Curable polymer compound and resin composition containing the compound

Abstract

To provide a curable polymer compound that can be thermally or photochemically cured via a radical initiator, exhibits alkali solubility, has low dielectric constant and dielectric loss tangent in a cured product thereof, and demonstrates high adhesion and high glass transition temperature.SOLUTION: Provided is a polymer compound represented by formula (1). (X represents a residue derived from an aromatic or aliphatic tetracarboxylic dianhydride, Y represents a residue derived from an aliphatic diol compound, and Z represents a carboxyl group or a structure represented by formula (2)).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer compound capable of undergoing a thermal or photocuring reaction when used in combination with a radical initiator. [Background technology]

[0002] Conventionally, epoxy resins, which have high adhesiveness, insulation properties, and heat resistance, have been widely used in electronic materials such as printed wiring boards. In the field of resists, a development method is generally adopted in which a specific part is cured using a photoinitiator, and then the uncured part is removed with an alkaline aqueous solution such as a TMAH (tetramethylammonium hydroxide) aqueous solution. Therefore, resist resins are required to be alkali-soluble, and resins are widely used in which acrylic acid is added to the epoxy groups of multifunctional epoxy resins, and the resulting alcoholic hydroxyl groups are reacted with acid anhydrides such as tetrahydrophthalic anhydride through half-esterification. These resins contain a large amount of highly polar carboxylic acid in the molecule, so that the dielectric tangent of the cured product is high and they cannot be used for high frequency applications. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 63-132915 [Patent Document 2] JP 2001-75274 A [Patent Document 3] JP 2017-122912 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent documents 1, 2 and 3 disclose polymerizable carboxyl group-containing polymer compounds obtained by reacting a diol compound, a polybasic acid anhydride having two acid anhydride groups in the molecule, and a (meth)acrylate having one hydroxyl group in the molecule as alkali-soluble curable resins. However, these polymer compounds have functional groups only at the molecular terminals, so the heat resistance of the cured product, such as the glass transition temperature, is low. Furthermore, the proportion of carboxylic acid is high, so the dielectric loss tangent is high, and the compound is not suitable for recent high-frequency applications that require a low dielectric loss tangent.

[0005] The present invention has been made in consideration of the above-mentioned points, and an object of the present invention is to provide a curable polymer compound that is soluble in an alkaline aqueous solution, and that has a low dielectric constant and dielectric tangent of a cured product, and has a high glass transition temperature and adhesive strength. [Means for solving the problem]

[0006] That is, the present invention relates to the following [1] to [5]. Note that in this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included. [1] A polymer compound represented by the following formula (1):

[0007] [ka]

[0008] (In formula (1), X's each independently represent a residue obtained by removing a carboxy group from an aromatic or aliphatic tetracarboxylic anhydride. Y's each independently represent a divalent residue obtained by removing a hydroxyl group from an aliphatic diol compound. A's each independently represent a divalent bonding group. Z's each independently represent a carboxy group or a structure represented by the following formula (2). R1's each independently represent a methyl group or a hydrogen atom. n is the average number of repeating units and is a real number of 0.1 to 20.)

[0009] [ka]

[0010] (In formula (2), * represents the bonding position with X in formula (1). R2 is a methyl group or a hydrogen atom.) [2] A resin composition comprising the polymer compound according to the above item [1] and a radical initiator. [3] The resin composition according to the above item [2], which contains a radical reactive monomer having one or more functional groups in one molecule. [4] The resin composition according to the above item [2], which contains a radically reactive polymer having two or more functional groups in one molecule. [5] A cured product of the resin composition described in any one of the preceding items [2] to [4]. Effect of the Invention

[0011] The polymer compound according to the present invention and a composition containing the same are soluble in an alkaline aqueous solution and can be cured by using a radical initiator in combination with heat or light energy, and the cured product of the composition can provide a polymer compound having excellent dielectric properties, heat resistance, and adhesiveness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The polymer compound of the present invention is represented by the following formula (1).

[0013] [ka]

[0014] In formula (1), X's each independently represent a residue of an aromatic or aliphatic tetracarboxylic anhydride obtained by removing a carboxy group. Y's each independently represent a divalent residue of an aliphatic diol compound obtained by removing a hydroxyl group. A's each independently represent a divalent linking group, and are preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms. Z's each independently represent a carboxy group or a structure of formula (2) below. R1's each independently represent a methyl group or a hydrogen atom. n is the average number of repeating units, and is preferably a real number of 0.1 to 20, and more preferably a real number of 0.5 to 10.

[0015] [ka]

[0016] In formula (2), * represents the bonding position with X in formula (1). R2 is a methyl group or a hydrogen atom.

[0017] The value of n in formula (1) can be determined by GPC (gel permeation chromatography) measurement.

[0018] The method for producing the polymer compound represented by the above formula (1) is not particularly limited, but it can be obtained as follows. An addition reaction is carried out by adding less than 1 mole of an aliphatic diol to 1 mole of an aromatic or aliphatic tetracarboxylic dianhydride to obtain an intermediate 1. An addition reaction is carried out with an equimolar amount of a compound containing an alcoholic hydroxyl group and a radically polymerizable double bond to obtain an intermediate 2. A part of the carboxylic acid present in the obtained intermediate 2 is subjected to a decarboxylation reaction with a compound having a radically polymerizable double bond and an isocyanate group in one molecule to obtain a polymer compound represented by the above formula (1).

[0019] Examples of aromatic or aliphatic tetracarboxylic dianhydrides include 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,5-cyclohexanetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, pyromellitic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-biphthalic anhydride, 3,4'-biphthalic anhydride, 4,4'-(ethynyl)di ... -1,2-)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 3,4'-oxydiphthalic anhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, ethylene glycol bis(anhydrotrimellitate), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene, and the like.

[0020] Examples of the aliphatic diol compound include ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-propanediol, 4,4'-bicyclohexanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,3-adamantanediol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,7-heptanediol, 2,5-hexanediol, 1,9-nonanediol, 1,18-octadecanediol, 2,4-dimethyl-2,4-pentanediol, 2-butene-1,4-diol, 1,16-hexadecanediol, and dimer diol. These may be used alone or in combination of two or more.

[0021] Intermediate 1 of the compound of the present invention is represented by the following formula (3) and can be obtained by charging an aliphatic diol compound in an amount of less than 1 mole per mole of an aromatic or aliphatic tetracarboxylic dianhydride and carrying out a half-esterification reaction.

[0022] [ka]

[0023] In formula (3), X, Y and n have the same meanings as in formula (1).

[0024] As for the amount of raw materials used in the above reaction, the amount of the aliphatic diol compound used is preferably 0.4 to 0.95 moles per mole of the aromatic tetracarboxylic dianhydride, and more preferably 0.5 to 0.9 moles. A solvent is preferably used during the reaction, and examples of the solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and γ-butyrolactone. The amount of the solvent used is preferably 0 to 300% by mass, and more preferably 20 to 200% by mass, based on the solid content.

[0025] Regarding the ratio of aromatic tetracarboxylic dianhydride to aliphatic diol compound, the higher the ratio of aliphatic diol compound, the higher the average molecular weight of the polymer intermediate, and the lower the ratio, the lower the average molecular weight, but both terminal residues of the intermediate always become acid anhydrides. The reaction temperature is usually 20 to 150°C, preferably 30 to 140°C, and the reaction time is usually 0.5 to 30 hours, preferably 1 to 20 hours. The end point of the reaction may be determined by GPC (gel permeation chromatography) when the peak of the raw material bismaleimide disappears and the molecular weight no longer increases from a certain value.

[0026] By adding a compound containing a radically polymerizable double bond and an alcoholic hydroxyl group in one molecule to intermediate 1, an addition reaction can be carried out between the acid anhydride group and the alcoholic hydroxyl group present in intermediate 1 to obtain intermediate 2 represented by the following formula (4).

[0027] [ka]

[0028] In formula (4), X, Y, A, R1, and n have the same meanings as in formula (1).

[0029] Examples of compounds containing a radically polymerizable double bond and an alcoholic hydroxyl group in one molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monomethacrylate, and N-(2-hydroxyethyl)acrylamide.

[0030] The amount of the compound containing a radically polymerizable double bond and an alcoholic hydroxyl group in one molecule used is equimolar to the equivalent of the acid anhydride group present in the intermediate. In order to obtain the polymer compound of the present invention, a predetermined amount of a compound containing a radically polymerizable double bond and an alcoholic hydroxyl group in one molecule is added to the reaction solution from which the intermediate has been obtained to cause an addition reaction. The reaction temperature is usually 20 to 150°C, preferably 30 to 140°C, and the reaction time is usually 0.5 to 30 hours, preferably 1 to 20 hours.

[0031] The polymer compound of the present invention can be obtained by subjecting the carboxylic acid present in the intermediate 2 obtained above to a decarboxylation reaction with a molecule containing an isocyanate group and a (meth)acrylic group in one molecule.

[0032] Examples of compounds containing an isocyanate group and a (meth)acrylic group in one molecule include 2-isocyanatoethyl methacrylate (product name Karenz MOI, manufactured by Showa Denko KK), and 2-isocyanatoethyl acrylate (product name Karenz AOI, manufactured by Showa Denko KK).

[0033] The amount of the compound containing an isocyanate group and a (meth)acrylic group in one molecule used is 5 to 60% by mole, preferably 10 to 50% by mole, based on the equivalent amount of the carboxylic acid present in the system. As a method for obtaining the polymer compound of the present invention, it is preferable to dilute the compound containing an isocyanate group and a (meth)acrylic group in one molecule in a solvent and dropwise add the diluted compound to the reaction solution of the intermediate 2 described above while paying attention to the rise in reaction temperature. The reaction temperature is preferably 0 to 110°C, and the reaction time is preferably 30 minutes to 5 hours.

[0034] The resin composition of the present invention contains the polymer compound of the present invention and a radical initiator. As the radical initiator, a thermal radical initiator or a photoradical initiator can be used. Preferred thermal radical initiators include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)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(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilyl peroxide.

[0035] 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 anthraquinone, 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; benzo Benzophenones such as phenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides and xanthones; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime).

[0036] The content of the radical initiator in the resin composition of the present invention is usually 0.1 to 10 parts by mass, and preferably 0.1 to 8 parts by mass, per 100 parts by mass of the polymer compound and the resin components such as the optional radical reactive monomer described below.

[0037] The resin composition of the present invention may be used in combination with a radical reactive monomer. By using a radical reactive monomer in combination, 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 is preferably one having one or more functional groups, and specific examples thereof 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, tricyclodecane dimethanol 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, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide amide, 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-maleimido-4'-acetoxysuccinimide- Diphenyl ether, 4-maleimide-4'-acetamido-diphenyl ether, 2-maleimide-6-acetamido-pyridine, 4-maleimide-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. These radical reactive monomers may be used alone or in combination of two or more.

[0038] The resin composition of the present invention may be used in combination with a radical reactive polymer. By using a radical reactive polymer in combination, the adhesiveness of the resin composition of the present invention and the heat resistance of the cured product can be improved. The radical reactive polymer is preferably one having two or more functional groups, and specific examples thereof include a copolymer of styrene and butadiene, a modified polyphenylene ether resin, an imide-extended bismaleimide, or a polymer compound represented by the following formula (5).

[0039] [ka]

[0040] (In formula (5), n is the average number of repeating units and is a real number from 1 to 20.)

[0041] The copolymer of styrene and butadiene may be a random copolymer (commonly known as SBR) or a block copolymer. It may also be a copolymer in which the double bonds derived from butadiene in the block copolymer are hydrogenated to form saturated hydrocarbons (commonly known as SEBS resin). The ratio of styrene to butadiene in the polymer is usually 10:90 to 90:10. The number average molecular weight is usually 1000 to 100,000. Specific examples of SBR products include Ricon 100, Ricon 181, and Ricon 184 from Cray Valley Corporation, and specific examples of SEBS resin products include the Tuftech series from Asahi Kasei Corporation and the G Polymer series from Kraton Corporation.

[0042] A preferred example of the modified polyphenylene ether resin is one having a methacryloyl group, an acryloyl group, or a vinyl group at both ends of the molecule and a number average molecular weight of 1000 to 10000. Specific examples include a compound represented by the following formula (6) having a methacryloyl group at both ends and a number average molecular weight of about 1700 (product name SA9000, manufactured by SABIC Japan LLC), and a compound represented by the following formula (7) having vinyl groups 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., Inc.).

[0043] [ka]

[0044] [ka]

[0045] The imide-extended bismaleimide resin used in the present invention can be obtained by a known method described in, for example, Japanese Patent No. 5328006. Specifically, the resin can be obtained by carrying out a dehydration condensation reaction of an aliphatic diamine and an aromatic or aliphatic tetracarboxylic dianhydride in an organic solvent using an acid catalyst in a molar ratio in which the aliphatic diamine is in excess, followed by dehydration condensation of amino groups present in the polymer terminals with maleic anhydride, and then removing the catalyst by washing with water.

[0046] 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, and 9,10-diaminophenanthrene, with dimer diamine being particularly preferred.

[0047] Specific examples of aromatic or aliphatic tetracarboxylic dianhydrides include pyromellitic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic 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'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-bisphenol A phthalic 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-cyclobutane Tetracarboxylic 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-dioxotetrahydrofuran-3-yl)-1,2,3, Examples of suitable dianhydrides include 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-tetrahydrofuran tetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norbornane acetic dianhydride, but pyromellitic anhydride and 1,2,4,5-cyclohexane tetracarboxylic dianhydride are particularly preferred. A specific product name is BMI-3000 by Designer Molecules, Inc.

[0048] In addition, since the polymer compound of the present invention is alkali-soluble, it can be used in combination with a conventional alkali-soluble curable resin. A specific example of the alkali-soluble curable resin is a half ester obtained by adding acrylic acid to the epoxy group of a polyfunctional epoxy resin and reacting the resulting alcoholic hydroxyl group with a polybasic acid anhydride.

[0049] Examples of polyfunctional epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aralkylphenol novolac type epoxy resins, biphenyl novolac type epoxy resins, triphenylmethane type epoxy resins, etc. Examples of the polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and chlorendic anhydride, and polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride.

[0050] The resin composition of the present invention may be used in combination with an organic solvent. Specific examples of the organic solvent 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, amide solvents such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N,N-dimethylimidazolidinone, and sulfones such as tetramethylene sulfone. 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 in the resin composition.

[0051] The resin composition of the present invention may be used in combination with a polymerization inhibitor to improve storage stability. The polymerization inhibitor that can be used in combination is not particularly limited as long as it is a generally known one, and examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil, and trimethylquinone, aromatic diols, and di-t-butylhydroxytoluene.

[0052] The resin composition of the present invention can be used by blending fillers and additives in amounts that do not impair the inherent performance, for the purpose of imparting desired performance depending on the application. The fillers may be in the form of fibers or powders, and examples of such fillers include silica, carbon black, alumina, talc, mica, glass beads, and glass hollow spheres.

[0053] The resin composition of the present invention can also be used in combination with a flame-retardant compound, an additive, 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, silicon-based compounds, and the like. Additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, gloss agents, and the like, and can be used in appropriate combination as desired.

[0054] The resin composition of the present invention can be applied or impregnated on various substrates. For example, when a thermal radical initiator is used, it can be applied on a PET film to form an interlayer insulating layer for a multilayer printed circuit board, applied on a polyimide film to form a coverlay, or applied and dried on a copper foil to form a resin-coated copper foil. It can also be impregnated into glass cloth, glass paper, carbon fiber, various nonwoven fabrics, and the like to form a printed wiring board or a prepreg for CFRP. Furthermore, by using a photoradical initiator, it is possible to develop a specific pattern by curing only the part irradiated with light of a specific wavelength and washing the other parts with an alkaline aqueous solution, and it can also be used as various resists such as a rewiring layer for semiconductors and a solder resist for printed circuit boards.

[0055] The interlayer insulating layer, coverlay, resin-coated copper foil, prepreg, and the like of the present invention can be heated and pressurized in a hot press or the like to form a cured product. EXAMPLES

[0056] The present invention will be described in more detail below with reference to examples and comparative examples. Unless otherwise specified, all parts are by weight. However, the present invention is not limited to these examples.

[0057] [Example 1 (Synthesis of polymer compound of the present invention)] A flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer was charged with 18.59 parts of dimer diol (product name Pripol 2033, manufactured by Croda), 14.7 parts of 4,4'-biphthalic anhydride, and 30 parts of cyclopentanone, and reacted at 100°C for 12 hours under a nitrogen atmosphere to obtain a cyclopentanone solution of intermediate 1 represented by the following formula (8). The value of n calculated from the number average molecular weight of 2220 by GPC was 2.3.

[0058] [ka]

[0059] 3.9 parts of 2-hydroxyethyl methacrylate was added to the solution of intermediate 1 and reacted at 100° C. for 5 hours to obtain a cyclopentanone solution of intermediate 2 having a structure represented by the following formula (9). The acid value of intermediate 2 was measured and found to be 151 mgKOH / g.

[0060] [ka]

[0061] The temperature of the reaction solution of the intermediate 2 was lowered to 50° C., and 4.65 parts of 2-isocyanatoethyl methacrylate (product name Karenz MOI, manufactured by Showa Denko K.K.) was added and reacted at 50° C. for 1 hour to obtain a cyclopentanone solution of the polymer compound of the present invention having a structure represented by the following formula (10). The amount of cyclopentanone was adjusted to a solid content concentration of 50%.

[0062] [ka]

[0063] The acid value of this polymer compound was 94 mgKOH / g. When calculated in comparison with the acid value of intermediate 2, it was found that, of Z in formula (10), 30 mol % was a structure represented by formula (11) below, and 70 mol % was a carboxy group.

[0064] [ka]

[0065] In formula (11), * represents the bonding position to the aromatic ring in formula (10).

[0066] [Comparative Example 1 (Synthesis of Comparative Polymer Compound)] In the synthesis procedure of Example 1, the reaction was stopped when a cyclopentanone solution of intermediate 2 was obtained, and the amount of cyclopentanone was adjusted to a solid content of 50%. The obtained resin was used as a comparative resin solution.

[0067] [Example 2, Comparative Example 2] (Alkaline solubility evaluation) 0.16 parts of each of the resin solutions obtained in Example 1 and Comparative Example 1 were placed in a 20 ml sample tube, and left to stand at 120°C under vacuum for 1 hour to completely evaporate the solvent. After that, 10 ml of a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) was added, and the time until complete dissolution was measured.

[0068] [Table 1]

[0069] [Example 3, Comparative Example 3 (Preparation of Resin Composition)] To 10 parts of the resin solutions obtained in Example 1 and Comparative Example 1, 0.1 parts of dicumyl peroxide as a radical initiator was added and mixed uniformly to obtain Resin Composition 1 of the present invention and Comparative Resin Composition 2.

[0070] (Evaluation of dielectric properties, heat resistance, and adhesive properties of cured resin compositions) Using an applicator, resin compositions 1 and 2 were applied to a thickness of 140 μm on the mirror surface of a copper foil having a thickness of 18 μm, and the solvent was dried by heating at 90 ° C for 10 minutes to obtain a copper foil having a film-like adhesive made of the resin composition. The film-like adhesive on the copper foil obtained above was heated and cured at 180 ° C for 1 hour using a vacuum oven, and then immersed in an etching solution to remove the copper foil, thereby obtaining a cured film-like adhesive having a thickness of 70 μm that can be handled as a film. The dielectric constant and dielectric loss tangent at 10 GHz of the cured product obtained above were measured by a cavity resonance method using a network analyzer 8719ET (manufactured by Agilent Technologies). The results are shown in Table 2. The glass transition temperature of the same sample was also measured using a TMA (thermomechanical analyzer). The results are shown in Table 1.

[0071] Resin compositions 1 and 2 were applied to a thickness of 50 μm on the matte side of a 12 μm thick, high-frequency low-roughness copper foil (CF-T4X-SV: manufactured by Fukuda Metal Foil Powder Co., Ltd.) using an applicator, and the solvent was dried by heating at 90° C. for 10 minutes to obtain a copper foil having a film-like adhesive made of the resin composition. The matte side of the same copper foil as above was placed on the adhesive side of the resin-coated copper foil obtained above, and the copper foil was heated and cured for 1 hour at a pressure of 3 MPa in a vacuum press, and the 90° peel strength (adhesive strength) between the copper foils was measured using an autograph AGX-50 (manufactured by Shimadzu Corporation). The results are shown in Table 2.

[0072] [Table 2]

[0073] As described above, the polymer compound of the present invention exhibits good solubility in an alkaline aqueous solution, and the composition exhibits excellent dielectric properties, adhesive properties and heat resistance when cured using a radical initiator.

Claims

1. A polymer compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), each X independently represents a residue obtained by removing a carboxy group from an aromatic or aliphatic tetracarboxylic acid anhydride. Each Y independently represents a divalent residue obtained by removing a hydroxyl group from an aliphatic diol compound. Each A independently represents a divalent linking group. Each Z independently represents a carboxy group or a structure represented by the following formula (2). R １ are each independently a methyl group or a hydrogen atom; n is the average number of repeating units and is a real number from 0.1 to 20. 【Chemistry 2】 (In formula (2), * represents the bonding position with X in formula (1). R ２ is a methyl group or a hydrogen atom.)

2. A resin composition comprising the polymer compound according to claim 1 and a radical initiator.

3. The resin composition according to claim 2, which contains a radical reactive monomer having one or more functional groups in one molecule.

4. The resin composition according to claim 2, which comprises a radically reactive polymer having two or more functional groups in one molecule.

5. A cured product of the resin composition according to any one of claims 2 to 4.

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