TW202315902A - Copolymer, curable resin composition, and cured object therefrom - Google Patents

Abstract

The present invention provides a (meth)acryloyl-group-containing copolymer exhibiting excellent electrical properties and having satisfactory curability, a curable resin composition, and a cured object obtained from the curable resin composition. The copolymer is a styrene-based copolymer having a (meth)acryloyl group at an end.

Description

Copolymer, curable resin composition and cured product thereof

The present invention relates to a copolymer having a (meth)acryl group, a curable resin composition and its cured product, which can be preferably used in electric-electronics such as semiconductor sealing materials, printed wiring boards, and build-up laminates. Parts, carbon fiber reinforced plastics, glass fiber reinforced plastics and other lightweight high-strength materials, three-dimensional (three dimensional, 3D) printing applications.

In recent years, due to the expansion of the field of use of laminated boards mounted with electric and electronic components, a wide range of characteristics and high-level requirements are required. The mainstream of existing semiconductor chips is mounted on a lead frame made of metal, but semiconductor chips with high processing capabilities such as central processing units (hereinafter referred to as CPU (central processing unit)) are often mounted on lead frames made of polymer materials. into laminated panels.

In particular, semiconductor packages (packages) (hereinafter referred to as PKG) used in smartphones and the like require thinner PKG substrates in order to meet the requirements for miniaturization, thinner thickness, and higher density. However, if the PKG substrate If the thickness is reduced, the rigidity will decrease, and therefore, problems such as large warpage may occur due to heating when PKG is soldered and mounted on a mother board (printed circuit board (PCB)). In order to reduce this problem, it is required to solder a PKG substrate material having a high Tg above the mounting temperature.

In addition, the fifth-generation communication system "5G", which is currently being accelerated, is expected to further promote large-capacity and high-speed communication. The demand for low dielectric loss tangent materials is increasing, at least a dielectric loss tangent below 0.005 is required at 10 GHz.

Furthermore, in the field of automobiles, electronicization is progressing, and precision electronic devices are sometimes arranged near the engine driving part, so a higher level of heat and humidity resistance is required. SiC semiconductors are beginning to be used in trains and air conditioners, and sealing materials for semiconductor elements are required to have extremely high heat resistance, so existing epoxy resin sealing materials cannot cope.

In this context, polymer materials that can have both heat resistance and low dielectric loss tangent properties are being studied. For example, Patent Document 1 proposes a composition including a maleimide resin and an acrylic group-containing phenol resin. However, in this case, since the phenolic hydroxyl group that does not participate in the reaction during the curing reaction remains, it cannot be said that the electrical characteristics are sufficient. In addition, Patent Document 2 discloses an allyl ether resin in which a hydroxyl group is substituted with an allyl group. However, allyl ether resins show Claisen rearrangement at 190°C and generate phenolic hydroxyl groups that do not contribute to the curing reaction at 200°C, which is a general substrate molding temperature. electrical characteristics.

In addition, in recent years, 3D printing has attracted attention as a method of three-dimensional modeling, and 3D printing has begun to be applied in fields requiring reliability such as aviation, space, automobiles, and connectors of electronic components used in these. printing method. In particular, studies on photocurable resins and thermosetting resins for applications represented by Stereo Lithography Apparatus (SLA) and Digital Light Processing (DLP) are ongoing. Therefore, in the previous method of transfer printing from the mold, the stability and accuracy of the shape are mainly required, but in the application of 3D printing, various requirements such as heat resistance, mechanical properties, toughness, flame retardancy, and electrical properties are required. characteristics, and its material development is ongoing. Moreover, when it is used for a structural member, the characteristic change by moisture absorption etc. becomes a problem. At present, acrylate resins or epoxy resins are used for such applications, but their hardened products contain a large amount of ester bonds, ether bonds, and further hydroxyl groups, and their moisture absorption properties are insufficient. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 04-359911 [Patent Document 2] International Publication No. 2016/002704

[Problem to be Solved by the Invention] The present invention has been made in view of such circumstances, and an object of the present invention is to provide a copolymer having a (meth)acryl group, a curable resin composition, and a cured product thereof, which exhibit excellent electrical characteristics and have good curability. [Means to solve the problem]

The inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, have found that a cured product containing a (meth)acrylate compound having a specific structure and a curable resin composition thereof has excellent low dielectric properties, thereby completing the present invention. invention.

That is, the present invention relates to the following [1] to [7]. Furthermore, in this application, "(numerical value 1) ~ (numerical value 2)" means that the upper and lower limits are included, and the so-called "(meth)acryl" refers to "acryl" and/or "methyl Acryl". [1] A styrene-based copolymer having a (meth)acryloyl group at the end. [2] A polystyrene-hydrogenated poly(butadiene/isoprene)-polystyrene copolymer having a (meth)acryl group at the end. [3] The copolymer as described in [1] or [2] above is represented by the following formula (1).

[chemical 1]

(In formula (1), X represents any one of (A) to (E) described in the following formula (2), and R represents a hydrogen atom or a methyl group. j, k, l, m, and n are repetition numbers The average value of , representing a real number from 1 to 100000. The order of the repeating units enclosed by k and l, or j, m and n is not limited, and the bonding method can be any of alternating, block, and random)

[4] 如前項[3]所述的共聚物，其中所述式（1）中，X為所述式（2）中記載的（A）。 [5] 一種硬化性樹脂組成物，含有如前項[1]至[4]中任一項所述的共聚物。 [6] 如前項[5]所述的硬化性樹脂組成物，含有自由基聚合起始劑。 [7] 一種硬化物，將如前項[1]至[4]中任一項所述的共聚物、或如前項[5]或[6]所述的硬化性樹脂組成物硬化而得。 [發明的效果] [Chem 2]

[4] The copolymer as described in [3] above, wherein in the formula (1), X is (A) described in the formula (2). [5] A curable resin composition comprising the copolymer as described in any one of [1] to [4]. [6] The curable resin composition as described in [5] above, which contains a radical polymerization initiator. [7] A cured product obtained by curing the copolymer described in any one of [1] to [4] above, or the curable resin composition described in [5] or [6] above. [Effect of the invention]

The copolymer having a (meth)acryl group of the present invention is excellent in curability, and its cured product has excellent low dielectric properties. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composites, and the like.

The present invention relates to a styrene-based copolymer having a (meth)acryl group at the terminal (hereinafter referred to as the copolymer of the present invention). Having a (meth)acryl group at a terminal means having a (meth)acryl group at one terminal or both terminals of the copolymer, preferably having a (meth)acryl group at one terminal. The styrene-based copolymer is not particularly limited as long as it has a styrene structure, and examples thereof include styrene-butadiene copolymers, styrene-isoprene copolymers, acrylonitrile-butadiene copolymers, and styrene-butadiene copolymers. ethylene-styrene copolymer, styrene-butyl acrylate copolymer, etc., preferably polystyrene-hydrogenated poly(butadiene/isoprene)-polystyrene copolymer.

The synthesis method of the copolymer of the present invention is not particularly limited, and it can be obtained from a styrene-based copolymer having a hydroxyl group at the end and an acid chloride having a (meth)acryl group, or an isocyanate having a (meth)acrylate group. derivative.

Specifically, an acid chloride having a (meth)acryl group or an isocyanate having a (meth)acryl group is mixed with a polystyrene-hydrogenated poly(butadiene/butadiene/butadiene/ Isoprene) - polystyrene copolymer reaction method obtained. In this case, the number of charged moles of the acid chloride (or isocyanate) to be reacted is preferably from 0.80 to 1.20, more preferably from 0.90 to 1.10, and still more preferably from 0.95 to 1.05, relative to the hydroxyl group contained in the raw material. In a region outside the above range, polar groups such as hydroxyl groups derived from remaining raw materials may degrade electrical characteristics.

Examples of solvents used include: aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate and butyl acetate. solvents; water-insoluble solvents such as ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more types may be used in combination. In addition, an aprotic polar solvent may be used in combination in addition to the above-mentioned water-insoluble solvent. For example, dimethylsulfide, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone etc., and two or more of them may be used in combination. Among them, it is preferable to use hydrocarbon-based solvents such as toluene, xylene, hexane, and cyclohexane.

When carrying out the esterification reaction using an acid chloride, in order to trap the hydrogen chloride produced|generated, you may use a basic compound, such as triethylamine, individually or in combination as needed. The amount to be added is preferably in the range of 0.1 to 10 mol, more preferably 0.5 to 5 mol, and still more preferably 0.9 to 4.0 mol, based on 1 mol of the acid chloride used. . When it is below the lower limit of the said range, the hydrogen chloride which generate|occur|produces may not be fully collect|collected. Since the amount of waste will increase when it is more than the upper limit of the said range, it is industrially unfavorable.

When implementing the urethanation using an isocyanate compound, it can implement without a catalyst, and you can also use a urethanization catalyst. The urethanization catalyst is not particularly limited, and examples thereof include nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; potassium acetate, zinc stearate, and octanoic acid Metal salts such as tin; organometallic compounds such as dibutyltin dilaurate, etc. When using a urethanization catalyst, the amount to be added is preferably in the range of 0.001 mol to 10 mol, more preferably 0.01 mol to 5.0 mol, based on 1 mol of the isocyanate compound used. mole, and more preferably 0.05 mole to 4.0 mole. The reaction rate may fall as it is below the lower limit of the said range. Since the amount of waste will increase when it is more than the upper limit of the said range, it is industrially unfavorable.

A water washing step may be performed before the solvent is distilled off as needed after the completion of the reaction. In addition, when a salt is generated, the solvent may be distilled off after removal by filtration. The target compound can be obtained by distilling off the solvent after performing purification steps such as washing with water or filtering if necessary.

As the polystyrene-hydrogenated poly(butadiene/isoprene)-polystyrene copolymer having a hydroxyl group at the terminal, any known copolymer can be used, for example, Septon ) HG252 (manufactured by Kuraray Co., Ltd.), etc. Septon HG252 (manufactured by Kuraray Co., Ltd.) is a polystyrene-hydrogenated poly(butadiene/isoprene)-polystyrene copolymer having a hydroxyl group at one end.

As the acid chloride having a (meth)acryl group or the isocyanate having a (meth)acryl group, known arbitrary ones can be used. Specifically, for example, acryl chloride, methacryl chloride, 2-isocyanatoethyl methacrylate (Karenz (Karenz) MOI: manufactured by Showa Denko Co., Ltd.), acrylic acid 2-isocyanate Ethyl cyanate (Karenz (Karenz) AOI: Manufactured by Showa Denko Co., Ltd.), 2-(2-methacryloxyethyloxy) ethyl isocyanate (Karenz (Karenz) MOI- EG: manufactured by Showa Denko Co., Ltd.), 1,1-(bisacryloxymethyl)ethyl isocyanate (Karenz (Karenz) BEI: manufactured by Showa Denko Co., Ltd.), and the like. From the viewpoint of improving heat resistance and compatibility, it is preferable to use a compound having a methacrylic group. For example, the listed methacryl chloride, 2-isocyanatoethyl methacrylate, and 2-(2-methacryloxyethyloxy)ethylisocyanate are examples of preferred compounds .

The copolymer of the present invention is particularly preferably represented by the following formula (1).

[Chem 3]

(In formula (1), X represents any one of (A) to (E) described in the following formula (2), and R represents a hydrogen atom or a methyl group. j, k, l, m, and n are repetition numbers The average value of , representing a real number from 1 to 100000. The order of the repeating units enclosed by k and l, or j, m and n is not limited, and the bonding method can be any of alternating, block, and random)

[chemical 4]

j, k, l, m, and n are usually numbers from 1 to 100,000, preferably from 1 to 90,000, and more preferably from 1 to 80,000. The order of the repeating units enclosed by k and l, or j, m and n is not limited, and the bonding mode is preferably random.

The weight average molecular weight (Mw) of the copolymer of the present invention is preferably at least 1,000 and less than 500,000, more preferably at least 2,500 and less than 400,000, particularly preferably at least 5,000 and less than 300,000. The number average molecular weight (Mn) of the copolymer of the present invention is preferably at least 1,000 and less than 500,000, more preferably at least 2,500 and less than 400,000, particularly preferably at least 5,000 and less than 300,000. When the number average molecular weight or weight average molecular weight is less than 500,000, the compatibility with other resins becomes good, and if it is more than 1,000, the target compound does not volatilize in the solvent distillation step or B-stage of the composition.

In addition, in the above formula (1), when X is further preferably any one of (A) to (C) or (E) described in the above formula (2), it is particularly preferably (A).

R represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving heat resistance and compatibility.

The curable resin composition of the present invention may also contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability can be improved, and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, fluidity can be easily ensured, and B-stage formation such as prepreg formation becomes easy without impairing the impregnation property in glass fiber cloth or the like. When the polymerization reaction proceeds excessively during prepreg formation, troubles such as difficulty in lamination in the lamination step tend to occur.

Usable polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, nitroxyl-based and other polymerization inhibitors. The polymerization inhibitor may be added when synthesizing the compound represented by the formula (1), or may be added after synthesis. Moreover, a polymerization inhibitor can be used individually or in combination of 2 or more types. The usage-amount of a polymerization inhibitor is 0.008-1 weight part normally with respect to 100 weight part of resin components, Preferably it is 0.01-0.5 weight part. These polymerization inhibitors may be used alone, respectively, or may be used in combination of two or more. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl-based are preferred.

Specific examples of phenolic polymerization inhibitors include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethyl Phenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol and other monophenols; 2,2'-methylene bis(4-methyl-6-tert-butylphenol), 2,2 '-Methylene bis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene Bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-Hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5- Di-tert-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3 -tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3, 5-di-tert-butyl-4-hydroxybenzylsulfonate ethyl) calcium and other bisphenols; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl ) butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3- (3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylbenzene base) butyric acid] ethylene glycol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5' -Di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other high molecular weight phenols.

As specific examples of sulfur-based polymerization inhibitors, 3,3'-dilauryl thiodipropionate, 3,3'-dimyristyl thiodipropionate, 3,3'-dilauryl thiodipropionate, Distearyl propionate, etc.

Specific examples of phosphorus-based polymerization inhibitors include: triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, Pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentyl Alkane tetrayl bis(2,4-di-tert-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-tert-butyl-4-methylphenyl) phosphite Phosphates, bis[2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite and other phosphites; 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxo Hetero-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and other oxaphosphaphenanthrene oxides wait.

Specific examples of hindered amine-based polymerization inhibitors include: Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, Adekastab LA-63P, Adekastab Adekastab LA-57, Adekastab LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Dinubin (Tinuvin) 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin ) 783FDL, Tinuvin 791FB, etc., but not limited thereto.

Specific examples of nitroso-based polymerization inhibitors include ammonium salts (cupferron) of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxylamine. ), etc., preferably the ammonium salt of N-nitrosophenylhydroxylamine (copperferrin).

Specific examples of nitroxyl radical-based polymerization inhibitors include di-tert-butyl nitrogen, 2,2,6,6-tetramethylpiperidine-1 -oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl , 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-Acetyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1- oxygen group, etc., but are not limited to these.

The curable resin composition of the present invention can use known arbitrary materials as curable resins other than the copolymer of the present invention. Specifically, phenol resins, epoxy resins, amine resins, active olefin-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate resins, acrylic resins, methallyl resins, Base resins, active ester resins, etc. may be used alone or in combination. In addition, it is preferable to contain an epoxy resin, an active olefin-containing resin, and a cyanate resin in terms of the balance of heat resistance, adhesiveness, and dielectric properties. By containing these curable resins, the brittleness of the cured product can be improved and the adhesiveness to metal can be improved, so that cracks in the package during solder reflow or in reliability tests such as cooling and heating cycles can be suppressed.

The amount of the curable resin used is preferably not more than 10 times by mass, more preferably not more than 5 times by mass, particularly preferably not more than 3 times by mass relative to the compound of the present invention. In addition, a preferable lower limit is 0.5 mass times or more, and more preferably 1 mass times or more. If it is 10 times by mass or less, the effects of heat resistance and dielectric properties of the compound described in the present invention can be effectively utilized.

As the phenol resin, epoxy resin, amine resin, activated olefin-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, and active ester resin, those exemplified below can be used.

Phenol resin: phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, hydroquinone, resorcinol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxy Naphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthylaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, Furfural, etc.); phenols and various diene compounds (dicyclopentadiene, terpenes, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene , divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene Ethanone, benzophenone, etc.) condensation products; by phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis( Methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1 , 4-bis (hydroxymethyl) benzene, etc.) polycondensation of phenolic resins obtained; polycondensates of bisphenols and various aldehydes; polyphenylene ether compounds.

As the polyphenylene ether compound, any known polyphenylene ether compound can be used, but from the viewpoint of heat resistance and electrical properties, a polyphenylene ether compound having an ethylenically unsaturated double bond is preferable, and a polyphenylene ether compound having an acrylic group, methyl group, etc. Polyphenylene ether compound with acrylic or styrene structure. Examples of commercially available products include SA-9000-111 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure). polyphenylene ether compounds), etc.

The number average molecular weight (Mn) of the polyphenylene ether compound is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, more preferably from 2,000 to 4,000. When the molecular weight is less than 500, there is a tendency that sufficient heat resistance cannot be obtained as heat resistance of the cured product. In addition, when the molecular weight exceeds 5,000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, so molding failure tends to occur easily. In addition, the reactivity also decreases, the curing reaction takes a long time, the unreacted substances that do not enter the curing system increase, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease.

When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, excellent heat resistance, moldability, etc. can be exhibited while maintaining excellent dielectric properties. In addition, the number average molecular weight here can be specifically measured using gel permeation chromatography etc.,.

The polyphenylene ether compound may be obtained by a polymerization reaction, or may be obtained by subjecting a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000 to a redistribution reaction. Moreover, radical polymerizability can also be imparted by using these as a raw material and reacting with the compound which has an ethylenically unsaturated double bond, such as methacryl chloride, acryl chloride, and chloromethylstyrene. The polyphenylene ether compound obtained by the redistribution reaction can be obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a free radical initiator and performing a redistribution reaction. The polyphenylene ether compound obtained by such a redistribution reaction has hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain, so not only can it maintain higher heat resistance, but it can also be used in It is preferable in terms of introducing a functional group into both ends of the molecular chain after modifying the compound having an ethylenically unsaturated double bond. In addition, a polyphenylene ether compound obtained by a polymerization reaction is preferable in terms of exhibiting excellent fluidity.

In the case of a polyphenylene ether compound obtained by a polymerization reaction, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting polymerization conditions and the like. In addition, in the case of the polyphenylene ether compound obtained by the redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction and the like. More specifically, adjustment of the compounding quantity of the phenolic compound used for a redistribution reaction, etc. are considered. That is, the larger the blending amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high-molecular-weight polyphenylene ether compound subjected to the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, and for example, bisphenol A, phenol novolak, cresol novolac, etc., which generally have two or more phenolic hydroxyl groups in the molecule, can be preferably used. multifunctional phenolic compounds. These may be used alone or in combination of two or more.

In addition, the content of the polyphenylene ether compound is not particularly limited, but is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, based on the total mass of curable resin components. When the content of the polyphenylene ether compound is 10% by mass to 90% by mass, a cured product that not only has excellent heat resistance and the like but also sufficiently exhibits the excellent dielectric properties of the polyphenylene ether compound can be obtained. good.

Epoxy resin: the phenol resin; glycidyl ether-based epoxy resin obtained by glycidylating alcohols, etc.; 4-vinyl-1-cyclohexene diepoxide or 3,4-cyclo Alicyclic epoxy resin represented by oxycyclohexylmethyl-3,4'-epoxycyclohexane carboxylate, etc.; tetraglycidyl diamino diphenylmethane (tetraglycidyl diamino diphenylmethane, TGDDM) or Glycidyl amine-based epoxy resin represented by triglycidyl-p-aminophenol, etc.; glycidyl ester-based epoxy resin.

Amine resins: diaminodiphenylmethane; diaminodiphenylmethane; isophorone diamine; naphthalene diamine; aniline novolak; Aniline resin obtained by the reaction of xylylene chloride); aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4 ,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxy Aniline resin obtained by reaction of benzene and 1,4-bis(hydroxymethyl)benzene, etc.).

Active olefin-containing resin: Polycondensation of the phenolic resin with an active olefin-containing halogen compound (chloromethylstyrene, allyl chloride, methylallyl chloride, acryl chloride, etc.) substances; phenols containing active olefins (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and Halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride (cyanuric chloride), etc.); epoxy resins or alcohols with substituted or un Polycondensates of substituted acrylates (acrylates, methacrylates, etc.); maleimide resins (4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide Amine, m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl Ether bismaleimide, 4,4'-diphenylbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4 -maleimide (phenoxy)benzene), neophenol (Xyloc) type maleimide resin (Anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenyl Alkyl-type maleimide resin (formed by distilling off the solvent under reduced pressure from a resin solution containing the maleimide resin (M2) described in Example 4 of JP-A-2009-001783 solidified), bisaminocumylbenzene-type maleimide (maleimide resin described in International Publication No. 2020/054601).

Isocyanate resin: p-phenylene diisocyanate, meta-xylene diisocyanate, p-xylene diisocyanate, meta-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane Aromatic diisocyanates such as diisocyanate and naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate Diisocyanates of aliphatic or alicyclic structure such as isocyanate and lysine diisocyanate; polyisocyanates such as biuret bodies of one or more isocyanate monomers or isocyanate bodies obtained by trimerizing said diisocyanate compounds; A polyisocyanate obtained by the urethane reaction of the isocyanate compound and the polyol compound.

Polyamide resin: selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactam (ε-caprolactam, ω-undecyl lactam, ω-laurolactam) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine Amine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine Amine, Tetradecanediamine, Pentadecanediamine, Hexadecanediamine, Heptadecanediamine, Octadecanediamine, Nonadecanediamine, Eicosanediamine, 2-Methyl-1 , 5-diaminopentane, 2-methyl-1,8-diaminooctane and other aliphatic diamines; cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3 -Alicyclic diamines such as methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylenediamine, etc.) and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, hexanoic acid) Aliphatic dicarboxylic acids such as diacid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid , 2-methyl terephthalic acid, 5-methyl isophthalic acid, isophthalic acid-5-sodium sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid and other aromatic dicarboxylic acids; A polymer in which at least one of the mixtures of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids is used as a main raw material.

Polyimide resin: the diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic Acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4 '-Diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic acid Dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetra Methylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride Formic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxybenzene base) phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3- Bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzenedi anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2- Bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis( 3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride , 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4, 9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1, 2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4' -Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid ) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1, 2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1 ,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3- Oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxo Tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4' - Polycondensate of biphenylbis(trimellitic monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride).

Cyanate resin: a cyanate compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, and dicyanoxynaphthalene , Dicyanooxybiphenyl, 2,2'-bis(4-cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)methane, bis(3,5-dimethyl-4-cyano oxyphenyl) methane, 2,2'-bis(3,5-dimethyl-4-cyanooxyphenyl)propane, 2,2'-bis(4-cyanooxyphenyl)ethane, 2,2'-Bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfide, phenol novolac cyanate , a phenol-dicyclopentadiene cocondensate having a hydroxyl group converted to a cyanate group, etc., but are not limited to these. Also, the cyanate compound whose synthesis method is described in JP-A-2005-264154 is particularly preferable as a cyanate compound because of its low hygroscopicity, flame retardancy, and excellent dielectric properties.

In order to trimerize the cyanate group to form a sym-triazine ring as needed, the cyanate resin may also contain zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, Zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate and other catalysts. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably in a range of 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total curable resin composition.

Active ester resin: A compound having one or more active ester groups in one molecule may be used as a curing agent for curable resins other than the compound represented by the formula (1) of the present invention, such as epoxy resin, if necessary. As active ester-based hardeners, phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds are preferred, which have two or more ester groups with high reactivity in one molecule. compound. The active ester-based hardener is preferably obtained by condensation reaction of at least any one of a carboxylic acid compound and a thiocarboxylic acid compound with at least one of a hydroxyl compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based hardeners obtained from a carboxylic acid compound and a hydroxyl compound are preferred, and those obtained from a carboxylic acid compound and at least any one of a phenol compound and a naphthol compound are preferred. active ester hardener.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methyl Bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, glucinol, dicyclopentanol Diene-type diphenol compounds, phenol novolaks, and the like. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Specific preferred examples of active ester hardeners include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, and active ester compounds containing acetylated phenol novolaks. Compounds, active ester compounds comprising benzoyl compounds of phenol novolaks. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The term "dicyclopentadiene-type diphenol structure" means a divalent structural unit including phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester hardeners include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T", which are active ester compounds containing a dicyclopentadiene-type diphenol structure , "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); "EXB9416-70BK", which is an active ester compound containing a naphthalene structure DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) which is an active ester compound containing acetylated phenol novolac; " "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) which is an active ester-based hardener which is an acetyl compound of phenol novolak; "EXB-9050L-62M" manufactured by DIC Corporation, which is an ester-based hardener, and the like.

The curable resin composition of the present invention may also use a curing accelerator (curing catalyst) in combination to improve curability. As a specific example of the hardening accelerator that can be used, in order to promote self-polymerization of curable resins such as olefin compounds and maleimide resins that can be radically polymerized, or radical polymerization with other components, it is preferable to use radical polymerization. starter. Examples of usable radical polymerization initiators include: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides, 1,3-bis(tertiary butylperoxyisopropyl)benzene and other dialkyl peroxides; tertiary butyl peroxybenzoate, 1,1-di-tertiary butyl Peroxyketals such as cyclohexane peroxide; α-cumylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxytrimethylacetate, 1,1 ,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, tertiary pentylperoxy-2-ethylhexanoate, tertiary butylperoxy-2-ethylhexanoate , tertiary pentyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary pentyl peroxybenzoic acid Alkyl peroxyesters such as esters; di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxyisopropyl carbonate Esters, 1,6-bis(tertiary butylperoxycarbonyloxy) hexane and other peroxycarbonates; tertiary butyl hydroperoxide, cumene hydroperoxide, tertiary butyl peroxyoctanoate , lauryl peroxide and other organic peroxides or azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethyl Known hardening accelerators of azo-based compounds such as valeronitrile), but are not particularly limited to these. Preferred are ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxycarbonates etc., more preferably dialkyl peroxides. The amount of the radical polymerization initiator added is preferably from 0.01 to 5 parts by mass, particularly preferably from 0.01 to 3 parts by mass, based on 100 parts by mass of the curable resin composition. When the amount of the radical polymerization initiator to be used is large, the molecular weight cannot be sufficiently increased during the polymerization reaction.

Moreover, you may add or use together the hardening accelerator other than a radical polymerization initiator as needed. Specific examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; Tertiary amines such as methylaminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7; triphenylphosphine, Tris(toluyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and other phosphines or phosphonium compounds, tributylphosphine and other organic phosphines, metal compounds such as tin octanoate, tetraphenyl Phosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate and other tetrasubstituted phosphonium-tetrasubstituted borates, 2-ethyl-4-methylimidazole-tetraphenylborate, N-methyl Tetraphenylboron salts such as morpholine-tetraphenylborate, carboxylic acid compounds such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, and salicylic acid, etc. From the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin, carboxylic acid compounds such as salicylic acid are preferred. 0.01-15 weight part of hardening accelerators are used as needed with respect to 100 weight part of epoxy resins.

In the curable resin composition of the present invention, a phosphorus-containing compound may also be contained as a flame retardancy imparting component. As the phosphorus-containing compound, either a reactive type or an additive type may be used. Specific examples of phosphorus-containing compounds include: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, tolyl diphenyl phosphate, cresyl-2 ,6-bis(xylyl)phosphate, 1,3-phenylene bis(bis(xylyl)phosphate), 1,4-phenylene bis(bis(xylyl)phosphate), 4,4'-biphenyl (di(xylyl) phosphate) and other phosphates; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2 , 5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphanes (phosphanes); the epoxy resin is obtained by reacting the active hydrogen of the phosphanes Phosphorus-containing epoxy compounds, red phosphorus, etc., are preferably phosphoric acid esters, phosphine or phosphorus-containing epoxy compounds, and are particularly preferably 1,3-phenylene bis(bis(xylyl)phosphate), 1,4-Phenylbis(bis(xylyl)phosphate), 4,4'-biphenyl(bis(xylyl)phosphate), or phosphorus-containing epoxy compounds. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound)/(total epoxy resin) 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a possibility of adversely affecting the hygroscopicity and dielectric properties of the cured product.

Furthermore, an optical stabilizer may be added to the curable resin composition of this invention as needed. The light stabilizer is preferably a hindered amine-based light stabilizer, particularly preferably a hindered amine light stabilizer (Hindered Amine Light Stabilizer, HALS). The HALS is not particularly limited, but typical examples include: dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4 -Piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine polycondensate, dimethyl succinate- 1-(2-Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2 ,2,6,6-tetramethyl-4-piperidinyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5 -Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) Sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl Base-4-piperidinyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2, 6,6-pentamethyl-4-piperidinyl) ester, etc. Only one type of HALS may be used, or two or more types may be used in combination.

Furthermore, in the curable resin composition of this invention, a binder resin can also be mix|blended as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy -NBR-based resins, polyamide-based resins, polyimide-based resins, silicone-based resins, etc., but are not limited to these. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the hardened product, and is preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the resin component, and more preferably 0.05 parts by mass if necessary. Parts by mass to 20 parts by mass.

Further, in the curable resin composition of the present invention, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, carbonized Silicon, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc (talc), clay, iron oxide, asbestos (asbestos), glass powder and other powders, or make them into spherical or crushed inorganic fillers. In addition, especially in the case of obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used in the curable resin composition is usually 80% by mass to 92% by mass, preferably 83% by mass % to 90% by mass.

In the curable resin composition of this invention, a well-known additive can be compounded as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, etc. Glue, silicone oil, surface treatment agent for filling materials like silane coupling agent, release agent, carbon black, phthalocyanine blue, phthalocyanine green and other colorants. The compounded amount of these additives is preferably not more than 1,000 parts by mass, more preferably not more than 700 parts by mass, relative to 100 parts by mass of the curable resin composition. From the viewpoint of low water absorption and electrical properties, polybutadiene and its modified products, polyphenylene ether, polystyrene, polyethylene, fluororesin, and the like are preferable. From the viewpoint of electrical properties, adhesiveness, and low water absorption, polybutadiene and its modified products are preferred. Specifically, for example, styrene butadiene copolymer (SBR: RICON-100, RICON-181, RICON-184 are Cray Valley ) company manufacturing, etc.), butadiene-based thermoplastic elastomers such as acrylonitrile butadiene copolymer; styrene butadiene styrene copolymer (SBS), hydrogenated styrene butadiene styrene copolymer, styrene isoprene Styrene-based thermoplastic elastomers such as diene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene/isoprene)-styrene copolymer, etc. These styrene-based thermoplastic elastomers may be used alone or in combination of two or more. Among these high molecular weight bodies, preferred are styrene butadiene styrene copolymer, hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer, hydrogenated styrene isoprene Styrene-based thermoplastic elastomers such as styrene copolymers, hydrogenated styrene (butadiene/isoprene) styrene copolymers, especially styrene-isoprene-styrene copolymers, hydrogenated styrene-butadiene-benzene Ethylene copolymers, hydrogenated styrene isoprene styrene copolymers, and hydrogenated styrene (butadiene/isoprene) styrene copolymers are more preferable because they have higher heat resistance and are less likely to be oxidized and deteriorated. Specifically, Septon 1020, Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, Septon 8004, Septon 8006, Septon 8007L, Septon HG252, Septon V9827, hybrar 7125 (hydrogenation) , Hybrar (hybrar) 7215F, Hybrar (hybrar) 7311F (all manufactured by Kuraray Co., Ltd.). In addition, the weight average molecular weight of the styrene-based thermoplastic elastomer is not particularly limited as long as it is 10,000 or more, but if it is too large, in addition to the polyphenylene ether compound, low molecular weight components with a weight average molecular weight of about 50 to 1,000 and weight average The compatibility of the oligomer component with a molecular weight of about 1,000 to 5,000 deteriorates and it becomes difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components in a predetermined ratio, and is usually pre-cured at 130°C to 180°C for 30 seconds to 500 seconds, and then heated at 150°C to 200°C. After curing for 2 hours to 15 hours at °C, a sufficient curing reaction proceeds to obtain the cured product of the present invention. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and the solvent may be removed to be cured.

The curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, and high adhesiveness. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, and high adhesiveness. Specifically, it can be effectively used as insulating materials, laminates (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), sealing materials, resists, etc. for all electrical and electronic parts Material. In addition, in addition to molding materials and composite materials, it can also be used in coating materials, adhesives, 3D printing and other fields. Especially in semiconductor sealing, solder reflow resistance is beneficial.

A semiconductor device is sealed with the curable resin composition of the present invention. Examples of the semiconductor device include a dual in-line package (DIP), a quad flat package (QFP), a ball grid array (BGA), and a chip size package ( chip size package, CSP), small outline package (small outline package, SOP), thin small outline package (thin small outline package, TSOP), thin quad flat package (thin quad flat package, TQFP), etc.

The method for producing the curable resin composition of the present invention is not particularly limited, and each component may be merely mixed uniformly, or prepolymerized. For example, prepolymerization is performed by heating the curable resin of the present invention in the presence or absence of a catalyst or in the presence or absence of a solvent. Similarly, in addition to the hardening resin of the present invention, hardeners such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenol resins, acid anhydride compounds, and other additives can also be added for prepolymerization. materialize. For mixing or prepolymerization of each component, for example, an extruder, a kneader, a roll, etc. are used in the absence of a solvent, and a reaction tank with a stirring device or the like is used in the presence of a solvent.

As a method of uniformly mixing, mixing is performed at a temperature in the range of 50° C. to 100° C. using a device such as a kneader, a roller, and a planetary mixer to obtain a uniform resin composition. The obtained resin composition can also be formed into a cylindrical ingot shape by a molding machine such as a tablet machine after being pulverized, or made into a granular powder or a powdery molded body, or these compositions It is melted on the surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to make a curable resin composition molded body. The obtained molded product was a non-tacky molded product at 0°C to 20°C, and even if it was stored at -25°C to 0°C for one week or more, the fluidity and curability hardly deteriorated. The obtained molded body can be molded into a cured product using a transfer molding machine or a compression molding machine.

An organic solvent may be added to the curable resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-formaldehyde The varnish is prepared in a solvent such as pyrrolidone, impregnated in glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates and heated and dried, and the obtained prepreg is hot-pressed By molding, a cured product of the curable resin composition of the present invention can be produced. The solvent at this time is used in the mixture of the curable resin composition of the present invention and the solvent, usually in an amount of 10% by weight to 70% by weight, preferably in an amount of 15% by weight to 70% by weight. In addition, if it is a liquid composition, a hardened resin cured product containing carbon fibers can also be directly obtained, for example, by resin transfer molding (RTM).

In addition, the curable composition of the present invention can also be used as a modifier of a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage, etc. Such a film-type resin composition is obtained by making the curable resin composition of the present invention into the curable resin composition varnish, coating it on a release film, removing the solvent under heating, and then B-staged. Available as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

The curable resin composition of the present invention can be heat-melted, reduced in viscosity, and impregnated with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and further include fibers of inorganic substances other than glass. or polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by Dupont Incorporated), wholly aromatic polyamides, polyesters; and polyparaphenylene Organic fibers such as polyparaphenylene benzoxazole (polyparaphenylene benzoxazole), polyimide, and carbon fibers are used, but are not particularly limited thereto. Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, a roving (roving), a chopped strand mat (chopped strand mat), etc. are mentioned. In addition, plain weave, basket weave, twill weave, etc. are known as the weaving method of the woven fabric, and it can be appropriately selected from these known weaving methods according to the intended use or performance. In addition, glass woven fabrics subjected to fiber opening treatment or surface-treated with a silane coupling agent or the like can be preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 mm to 0.4 mm. In addition, a prepreg can also be obtained by impregnating the reinforcing fiber with the above-mentioned varnish, followed by heating and drying.

The laminated board of the present embodiment includes one or more prepregs. The laminate is not particularly limited as long as it includes one or more prepregs, and may have any other layers. A generally known method can be suitably applied as a method for producing a laminate, and it is not particularly limited. For example, when forming a metal foil-attached laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used, and the prepregs can be laminated and heated. Press forming to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65°C to 300°C, more preferably 120°C to 270°C. In addition, the pressure of the pressurization is not particularly limited. If the pressurization is too high, it will be difficult to adjust the solid content of the resin of the laminated board, and the quality will not be stable. If the pressure is too small, the air bubbles and the adhesion between the laminated layers will be deteriorated. Therefore, it is preferably 2.0 MPa to 5.0 MPa, more preferably 2.5 MPa to 4.0 MPa. The laminated board of this embodiment can be suitably used as the laminated board with metal foil mentioned later by including the layer which has a metal foil. The prepreg is cut into a desired shape, and laminated with copper foil or the like as necessary, while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. The curable resin composition is heated and hardened to obtain a laminate (printed wiring board) for electrical and electronic use or a carbon fiber reinforced material.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition described in the present invention shows excellent heat resistance and dielectric properties, so it can be preferably used for sealing materials for semiconductor elements, sealing materials for liquid crystal display elements, organic electroluminescence (electroluminescence, EL) component sealing materials, printed wiring boards, build-up laminates and other electrical-electronic parts, or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics. [Example]

Next, the present invention will be described more specifically by way of examples. Hereinafter, unless otherwise specified, a part is a mass part. In addition, this invention is not limited to these Examples. Various analysis methods used in Examples are described below. <Weight average molecular weight (Mw), number average molecular weight (Mn)> Calculated by polystyrene conversion using polystyrene standard solution. Gel permeation chromatography (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation) Column: Shodex KF-603, KF-602×2, KF-601×2 Connecting eluent: tetrahydrofuran Flow rate: 0.5ml/min. Column temperature: 40°C Detector: RI (Differential Refractive Detector)

[Example 1] 100 parts of toluene, Septon HG252 (Kuraray) stock Co., Ltd., hydroxyl equivalent 40000 g/eq.) 20 parts, methacryl chloride 0.05 parts, react at 25°C for 2 hours while stirring, react at 60°C for 3 hours, and react at 70°C for 12 Hours, a toluene solution of the target compound (S1: solid content 20 wt%) was obtained. The GPC of the toluene solution of the obtained compound is shown in FIG. 1 . The number average molecular weight Mn of the present compound measured by GPC was 118709, and the weight average molecular weight Mw was 131690.

[Example 2] 100 parts of toluene and 20 parts of Septon HG252 (manufactured by Kuraray Co., Ltd., hydroxyl equivalent 40,000 g/eq.) were added while purging the flask equipped with a thermometer, cooling tube, and stirrer with nitrogen gas. , Karenz (Karenz) MOI (manufactured by Showa Denko Co., Ltd.) 0.08 parts, reacted at 80° C. for 3 hours while stirring, to obtain a toluene solution of the target compound (S2: solid content 20 wt %). The GPC of the toluene solution of the obtained compound is shown in FIG. 2 . The number average molecular weight Mn of the present compound measured by GPC was 169,000, and the weight average molecular weight Mw was 187,609.

[Example 3, Comparative Example 1 to Comparative Example 2] After mixing the materials according to the ratio shown in Table 1, the resin solution was coated on a polyimide film (Kapton: manufactured by Toray Dupont), and then kept at 120°C for 10 minutes to dry the solvent. Then, it was cured at 250° C. for 2 hours, and various tests were performed. Furthermore, for Comparative Example 2, compounding and kneading were carried out according to the ratio shown in Table 1, and after transfer molding at 175°C, it was cured at 160°C for 2 hours, and then cured at 180°C for 6 hours.

＜Dielectric constant test, dielectric loss tangent test＞ Using a 10 GHz cavity resonator manufactured by ATE Co., Ltd., the test was performed by the cavity resonator perturbation method. The results are shown in Table 1.

[Table 1] Example 3 Comparative example 1 Comparative example 2 Olefin resin S1 100 SA-9000 100 epoxy resin NC-3000-L 100 Phenolic resin GPH-65 74 solvent Toluene 100 imidazole 2E-4MZ 2.6 Thermal radical polymerization initiator DCP 0.02 1 Evaluation results Dielectric constant 2.3 2.5 3.1 Dielectric loss tangent 0.0016 0.0032 0.018 ･SA-9000: Terminal methacrylated polyphenylene ether (manufactured by Saudi Basic Industries Corporation (SABIC)) ･NC-3000-L: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. Co., Ltd.) ･GPH-65: Biphenyl aralkyl type phenolic resin (manufactured by Nippon Kayaku Co., Ltd.) ･2E4MZ: 2-ethyl-4-methylimidazole (hardening accelerator, manufactured by Shikoku Chemicals Co., Ltd.) ･DCP: Dicumyl Peroxide

From the results in Table 1, it was confirmed that Example 3 was excellent in electrical characteristics.

[Example 4, Comparative Example 3 to Comparative Example 4] In order to confirm that the copolymer of the present invention has thermosetting properties, an acetone solubility test of the cured film was implemented. Generally speaking, thermosetting resins will form insoluble and infusible cured products after curing. After preparing each material according to the ratio shown in Table 2, the resin solution was coated on a polyimide film (Kapton: manufactured by Toray Dupont), and then kept at 120°C for 10 minutes to dry the solvent. Then, heating was performed at 250° C. for 2 hours, and it was confirmed whether or not the obtained film was dissolved in acetone. The case where it was not dissolved in acetone was judged as ◯, and the case where it was dissolved in acetone was judged as x, and the results are shown in Table 2.

[Table 2] Example 4 Comparative example 3 Comparative example 4 S1 100 Septon HG252 20 20 toluene 80 80 DCP 0.02 0.02 Evaluation results Solubility ○ x x

From the results in Table 2, it was confirmed that Example 4 was cured under predetermined curing conditions. [Industrial availability]

The compounds of the present invention, curable resin compositions, and cured products thereof are used as insulating materials for electrical and electronic parts (high-reliability semiconductor sealing materials, etc.) and laminates (printed wiring boards, substrates for BGA, build-up substrates, etc.), It is useful for various composite materials represented by carbon fiber reinforced plastic (carbon fiber reinforced plastic, CFRP), coating, 3D printing, etc.

none

FIG. 1 shows a GPC chart of Synthesis Example 1. FIG. 2 shows a GPC chart of Synthesis Example 2.

Claims (7)

A copolymer which is a styrene-based copolymer having a (meth)acryloyl group at a terminal. A copolymer which is a polystyrene-hydrogenated poly(butadiene/isoprene)-polystyrene copolymer having a (meth)acryl group at a terminal. The copolymer as described in claim 1 or claim 2, represented by the following formula (1):

In the formula (1), X represents any one of (A) to (E) described in the following formula (2), R represents a hydrogen atom or a methyl group; j, k, l, m, n are repetition numbers The average value represents a real number from 1 to 100,000; the order of the repeating units enclosed by k and l, or j, m and n is not limited, and the bonding method can be any of alternating, block, and random,

. The copolymer according to claim 3, wherein in the formula (1), X is (A) described in the formula (2). A curable resin composition containing the copolymer described in any one of claim 1 to claim 4. The curable resin composition according to claim 5, which contains a radical polymerization initiator. A cured product obtained by curing the copolymer according to any one of claims 1 to 4, or the curable resin composition according to claim 5 or 6.

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