and the like.

The resin composition of the present invention can further contain flame retardant compounds, additives, and the like. These are not particularly limited as long as they are commonly used. For example, flame-retardant compounds include bromine compounds such as 4,4-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicon compounds. is mentioned. Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, and brighteners. etc., it is also possible to use them in combination as desired.

The resin composition of the present invention can be used by coating or impregnating various substrates. 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 it on a PET film, as a coverlay by coating it on a polyimide film, or by coating and drying it on a copper foil. It can be used as an attached copper foil. Further, by impregnating glass cloth, glass paper, carbon fiber, various non-woven fabrics, etc., it can be used as a printed wiring board or CFRP prepreg. Furthermore, it can be used as various resists by using a photoradical initiator.

The interlayer insulating layer, coverlay, resin-coated copper foil, prepreg, and the like of the present invention can be cured by heating and pressurizing with a hot press or the like.

The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

Example 1 (Synthesis of polymer compound of the present invention)
3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (product name: BMI-70 Kay・Ai Kasei Co., Ltd.) 22.10 parts (0.05 mol), dimer diamine (product name Priamine 1074 Croda) 20.18 parts (0.0375 mol), and toluene 20 parts were added, and a nitrogen atmosphere was added. By reacting at 100° C. for 8 hours, copolymer 1 represented by the following formula (7) (a copolymer corresponding to the copolymer (C), which is an intermediate raw material of the polymer compound of the present invention, is obtained. , Y in formula (7) represents a residue obtained by removing two amino groups from dimer diamine.) was obtained as a toluene solution. This copolymer 1 had a number average molecular weight of 2,700 and a weight average molecular weight of 15,100. The value of n in formula (7) is calculated to be 2.5 from the number average molecular weight. To the toluene solution of this copolymer, 1.16 parts (0.0075 mol) of Karenz MOI (manufactured by Showa Denko KK) was added and allowed to react at 60°C for 1 hour. mol) was added and further reacted at 60° C. for 1 hour. After adding 100 parts of toluene to dilute the reaction solution, 50 parts of pure water was added and washed with water while stirring to remove by-produced acetic acid. After repeating washing with water until the aqueous layer became neutral, the toluene solution was concentrated to obtain a 25% by mass toluene solution of the polymer compound of the present invention. In the resulting polymer compound, 10% of X in Formula (1) is presumed to be the Karenz MOI-derived moiety and the remainder to be acetyl groups.

Comparative Example 1 (Synthesis of polymer compound for comparison)
For comparison, in the same manner as in 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 added was changed to 7.65 parts (0.075 mol). A 25% by mass toluene solution of the polymer compound was obtained. It is presumed that all of the X's in formula (1) are acetyl groups in the obtained polymer compound.

Example 2, Comparative Example 2 (Preparation of resin composition)
To 10 parts of the polymer compound solution obtained in Example 1 and Comparative Example 1, 0.05 part of dicumyl peroxide as a radical initiator was added and uniformly mixed to obtain the resin composition of the present invention and the comparative resin composition. A resin composition was obtained, respectively.

(Evaluation of dielectric properties, glass transition temperature and linear expansion coefficient (α1) of cured product of resin composition)
Using an applicator, each of the resin compositions obtained in Example 2 and Comparative Example 2 was applied to a mirror surface of a copper foil having a thickness of 18 μm to a thickness of 280 μm, and heated at 90° C. for 10 minutes to dry the solvent. to obtain a film-like adhesive. The film-like adhesive on the copper foil obtained above was cured by heating at 180° C. for 1 hour using a vacuum oven, and then the copper foil was removed by immersion in an etchant. A cured product with a thickness of 70 μm that can be handled as a film was obtained from both the film-like adhesive of the present invention and the film-like adhesive for comparison, so the dielectric properties of the cured products obtained above were evaluated. Dielectric properties were obtained by measuring dielectric constant and dielectric loss tangent at 10 GHz by cavity resonance method using network analyzer 8719ET (manufactured by Agilent Technologies). Also, the glass transition temperature and linear expansion coefficient (α1) of the cured film adhesive were obtained using a TMA (thermo-mechanical measurement apparatus).
Table 1 shows the results.

(Evaluation of adhesive strength and heat resistance of cured product of resin composition)
Using an applicator, the resin compositions obtained in Example 2 and Comparative Example 2 are applied to the matte surface of a 12 μm thick high-frequency low-roughness copper foil (CF-T4X-SV: manufactured by Fukuda Metal Foil & Powder Co., Ltd.). A copper foil having a film-like adhesive made of the resin composition of the present invention was obtained by coating each layer with a thickness of 50 μm and drying the solvent by heating at 90° C. for 10 minutes. On the adhesive side of the copper foil obtained above, the matte side of another copper foil (the copper foil used was the same type of copper foil) was superposed and heat-cured in a vacuum press at a pressure of 3 MPa for 1 hour. After that, the 90° peeling strength (adhesive strength) between the copper foils was measured using Autograph AGX-50 (manufactured by Shimadzu Corporation). A 3 cm square piece of the laminated copper foil was cut out and floated in a solder bath at 288° C., and the time until an abnormality such as swelling or peeling occurred on the copper foil was measured. Table 1 shows the results.

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 parts of dicumyl peroxide as a radical initiator and 0.5 parts of butadiene-styrene copolymer LYCON 100 (manufactured by Clay Valley) were added. was added and uniformly mixed 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 radical initiator and 0.5 part of modified polyphenylene ether resin SA-9000 (manufactured by Subic LLC) were added. The resin composition of the present invention was obtained by mixing them uniformly.

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 radical initiator and imide-extended bismaleimide resin BMI-3000 (manufactured by Designer Molecules Inc.) ) was added and uniformly mixed to obtain the resin composition of the present invention.

(Evaluation of cured product of resin composition)
In the same manner as the above "Evaluation of dielectric properties, glass transition temperature and coefficient of linear expansion (α1) of the cured product of the resin composition" and "Evaluation of adhesive strength and heat resistance of the cured product of the resin composition", Examples Various properties of the resin compositions obtained in 3 to 5 were evaluated. Table 2 shows the results.

As described above, the polymer compound of the present invention can be made into a flexible film by curing together with a radical initiator, and the cured product has excellent dielectric properties, adhesiveness and heat resistance. showed that.

Claims

Formula (1) below

(In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a methyl group, ethyl group, isopropyl group or tertiary butyl group. X each independently represents an acetyl group or the following formula (2)

(In formula (2), R5 represents a hydrogen atom or a methyl group.)
At least one of the multiple X's is an acetyl group, and 5% or more of the multiple X's are structures represented by formula (2). Y represents a residue obtained by removing two amino groups from a diamino compound. n is the average number of repeating units and ranges from 1 to 100; ) is a polymer compound represented by
A resin composition comprising the polymer compound according to claim 1 and a radical initiator.
3. The resin composition according to claim 2, further comprising a radically reactive monomer having a radically reactive functional group.
3. The resin composition according to claim 2, further comprising a radical-reactive polymer having two or more radical-reactive functional groups in one molecule.
A film adhesive comprising the resin composition according to any one of claims 2 to 4.
A cured product of the resin composition according to any one of claims 2 to 4.
A cured product of the film adhesive according to claim 5 .