JP2023069669A - Resin composition including curable compound - Google Patents

Abstract

To provide a resin composition that has sufficient flexibility to be made into a film, has a low dielectric constant and dielectric loss tangent, and can form a cured product with a high glass transition temperature.SOLUTION: A resin composition contains a copolymer of styrene and (meth)acryloyloxyphenyl (meth)acrylate, a compound represented by the formula (2) in the figure, and a radical initiator. (In the formula, p is an average of the numbers of repeating units, each of which independently ranges from 1 to 20.)SELECTED DRAWING: None

Description

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. , relates to compositions of compounds with excellent heat resistance.

A phenoxy resin is a polymer compound having 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 polytetrafluoroethane (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. In Patent Document 3, a random copolymer of a monomer having 70% by weight or less of one ethylenically unsaturated group and a (meth)acrylate having 30% by weight or more of one or more aliphatic hydroxyl groups A curable polymer compound obtained by esterifying a monomer having one or more ethylenically unsaturated groups and one carboxyl group to an aliphatic hydroxyl group of is described. As a result of a follow-up test, the cured product of the curable polymer compound obtained by the structural formula of the document had a low dielectric loss tangent at 10 GHz of around 0.005. is not fully satisfied.

JP 2005-001274 A JP 2014-060449 A JP-A-10-017812

The present invention has been made in view of the above points, and a resin composition that has sufficient flexibility to be formed into a film, has a low dielectric constant and dielectric loss tangent, and provides a cured product with a high glass transition temperature. It is intended to provide goods.

As a result of intensive studies, the present inventors have found that a hydroxyl group possessed by a copolymer obtained by copolymerizing a compound in which one hydroxyl group of a dihydroxybenzene compound is (meth)acrylated with styrene, and (meth)acrylic acid chloride The inventors have found that a resin composition containing a polyfunctional compound having a styrene structure and a compound that is a dehydrochlorination condensate with a chloride group possessed by can solve the above problems, and completed the present invention.
That is, the present invention
(1) Formula (1) below

(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group; m and n are the average number of repeating units and are each independently in the range of 1 to 2,000.) The compound and the following formula (2)

(Wherein, p is the average number of repeating units and is independently in the range of 1 to 20.) A resin composition containing a compound represented by and a radical initiator,
(2) A film adhesive made of the resin composition described in (1) above, and (3) A cured product of the resin composition described in (1) or a cured film adhesive described in (2) above. ,
Regarding.

The resin composition of the present invention can be cured by applying heat or light energy, and the cured product exhibits excellent dielectric properties and heat resistance.

Embodiments of the present invention are described below.
The resin composition of the present invention contains the compound represented by the above formula (1).
The compound represented by the formula (1), which is an essential component of the resin composition of the present invention, is a random copolymer of (meth)acrylate having a phenolic hydroxyl group and styrene (hereinafter also simply referred to as "copolymer" It can be obtained as a dehydrochlorination reaction product of an intermediate raw material of (meth)acrylic acid chloride.
First, the copolymer (intermediate raw material) will be described.

The (meth)acrylate having a phenolic hydroxyl group, which is a raw material for the copolymer, is not particularly limited as long as it is a compound having a phenolic hydroxyl group and a (meth)acryloyl group in one molecule, such as 4-hydroxyphenyl methacrylate. , 2-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate and the like, with 4-hydroxyphenyl methacrylate being preferred.
In this specification, the term "(meth)acrylate" means "acrylate and/or methacrylate".

The following formula (3) is a structural formula of a random copolymer of hydroxyphenyl (meth)acrylate and styrene, and R ₁ , m and n in formula (3) are R ₁ , m and n in formula (1). has the same meaning as n. As the compound represented by the formula (1) of the present invention (compound having a structure represented by the formula (1)), a copolymer represented by the following formula (3) is used as an intermediate material. ) are preferred.

A method for copolymerizing (meth)acrylate having a phenolic hydroxyl group with styrene is not particularly limited as long as it is a known copolymerization method, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization.
Solvents usable for solution polymerization include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, N,N-dimethylformamide and γ-butyrolactone. be done. Water and a surfactant are usually used for emulsion polymerization and suspension polymerization, and the copolymerization reaction is carried out in a state in which the raw material components are emulsified or suspended in water.

The copolymerization reaction may be radical polymerization, cationic polymerization or anionic polymerization. In the case of radical polymerization, it is preferable to use a radical polymerization initiator. Specific examples of radical polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvalero nitrile), 1,1′-azobis(cyclohexane-1-carbonitrile, 2,2′-azobis[2-(2-imidazolin-2-yl)propane]
dihydrochloride, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide and the like.
The amount of the radical polymerization initiator to be blended is usually 0.001 to 5 parts by mass per 100 parts by mass of the raw material component of the copolymer. The polymerization temperature is usually 50 to 250°C, preferably 60 to 200°C, and the polymerization time is usually 0.5 to 30 hours, preferably 1 to 20 hours. The radical polymerization reaction is preferably carried out in a nitrogen gas atmosphere in order to prevent polymerization inhibition by oxygen in the air.

Specific examples of cationic _{polymerization} initiators include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as _CF3COOH and _CCl3COOH , and super strong acids such as _CF3SO3H and _HClO4 . Specific examples of anionic polymerization initiators include butyllithium, Na-naphthalene complexes, alkali metals, alkyllithium compounds, sodium amides, Grignard reagents and lithium alkoxides. However, ionic initiators used in cationic polymerization and anionic polymerization may remain in the copolymer even after the polymerization reaction and adversely affect the dielectric properties and insulation properties. Synthesis of a copolymer that is an intermediate raw material for the compound to be obtained is preferably carried out by radical polymerization.
The amount of the cationic polymerization initiator or the anionic polymerization initiator to be blended is usually 0.01 to 5 parts by mass with respect to 100 parts by mass of raw material components of the copolymer. The polymerization temperature is usually 40 to 150°C, preferably 50 to 120°C, and the polymerization time is usually 0.5 to 20 hours, preferably 1 to 15 hours.

The number average molecular weight of the copolymer is usually 3,000 to 300,000, preferably 5,000 to 200,000.
In order to obtain a copolymer having a number average molecular weight within the above range, it is preferable to adjust the amount of the initiator used in synthesizing the copolymer to an appropriate amount. The amount of the initiator required to obtain a copolymer having a number average molecular weight within the above range depends on the type of (meth)acrylate having a phenolic hydroxyl group and the (meth)acrylate and styrene having a hydroxyl group used in the copolymerization reaction. Although it cannot be generalized because it depends on the amount of the initiator, it is generally known that a copolymer with a large molecular weight can be obtained by reducing the amount of the initiator. It suffices to select the blending amount of the initiator that allows the polymer to be obtained.

The ratio of the (meth)acrylate having a phenolic hydroxyl group and the styrene used when synthesizing the copolymer is not particularly limited, but the amount (mass) of styrene used is usually 4 to 99 of the mass of the (meth)acrylate having a hydroxyl group. 0.5 times, preferably 4.5 to 99.7 times. Formula ( A compound represented by 1) is obtained.

The compound represented by the formula (1) is a phenolic hydroxyl group possessed by the copolymer (this hydroxyl group is a hydroxyl group possessed by the raw material (meth)acrylate having a phenolic hydroxyl group) and ( It is obtained by a dehydrochlorination reaction with the chloride group of meth)acrylic acid chloride.

The ratio of the copolymer and (meth)acrylic acid chloride used when synthesizing the compound represented by formula (1) is not particularly limited, but when the (meth)acrylic acid chloride is excessive relative to the hydroxyl groups possessed by the copolymer If it is insufficient, the (meth)acrylic acid chloride remaining unreacted in the compound or the hydroxyl group remaining without reacting with (meth)acrylic acid chloride may adversely affect the properties of the cured product. , it is preferable to use (meth)acrylic acid chloride in an amount equivalent to the hydroxyl groups possessed by the copolymer.

The reaction between the copolymer and (meth)acrylic acid chloride may be carried out by adding (meth)acrylic acid chloride to a solution of the copolymer in an organic solvent while stirring. The organic solvent that can be used here is not particularly limited as long as it can dissolve the copolymer and (meth)acrylic acid chloride. The copolymer solution may be used as it is. The concentration of the copolymer solution to be reacted with (meth)acrylic acid chloride is usually 10 to 90 mass %, preferably 20 to 80 mass %. The reaction temperature is generally 30 to 120°C, preferably 40 to 110°C, and the reaction time is generally 0.5 to 4 hours, preferably 1 to 3 hours.

Since the reaction between the copolymer and (meth)acrylic acid chloride is a dehydrochlorination reaction, a tertiary amine such as triethylamine or pyridine is added in advance to the reaction solution in order to trap the generated hydrochloric acid and further promote the reaction. It is preferable to add. The amount of the tertiary amine to be used is preferably equimolar to 4-fold mol, more preferably equimolar to 3-fold mol, to (meth)acrylic acid chloride. Hydrochloric acid generated during the reaction precipitates as an amine hydrochloride and can be removed by filtration after the reaction. Excess tertiary amine can be distilled out of the system under heating and reduced pressure after filtration.

In order to prevent polymerization reaction between (meth)acryloyl groups in the polymer compound represented by formula (1) and improve storage stability, a polymerization inhibitor is added to the compound solution after completion of the synthesis reaction. A small amount is preferred. Specific examples of polymerization inhibitors include hydroquinone, para-methoxyphenol, methylhydroquinone, di-t-butylhydroxytoluene, t-butylhydroquinone, 2-t-butyl-1,4-benzoquinone, 1,4-benzoquinone, 1 ,1-diphenyl-2-picrylhydrazyl free radical, 6-t-butyl-2,4-xylenol, 4-t-butylpyrocatechol, 2,6-di-t-butylphenol, 2,6-di- and t-butyl-p-cresol and phenothiazine.

The number average molecular weight range of the compound represented by formula (1) thus obtained is preferably 11,000 to 300,000, more preferably 15,000 to 200,000. If the molecular weight is smaller than the above range, the adhesiveness to the low-roughness copper foil will be low, and if it is larger, the viscosity will increase, making coating difficult.
In addition, the molecular weight in this specification means the value calculated by polystyrene conversion based on the measurement result of GPC.

The content of the compound represented by formula (1) in the resin composition of the present invention is 30 with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) (described later). 90 mass % is preferable, and 40 to 90 mass % is more preferable.

The resin composition of the present invention contains the compound represented by the above formula (2).
The compound represented by the formula (2), which is an essential component of the resin composition of the present invention, is a compound represented by the following formula (4) (in formula (4), Z represents a halogen atom). It can be obtained by a hydrogen halide reaction. Z is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom from the viewpoint of the stability of the compound represented by formula (4) and the ease with which the dehydrohalogenation reaction proceeds.

The dehydrohalogenation reaction of the compound represented by formula (4) is carried out in a solvent in the presence of a catalyst.

Solvents used in the dehydrohalogenation reaction include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, and esters such as ethyl acetate and butyl acetate. non-water-soluble solvents such as solvent-based solvents and ketone-based solvents such as methyl isobutyl ketone and cyclopentanone, but not limited thereto, and two or more of them may be used in combination.
In addition to the water-insoluble solvent described above, an aprotic polar solvent may be used in combination. Specific examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, and 1,3-dimethyl-2-imidazo. Examples include lysinone and N-methylpyrrolidone, and two or more of these may be used in combination. When an aprotic polar solvent is used together, it is preferable to use one having a boiling point higher than that of the water-insoluble solvent.

Although the catalyst used for the dehydrohalogenation reaction is not particularly limited, basic catalysts such as sodium hydroxide, potassium hydroxide and potassium carbonate are preferred. In order to promote the progress of the dehydrohalogenation reaction, an aprotic polar solvent is used in large excess relative to the compound represented by the formula (4), or the dehydrohalogenation reaction is performed two or more times. It may be repeated multiple times. As a method for repeatedly performing the dehydrohalogenation reaction, for example, the solution obtained by performing the dehydrohalogenation reaction of the compound represented by the above formula (4) in the presence of a base catalyst in an organic solvent is washed with water, A method of returning the mixture to the reaction vessel, adding a base catalyst, and reacting the mixture again can be used. By increasing the degree of progress of the dehydrohalogenation reaction, it is possible to reduce the amount of halogen remaining in the reaction product (compound represented by formula (2)). The amount of halogen remaining in the reaction product is preferably 1 to 10,000 ppm, more preferably 1 to 1,000 ppm, even more preferably 1 to 500 ppm.

Although the method for producing the compound represented by the formula (4) is not particularly limited, for example, a compound having a 2-bromoethylbenzene structure and a bishalogenated methylaryl compound are treated under an acid catalyst such as hydrochloric acid, sulfonic acid and activated clay. Alternatively, a compound having a 2-bromoethylbenzene structure and a bishydroxymethylaryl compound may be reacted under an acid catalyst such as hydrochloric acid, sulfonic acid and activated clay. When a sulfonic acid or the like is used as a catalyst, the extraction step may be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide.
In the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or an aromatic hydrocarbon solvent may be used in combination with a non-aromatic hydrocarbon solvent such as cyclohexane or toluene. After the extraction, the organic layer is washed with water until the waste water becomes neutral, and the solvent and excess compounds having a 2-bromoethylbenzene structure are distilled off using an evaporator or the like, so that at least two or more 2- A compound represented by formula (4) having a bromoethylethylbenzene structure can be obtained.

Compounds having a 2-bromoethylbenzene structure include 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)- 4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene and Examples include, but are not limited to, 1-(2-bromoethyl)-2,6-dimethylbenzene.
If the number of carbon atoms in the compound having a 2-bromoethylbenzene structure is large, the solvent solubility is improved, but the heat resistance is lowered. more preferably unsubstituted or substituted with an alkyl group having 1 or 2 carbon atoms, and even more preferably unsubstituted or substituted with a methyl group.

Bishalogenated methylaryl compounds include о-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, о-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, о- xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide and the like, and chloride compounds or bromide compounds are preferred. .

Bishydroxymethylaryl compounds include, but are not limited to, o-benzenedimethanol, m-benzenedimethanol and p-benzenedimethanol. These may be used alone or in combination of two or more.
The amount of the bishydroxymethylaryl compound used is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, relative to the compound having a 2-bromoethylbenzene structure.

When reacting a compound having a 2-bromoethylbenzene structure with a methylaryl halide compound, if necessary, catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid and methanesulfonic acid, as well as aluminum chloride and zinc chloride Lewis acid, activated clay, acid clay, white carbon, solid acid such as zeolite and silica alumina, acidic ion exchange resin, and the like can be used. These may be used alone or in combination of two or more. The amount of catalyst used is generally 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, per 1 mol of the compound having a 2-bromoethylbenzene structure. If the amount of the catalyst used is too large, the viscosity of the reaction solution may become too high and stirring may become difficult.

The reaction between a compound having a 2-bromoethylbenzene structure and a methylaryl halide compound may be carried out in an organic solvent such as hexane, cyclohexane, octane, toluene, xylene, or the like, or may be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of a compound having a 2-bromoethylbenzene structure, a methylaryl halide compound, and a solvent, water is removed from the system by azeotropy when the catalyst contains water. After that, the reaction is usually carried out at 40 to 180°C, preferably 50 to 170°C for 0.5 to 20 hours. After completion of the reaction, the acidic catalyst may be neutralized with an alkaline aqueous solution, but the washing step may proceed without neutralization. As for the water washing step, a water-insoluble organic solvent may be added to the oil layer, and water washing may be repeated until the wastewater becomes neutral.

The content of the compound represented by formula (2) in the resin composition of the present invention is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on the solid content of the resin composition.
The number average molecular weight of the compound represented by formula (2) is preferably 200 or more and less than 5,000, more preferably 300 or more and less than 3,000.

The resin composition of the present invention contains 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.

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 the compound represented by the formula (1), the compound represented by the formula (2), and the resin components such as radical reactive monomers, which are optional components described later. It is usually 0.1 to 10 parts by mass, preferably 0.1 to 8 parts by mass, per 100 parts by mass in total.

In addition to the compound represented by Formula (1), the compound represented by Formula (2), and the radical initiator, the resin composition of the present invention may contain a monomer or polymer having radical reactivity. By using a radical reactive monomer or polymer together, 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 preferably has a number average molecular weight of less than 500 and has one or more functional groups. Specific examples thereof include acenaphthylene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Methacrylate, 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 pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, triallyl cyanurate Nurate, 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-acetoxy succinimide-benzene, 4-maleimido-4'-acetoxysuccinimide-diphenylmethane, 4-maleimido-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, silylmaleimide, 2,6-xylenemaleimide, 4,4'-bismaleimidediphenylmethane, and the like.

The radical-reactive polymer preferably has a number-average molecular weight of 500 or more and two or more functional groups. Specific examples thereof include a copolymer of styrene and butadiene, or a modified polymer having an unsaturated double bond at the terminal. Polyphenylene ethers are mentioned.
The copolymer of styrene and butadiene may be a random copolymer or a block copolymer. 1,000 to 10,000. Specific product examples of copolymers of styrene and butadiene include Ricon 100, Ricon 181 and Ricon 184 manufactured by Clay Valley.

The modified polyphenylene ether compound having a group containing an unsaturated double bond at its terminal has a methacryloyl group, an acryloyl group, or a vinyl group at both ends of the molecule and has a number average molecular weight of 1,000 to 10,000. is preferred.
Specific examples of modified polyphenylene ether compounds having groups containing unsaturated double bonds at their ends include polyphenylene ether having methacryloyl groups at both ends and a number average molecular weight of about 1700 (product name: SA9000, manufactured by SABIC Japan LLC. ), or a polyphenylene ether having a vinyl group at both ends and a number average molecular weight of about 1200 or 2200 (product name: OPE-2St 1200 or OPE-2St 2200, manufactured by Mitsubishi Gas Chemical Co., Ltd.).
These radical reactive polymers may be used alone or in combination of two or more. Moreover, you may use together with a radical reactive monomer.

An organic solvent may be used in combination with the resin composition of the present invention. Specific examples of organic solvents include aromatic solvents such as toluene and xylene; solvents, 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), Amide solvents such as N,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.

A polymerization inhibitor may be used in combination with the resin composition of the present invention 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 also be used in combination with 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. are 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 resin composition of the present invention can also be used as a film adhesive.
The film-like adhesive of the present invention is prepared by applying the resin composition of the present invention containing a solvent to a substrate such as a PET film, removing the solvent under heating conditions that do not cure the resin composition, and then peeling off the substrate. obtained by

The resin composition and film-like adhesive of the present invention can be made into a cured product by heating and pressure molding with a hot press machine or the like, or by irradiating with light.

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

Synthesis Example 1 (Synthesis of a compound represented by the following formula (6) in which R ₁ and R ₂ in formula (1) are methyl groups)
(Step 1-1) Synthesis of a copolymer represented by the following formula (5) (copolymer 1) In a flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube and a stirrer, 98.2 parts of styrene. , 1.8 parts of 4-hydroxyphenyl methacrylate, 0.05 parts of azobisisobutyronitrile and 40 parts of toluene are added and reacted at 125 ° C. for 7 hours in a nitrogen atmosphere, represented by the following formula (5) A toluene solution of copolymer 1 was obtained. A procedure of adding 50 parts of anisole to this toluene solution and distilling off part of the toluene, unreacted styrene and anisole under heating and reduced pressure was repeated four times to obtain 120 parts of an anisole solution of copolymer 1. Analysis of the anisole solution obtained above by gas chromatography showed the absence of toluene and styrene. A portion of this anisole solution was heated under reduced pressure, and the obtained amount of copolymer 1 calculated from the mass of the dry solid content was 70.2 parts, considering that the unreacted styrene was 28 parts. Copolymer 1 was a copolymer of 68.4 parts of styrene and 1.8 parts of 4-hydroxyphenyl monomethacrylate. The dry solid content obtained above had a number average molecular weight of 92,000 and a weight average molecular weight of 245,000. The value of n in formula (5) calculated from the copolymerization ratio of styrene and 4-hydroxyphenyl monomethacrylate and the number average molecular weight was 863 and the value of m was 13.

(Step 1-2) Synthesis of compound (compound 1) represented by the following formula (6) After diluting by adding 500 parts of toluene to the anisole solution of copolymer 1 obtained in step 1-1, triethylamine 1 .32 parts and 1.052 parts of methacrylic acid chloride were added and reacted at 80° C. for 1 hour while stirring. After the reaction, after removing the triethylamine hydrochloride produced by pressure filtration, triethylamine and excess toluene are distilled off with a rotary evaporator, and toluene is added to adjust the solid content concentration. 285 parts of a 25% by mass solution of the represented compound (compound 1) was obtained. Compound 1 had a number average molecular weight of 93,000 and a weight average molecular weight of 247,000.

Synthesis Example 2 (synthesis of compound represented by formula (2))
(Step 2-1) Synthesis of a precursor compound represented by the following formula (7), wherein Z in formula (4) is a bromine atom: 2-bromoethylbenzene ( Tokyo Kasei Co., Ltd.) 296 parts, α,α'-dichloro-p-xylene (Tokyo Kasei Co., Ltd.) 70 parts and methanesulfonic acid (Tokyo Kasei Co., Ltd.) 18.4 parts were charged and reacted at 130 ° C. for 8 hours. rice field. After allowing to cool, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with 1,200 parts of toluene, and the organic layer was washed with 100 parts of water five times. By distilling off the solvent and excess 2-bromoethylbenzene under heating and reduced pressure, 160 parts of an olefin compound precursor (BEB-1) having a 2-bromoethylbenzene structure represented by the following formula (7) was obtained as a liquid resin. rice field. The obtained compound represented by formula (7) had a number average molecular weight of 540 and a weight average molecular weight of 650, and the value of p in formula (7) calculated from the value of the number average molecular weight was 0.81. .

(Step 2-2) Synthesis of a compound (compound 2) represented by the following formula (8): 22 parts of BEB-1 obtained in step 2-1 was added to a flask equipped with a thermometer, condenser, and stirrer, 50 parts of toluene, 150 parts of dimethylsulfoxide, 15 parts of water and 5.4 parts of sodium hydroxide were added, and the mixture was reacted at 40° C. for 5 hours while stirring. After standing to cool, 100 parts of toluene is added, the organic layer is washed with 100 parts of water five times, and the solvent is distilled off under heating and reduced pressure to obtain a liquid having a styrene structure represented by the following formula (8) as a functional group. 13 parts of an olefin compound (compound 2) were obtained. The compound 2 thus obtained had a number average molecular weight of 430 and a weight average molecular weight of 580.

Example 1 (Preparation of the resin composition of the present invention)
To 10 parts of the 25% solution of compound 1 obtained in Synthesis Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 0.3 parts of compound 2 obtained in Synthesis Example 2 are added and mixed uniformly. Thus, a resin composition 1 of the present invention was obtained.

Example 2 (Preparation of the resin composition of the present invention)
To 10 parts of the 25% solution of compound 1 obtained in Example 1, 0.05 parts of dicumyl peroxide as a radical initiator and 0.6 parts of compound 2 obtained in Synthesis Example 2 are added and mixed uniformly. Thus, a resin composition 2 of the present invention was obtained.

Comparative Example 1 (Preparation of resin composition for comparison)
To 10 parts of the 25% solution of Compound 1 obtained in Synthesis Example 1, 0.05 part of dicumyl peroxide as a radical initiator was added and uniformly mixed to obtain Resin Composition 3 for comparison.

(Evaluation of Dielectric Properties, Glass Transition Temperature and Linear Expansion Coefficient of Cured Resin Composition)
Each of the resin compositions 1 to 3 obtained in Examples 1 and 2 and Comparative Example 1 was applied to a polyimide film having a thickness of 18 μm using an applicator to a thickness of 280 μm, and was heated to 150° C. using a vacuum oven. After heat curing for a period of time, the cured product was peeled off from the polyimide film. A cured product with a thickness of 70 μm that can be handled as a film was obtained from each composition, and the dielectric properties were evaluated. The dielectric properties were evaluated by measuring the dielectric constant and dielectric loss tangent at 10 GHz by the cavity resonance method using a network analyzer 8719ET (manufactured by Agilent Technologies). Also, the glass transition temperature and α1 (linear expansion coefficient in the glassy region) were measured using a TMA (thermo-mechanical property apparatus). Table 1 shows the results.

As described above, the cured product of the resin composition of the present invention formed a flexible film and exhibited excellent dielectric properties and heat resistance.

Claims (3)

Formula (1) below

(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group; m and n are the average number of repeating units and are each independently in the range of 1 to 2,000.) The compound and the following formula (2)

(In the formula, p is the average number of repeating units and each independently ranges from 1 to 20.) A resin composition comprising a radical initiator and a compound represented by: A film adhesive comprising the resin composition according to claim 1 . The cured product of the resin composition according to claim 1 or the film adhesive according to claim 2.