Curable resin composition for printed wiring board and cured product thereof

Abstract

The present invention provides a copolymer having a (meth)acryloyl group, which exhibits excellent electrical properties and has good curability, a curable resin composition, and a cured product thereof. A styrene-based copolymer having a (meth)acryloyl group at a terminal.

Description

Technical Field

[0001] The present invention relates to a copolymer having a (meth)acryloyl group, a curable resin composition and a cured product thereof, which can be preferably used in semiconductor sealing materials, printed wiring substrates, electrical-electronic parts such as build-up laminates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and three-dimensional (3D) printing applications. Background Art

[0002] In recent years, laminated boards equipped with electrical and electronic components have been required to have a wide range of characteristics and to be more sophisticated due to the expansion of their application areas. The mainstream of existing semiconductor chips is mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs (central processing units)) are mostly mounted on laminated boards made of polymer materials.

[0003] In particular, in semiconductor packages (hereinafter referred to as PKG) used in smart phones, in order to meet the requirements of miniaturization, thinning and high density, the PKG substrate is required to be thinner, but if the PKG substrate is thinner, the rigidity will decrease, so the heating when the PKG is soldered and mounted on the motherboard (printed circuit board (PCB)) will cause large warping and other undesirable conditions. In order to reduce the above-mentioned problems, a PKG substrate material with a high Tg above the soldering mounting temperature is required.

[0004] In addition, the fifth-generation communication system "5G", which is currently being developed at an accelerated pace, is expected to further promote large-capacity and high-speed communications. The demand for low dielectric loss tangent materials is increasing, and at least a dielectric loss tangent of 0.005 or less at 10GHz is required.

[0005] Furthermore, in the automotive field, electronicization is advancing, and sometimes precision electronic equipment is installed near the engine drive unit, which requires a higher level of heat and humidity resistance. SiC semiconductors are beginning to be used in electric vehicles and air conditioners, and the sealing materials for semiconductor elements require extremely high heat resistance, so existing epoxy resin sealing materials are no longer able to cope with it.

[0006] In this context, polymer materials that have both heat resistance and low dielectric loss tangent properties are being studied. For example, Patent Document 1 proposes a composition comprising a maleimide resin and a phenolic resin containing an acrylic group. However, in the case described, since the phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, it cannot be said that the electrical properties are sufficient. In addition, Patent Document 2 discloses an allyl ether resin that uses an allyl group to replace the hydroxyl group. However, the allyl ether resin shows that it causes Claisen Rearrangement at 190°C, and at the general substrate molding temperature of 200°C, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties cannot be satisfied.

[0007] In addition, in recent years, 3D printing has attracted much attention as a method of three-dimensional modeling. In the fields requiring reliability such as aviation, aerospace, automobiles, and connectors of electronic parts used in these, the 3D printing method has begun to be applied. In particular, research on the use of photocurable resins and thermosetting resins in applications represented by stereolithography (SLA) or digital light processing (DLP) is underway. Therefore, in the previous self-mold transfer method, the stability and correctness of the shape are mainly required, but in the use of 3D printing, various properties such as heat resistance, mechanical properties, toughness, flame retardancy, and electrical properties are required, and its material development is underway. In addition, in the case of structural components, the change of properties caused by moisture absorption and the like becomes a topic. At present, acrylic resins or epoxy resins are used in such applications, but their hardened materials contain a large number of ester bonds, ether bonds, and then hydroxyl groups, and the moisture absorption properties are insufficient.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Laid-Open No. 04-359911

[0011] Patent Document 2: International Publication No. 2016 / 002704 Summary of the invention

[0012] Problems to be solved by the invention

[0013] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a copolymer having a (meth)acryloyl group, a curable resin composition, and a cured product thereof, which exhibit excellent electrical properties and have good curability.

[0014] Technical means of solving problems

[0015] The present inventors have conducted intensive studies to solve the above problems and have found that a (meth)acrylate compound having a specific structure and a curable resin composition thereof have excellent low dielectric properties in a cured product, thereby completing the present invention.

[0016] That is, the present invention relates to the following [1] to [7]. In the present application, "(numerical value 1) to (numerical value 2)" means that the upper and lower limits are included, and the so-called "(meth)acryloyl group" means "acryloyl group" and / or "methacryloyl group". [1]

[0018] A styrene-based copolymer having a (meth)acryloyl group at a terminal. [2]

[0020] A polystyrene-hydrogenated poly(butadiene / isoprene)-polystyrene copolymer having a (meth)acryloyl group at a terminal. [3]

[0022] The copolymer according to the above item [1] or [2] is represented by the following formula (1).

[0023] [Chemistry 1]

[0024]

[0025] (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 average values ​​of the number of repetitions, and represent real numbers from 1 to 100,000. The order of each repeating unit enclosed by k and l, or j, m, and n is not limited, and the bonding method may be any of alternating, block, and random.)

[0026] [Chemistry 2]

[0027] [4]

[0029] The copolymer according to the above item [3], wherein in the formula (1), X is (A) described in the formula (2). [5]

[0031] A curable resin composition comprising the copolymer according to any one of the above items [1] to [4]. [6]

[0033] The curable resin composition according to the aforementioned item [5], further comprising a radical polymerization initiator. [7]

[0035] A cured product obtained by curing the copolymer according to any one of the above items [1] to [4] or the curable resin composition according to the above item [5] or [6].

[0036] Effects of the Invention

[0037] The copolymer having a (meth)acryloyl group of the present invention has excellent curability, and its cured product has excellent low dielectric properties, and is therefore a useful material for sealing of electric and electronic parts, circuit boards, carbon fiber composites, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The GPC chart of Synthesis Example 1 is shown.

[0039] Figure 2 The GPC chart of Synthesis Example 2 is shown. DETAILED DESCRIPTION

[0040] The present invention relates to a styrene-based copolymer having a (meth)acryloyl group at a terminal (hereinafter referred to as the copolymer of the present invention).

[0041] The term "having a (meth)acryloyl group at a terminal" means having a (meth)acryloyl group at one terminal or both terminals of the copolymer, and preferably having a (meth)acryloyl group at one terminal.

[0042] The styrene-based copolymer is not particularly limited as long as it is a copolymer having a styrene structure, and examples thereof include styrene-butadiene copolymers, styrene-isoprene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-butyl acrylate copolymers, etc. A preferred copolymer is polystyrene-hydrogenated poly(butadiene / isoprene)-polystyrene copolymer.

[0043] The method for synthesizing the copolymer of the present invention is not particularly limited, and the copolymer can be derived from a styrene-based copolymer having a hydroxyl group at a terminal and an acid chloride having a (meth)acryloyl group or an isocyanate having a (meth)acrylate group.

[0044] Specifically, it can be obtained by reacting an acid chloride having a (meth) acryloyl group or an isocyanate having a (meth) acryloyl group with a polystyrene-hydrogenated poly (butadiene / isoprene)-polystyrene copolymer having a hydroxyl group at the end in a solvent. At this time, the number of moles of the acid chloride (or isocyanate) as the reaction object is preferably 0.80 to 1.20, more preferably 0.90 to 1.10, and further preferably 0.95 to 1.05 relative to the hydroxyl group contained in the raw material. In the region outside the range, polar groups such as hydroxyl groups derived from the remaining raw materials may deteriorate the electrical properties.

[0045] As the solvent used, for example, aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; non-water-soluble solvents such as ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more thereof may be used in combination. In addition, in addition to the non-water-soluble solvents, non-protonic polar solvents may also be used in combination. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. may be listed, and two or more thereof may also be used in combination. Among the above, it is preferred to use hydrocarbon solvents such as toluene, xylene, hexane, and cyclohexane.

[0046] In the case of implementing the esterification reaction using an acid chloride, in order to capture the generated hydrogen chloride, a basic compound such as triethylamine may be used alone or in combination as needed. As the amount added, relative to 1 mole of the acid chloride used, it is preferably in the range of 0.1 to 10 moles, more preferably 0.5 to 5 moles, and further preferably 0.9 to 4.0 moles. If it is below the lower limit of the range, the generated hydrogen chloride cannot be fully captured. If it is above the upper limit of the range, the amount of waste will increase, so it is not preferred in industry.

[0047] In the case of implementing the carbamate formation using an isocyanate compound, it can be implemented without a catalyst or using a carbamate formation catalyst. As the carbamate formation catalyst, there is no particular limitation, and examples thereof include: nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate, and tin octoate; organic metal compounds such as dibutyltin dilaurate, etc. In the case of using a carbamate formation catalyst, the addition amount is preferably in the range of 0.001 mol to 10 mol, more preferably 0.01 mol to 5.0 mol, and further preferably 0.05 mol to 4.0 mol, relative to 1 mol of the isocyanate compound used. If it is below the lower limit of the range, the reaction rate may decrease. If it is above the upper limit of the range, the amount of waste will increase, so it is not preferred in industry.

[0048] After the reaction is completed, a washing step may be performed before the solvent is distilled off as needed. In addition, in the case of salts, the solvent may be removed by filtration and then distilled off. The target compound may be obtained by distilling off the solvent after the purification steps such as washing or filtration are performed as needed.

[0049] As the polystyrene-hydrogenated poly(butadiene / isoprene)-polystyrene copolymer having a hydroxyl group at the end, any copolymer can be used as long as it is an existing copolymer, and examples thereof include Septon HG252 (manufactured by Kuraray Co., Ltd.). Septon HG252 (manufactured by Kuraray Co., Ltd.) is a polystyrene-hydrogenated poly(butadiene / isoprene)-polystyrene copolymer having a hydroxyl group at one end.

[0050] As an acid chloride having a (meth) acryloyl group or an isocyanate having a (meth) acryloyl group, any existing isocyanate can be used. Specifically, for example, acryloyl chloride, methacryloyl chloride, 2-isocyanatoethyl methacrylate (Karenz MOI: manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Karenz AOI: manufactured by Showa Denko Co., Ltd.), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz MOI-EG: manufactured by Showa Denko Co., Ltd.), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI: manufactured by Showa Denko Co., Ltd.), etc. From the viewpoint of improving heat resistance and compatibility, it is preferred to use a compound having a methacrylic group. For example, the methacryloyl chloride, 2-isocyanatoethyl methacrylate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate listed above are examples of preferred compounds.

[0051] The copolymer of the present invention is particularly preferably represented by the following formula (1).

[0052] [Chemistry 3]

[0053]

[0054] (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 average values ​​of the number of repetitions, and represent real numbers from 1 to 100,000. The order of each repeating unit enclosed by k and l, or j, m, and n is not limited, and the bonding method may be any of alternating, block, and random.)

[0055] [Chemistry 4]

[0056]

[0057] j, k, l, m, and n are usually 1 to 100000, preferably 1 to 90000, and more preferably 1 to 80000. The order of the repeating units enclosed by k and l, or j, m, and n is not limited, and the bonding pattern is preferably random.

[0058] The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 1000 or more and less than 500000, more preferably 2500 or more and less than 400000, and particularly preferably 5000 or more and less than 300000. The number average molecular weight (Mn) of the copolymer of the present invention is preferably 1000 or more and less than 500000, more preferably 2500 or more and less than 400000, and particularly preferably 5000 or more and less than 300000. If the number average molecular weight or weight average molecular weight is less than 500000, the compatibility with other resins becomes good, and if it is 1000 or more, the target compound will not volatilize during the solvent distillation removal step or the B-stage of the composition.

[0059] In the above formula (1), X is preferably any one of (A) to (C) or (E) described in the above formula (2), and is particularly preferably (A).

[0060] R represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving heat resistance and compatibility.

[0061] The curable resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability can be improved and the reaction start temperature can be controlled. By controlling the reaction start temperature, it is easy to ensure fluidity, and it becomes easy to perform B-stage such as prepreg without impairing the impregnation property in glass fiber cloth, etc. If the polymerization reaction proceeds excessively during prepreg, it is easy to cause disadvantages such as lamination becoming difficult in the lamination process.

[0062] As polymerization inhibitors that can be used, there are phenolic, sulfur, phosphorus, hindered amine, nitroso, nitroxyl free radical and other polymerization inhibitors. The polymerization inhibitor can be added when synthesizing the compound represented by the formula (1), or it can be added after the synthesis. In addition, the polymerization inhibitor can be used alone or in combination of two or more. The amount of the polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, relative to 100 parts by weight of the resin component. These polymerization inhibitors can be used alone or in combination of two or more. In the present invention, phenolic, hindered amine, nitroso, and nitroxyl free radical are preferred.

[0063] Specific examples of phenolic polymerization inhibitors include monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, 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, and 2,4-bis[(octylthio)methyl]-o-cresol; and 2,2′-methylenebis(4 -methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(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-hydrocinnamic acid), 2,2-thiobis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(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-hydrocinnamic acid), bisphenols such as bis(3,5-di-tert-butyl-4-hydroxybenzyl sulfonate), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-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, and calcium bis(3,5-di-tert-butyl-4-hydroxybenzyl sulfonate); 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5- High molecular weight phenols such as 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-butylphenyl)butyrate]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, and tocopherol.

[0064] Specific examples of the sulfur-based polymerization inhibitor include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

[0065] Specific examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butyl-4-methylphenyl)phosphite. , phosphites such as bis[2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0066] Specific examples of hindered amine 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 LA-77G, Adekastab LA-72, Adekastab LA-68, Adekastab LA-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc., but not limited to these.

[0067] Specific examples of the nitroso polymerization inhibitor include p-nitrosophenol, N-nitrosodiphenylamine, and ammonium salts of N-nitrosophenylhydroxylamine (cupferron). Among them, ammonium salts of N-nitrosophenylhydroxylamine (cupferron) are preferred.

[0068] Specific examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidin-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-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl, but are not limited to these.

[0069] The curable resin composition of the present invention can use any existing material as the curable resin other than the copolymer of the present invention. Specifically, phenol resin, epoxy resin, amine resin, resin containing active olefin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, acrylic resin, methallyl resin, active ester resin, etc. can be listed. One or more can be used. In addition, in terms of the balance of heat resistance, adhesion, and dielectric properties, it is preferred to contain epoxy resin, resin containing active olefin, and cyanate resin. By containing these curable resins, the brittleness of the hardened material can be improved and the adhesion to the metal can be improved, and the cracks of the package in the reliability test such as solder reflow or hot and cold cycle can be suppressed.

[0070] The amount of the curable resin used is preferably within a mass range of 10 times or less, more preferably within a mass range of 5 times or less, and particularly preferably within a mass range of 3 times or less relative to the compound of the present invention. In addition, the preferred lower limit is 0.5 times or more, more preferably 1 times or more. If it is 10 times or less, the heat resistance or dielectric properties of the compound described in the present invention can be effectively utilized.

[0071] As the phenol resin, epoxy resin, amine resin, active olefin-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, and active ester resin, the phenol resins exemplified below can be used.

[0072] Phenolic resins: polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.); polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, diethylhexane ... Polymers of phenols (such as butylene biphenyl, diisopropyl biphenyl, butadiene, isoprene, etc.); polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); phenol resins obtained by polycondensation of phenols and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), or substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene); polycondensates of bisphenols and various aldehydes; polyphenylene ether compounds.

[0073] As the polyphenylene ether compound, any existing 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 preferred, and a polyphenylene ether compound having an acrylic group, a methacrylic group or a styrene structure is further preferred. As commercially available products, SA-9000-111 (manufactured by Saudi Basic Industries (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) etc. can be cited.

[0074] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. In addition, if the molecular weight is greater than 5000, the melt viscosity becomes high, and sufficient fluidity cannot be obtained, so there is a tendency to be poorly formed. In addition, the reactivity is also reduced, the curing reaction requires a long time, the amount of unreacted substances that do not enter the curing system increases, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease.

[0075] When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to maintain excellent dielectric properties while exhibiting excellent heat resistance and moldability, etc. The number average molecular weight here can be specifically measured using gel permeation chromatography or the like.

[0076] The polyphenylene ether compound may be a compound obtained by polymerization reaction, or a compound obtained by redistributing a polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. In addition, free radical polymerizability may be imparted by reacting these as raw materials with compounds having ethylenically unsaturated double bonds such as methacryloyl chloride, acryloyl chloride, chloromethylstyrene, etc. The polyphenylene ether compound obtained by redistribution reaction may be obtained by, for example, 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 the redistribution reaction has hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain, so that not only higher heat resistance can be maintained, but also functional groups can be introduced at both ends of the molecular chain after modification using a compound having ethylenically unsaturated double bonds, which is preferred in terms of the above aspect. In addition, the polyphenylene ether compound obtained by polymerization reaction shows excellent fluidity, which is preferred in terms of the above aspect.

[0077] 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 the polymerization conditions, etc. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is considered to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the more the amount of the phenolic compound is, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, as a high molecular weight polyphenylene ether compound subjected to the redistribution reaction, poly (2,6-dimethyl-1,4-phenylene ether) can be used. In addition, as the phenolic compound used in the redistribution reaction, there is no particular limitation, and preferably a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc. can be used. These can be used alone or in combination of two or more.

[0078] In addition, the content of the polyphenylene ether compound is not particularly limited, but is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, relative to the total mass of the curable resin component. If the content of the polyphenylene ether compound is 10% to 90% by mass, a cured product having excellent heat resistance and the like and fully utilizing the excellent dielectric properties of the polyphenylene ether compound can be obtained, which is preferred in terms of the above aspect.

[0079] Epoxy resin: the above-mentioned phenol resin; glycidyl ether epoxy resin obtained by glycidylating alcohols; alicyclic epoxy resin represented by 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate; glycidylamine epoxy resin represented by tetraglycidyl diaminodiphenylmethane (TGDDM) or triglycidyl-p-aminophenol; glycidyl ester epoxy resin.

[0080] Amine resin: diaminodiphenylmethane; diaminodiphenyl sulfone; isophoronediamine; naphthalene diamine; aniline novolac; o-ethylaniline novolac; aniline resin obtained by the reaction of aniline with xylylene chloride; aniline resin obtained by the reaction of aniline described in Japanese Patent No. 6429862 with 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.).

[0081] Resins containing active olefins: polycondensates of the phenol resin and halogen compounds containing active olefins (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, etc.); polycondensates of 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, etc.) condensation products; condensation products of epoxy resins or alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.); maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, metaphenylene bismaleimide, 2,2'-bis[4-(4-maleimide) phenylpropane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene), new phenol (Xyloc) type maleimide resin (Annili Anilix maleimide, manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), biphenyl aralkyl type maleimide resin (solidified by removing the solvent from the resin solution containing maleimide resin (M2) described in Example 4 of Japanese Patent Publication No. 2009-001783 under reduced pressure), bisaminocumylbenzene type maleimide (maleimide resin described in International Publication No. 2020 / 054601).

[0082] Isocyanate resin: aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc.; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, etc.; polyisocyanates such as biuret forms of one or more isocyanate monomers or isocyanate forms obtained by trimerizing the diisocyanate compounds; polyisocyanates obtained by urethanization reaction of the isocyanate compounds with polyol compounds.

[0083] Polyamide resin: selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanealactam, ω-laurolactam) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, etc.); cyclopentanediamine alicyclic diamines such as hexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylene diamine; and a mixture of dicarboxylic acids (aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids) as main raw materials.

[0084] Polyimide resin: the diamine and tetracarboxylic acid dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylene-4,4'-diphthalic acid dianhydride, 2,2'-propylene-4,4 '-Diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic dianhydride, 1,4-bis[ 2-(3,4-dicarboxyphenyl)-2-propyl]phthalic 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-naphthalenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, 2,3,6, 7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic 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 acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride) polycondensate.

[0085] Cyanate resin: a cyanate compound obtained by reacting a phenol resin with a cyanogen halide, and specific examples thereof include dicyanatobenzene, tricyanatobenzene, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl)sulfide, phenol novolac cyanate, and a compound obtained by converting a hydroxyl group of a phenol-dicyclopentadiene co-condensate into a cyanate group, but the present invention is not limited thereto. In addition, the cyanate compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferred as the cyanate compound because of its low hygroscopicity, flame retardancy, and excellent dielectric properties.

[0086] In order to trimerize the cyanate group to form a s-triazine ring as needed, the cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, etc. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the curable resin composition.

[0087] Active ester resin: A compound having one or more active ester groups in one molecule may be used as a hardener for curable resins other than the compound represented by the formula (1) of the present invention such as epoxy resins, as needed. As active ester hardeners, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are preferred. The active ester hardener is preferably obtained by a condensation reaction of at least 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, an active ester hardener obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester hardener obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound is preferred.

[0088] 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.

[0089] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated 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, pyroglucinol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

[0090] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" means a divalent structural unit containing phenylene-dicyclopentylene-phenylene.

[0091] Examples of commercially available active ester hardeners include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC Corporation), which are active ester compounds containing a naphthalene structure. ; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener for an acetylated product of phenol novolac; "EXB-9050L-62M" manufactured by DIC Corporation as an active ester hardener containing a phosphorus atom, etc.

[0092] The curable resin composition of the present invention may also be used in combination with a curing accelerator (curing catalyst) to improve the curability. As a specific example of the curing accelerator that can be used, a free radical polymerization initiator is preferably used to promote the self-polymerization of a curable resin that can be free radically polymerized, such as an olefin compound or a maleimide resin, or the free radical polymerization with other components. Examples of the free radical polymerization initiator that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxyketals such as tert-butyl peroxybenzoate and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylbutyl peroxy The present invention can be used as an existing curing accelerator of an organic peroxide such as tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-amyl peroxybenzoate, etc., but is not particularly limited thereto. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxycarbonates, etc. are preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight cannot be sufficiently increased during the polymerization reaction.

[0093] In addition, a hardening accelerator other than the free radical polymerization initiator may be added or used in combination as needed. Specific examples of hardening accelerators that can be used include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, and 1,8-diazabicyclo(5,4,0)undecene-7; triphenylphosphine, tri(toluoyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate Phosphine or phosphonium compounds, organic phosphine such as tributylphosphine, metal compounds such as tin octoate, tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate and other tetrasubstituted phosphonium-tetrasubstituted borates, 2-ethyl-4-methylimidazole-tetraphenylborate, N-methylmorpholine-tetraphenylborate and other tetraphenylboron salts, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, salicylic acid and other carboxylic acid compounds, etc. From the viewpoint of promoting the curing reaction of the amine compound and the epoxy resin, a carboxylic acid compound such as salicylic acid is preferred. The curing accelerator is used in an amount of 0.01 to 15 parts by weight relative to 100 parts by weight of the epoxy resin as needed.

[0094] The curable resin composition of the present invention may also contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive compound or an additive compound. Specific examples of phosphorus-containing compounds include: trimethyl phosphate, triethyl phosphate, tritolyl phosphate, tri(xylyl) phosphate, tolyl diphenyl phosphate, tolyl-2,6-di(xylyl) phosphate, 1,3-phenylene bis(di(xylyl) phosphate), 1,4-phenylene bis(di(xylyl) phosphate), 4,4'-biphenyl(di(xylyl) phosphate) and other phosphates; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-( Phosphanes such as 2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with active hydrogen of the above-mentioned phosphanes, red phosphorus, etc., preferably phosphates, phosphanes or phosphorus-containing epoxy compounds, and particularly preferably 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4'-biphenyl(di(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) of 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, there is a risk of adversely affecting the hygroscopicity and dielectric properties of the cured product.

[0095] Furthermore, a light stabilizer may be added to the curable resin composition of the present invention as needed. The light stabilizer is preferably a hindered amine light stabilizer, and particularly preferably a hindered amine light stabilizer (HALS). The HALS is not particularly limited, and typical examples include a condensation product of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a condensation product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidyl, and poly{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2, HALS may be used alone or in combination of two or more.

[0096] Furthermore, in the curable resin composition of the present invention, a binder resin may be formulated 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 resins, polyamide resins, polyimide resins, silicone resins, etc., but are not limited to these. The amount of the binder resin formulated is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass relative to 100 parts by mass of the resin component, and more preferably 0.05 to 20 parts by mass as needed.

[0097] Furthermore, in the curable resin composition of the present invention, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, glass powder and other powders, or inorganic fillers in the form of spheres or crushed forms thereof may be added as needed. In addition, in particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used in the curable resin composition is usually in the range of 80% to 92% by mass, preferably 83% to 90% by mass.

[0098] In the curable resin composition of the present invention, existing additives may be formulated as needed. Specific examples of usable additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine green and other colorants. The amount of these additives formulated is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, relative to 100 parts by mass of the curable resin composition. From the viewpoint of low water absorption and electrical properties, polybutadiene and modified products thereof, polyphenylene ether, polystyrene, polyethylene, fluororesin and the like are preferred. From the viewpoint of electrical properties, adhesion and low water absorption, polybutadiene and modified products thereof are preferred. Specifically, for example, butadiene-based thermoplastic elastomers such as styrene butadiene copolymers (SBR: RICON-100, RICON-181, and RICON-184 are all manufactured by Cray Valley, etc.), acrylonitrile butadiene copolymers, and styrene-based thermoplastic elastomers such as styrene butadiene styrene copolymers (SBS), hydrogenated styrene butadiene styrene copolymers, styrene isoprene styrene copolymers (SIS), hydrogenated styrene isoprene styrene copolymers, and hydrogenated styrene (butadiene / isoprene) styrene copolymers can be used alone or in combination of two or more. Among these high molecular weight bodies, preferred are styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene-(butadiene / isoprene)-styrene copolymers. In particular, styrene-isoprene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene-(butadiene / isoprene)-styrene copolymers are more preferred because they have higher heat resistance and are less susceptible to oxidative degradation.Specifically, they are Septon 1020, Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, Septon 4003, Septon 4044, Septon 4055, Septon 40 77. Septon 4099, Septon 8004, Septon 8006, Septon 8007L, Septon HG252, Septon V9827, Hybrar 7125 (hydrogenated), Hybrar 7215F, Hybrar 7311F (all manufactured by Kuraray Co., Ltd.). The weight average molecular weight of the styrene-based thermoplastic elastomer is not particularly limited as long as it is 10,000 or more. However, if it is too large, the compatibility with low molecular weight components having a weight average molecular weight of about 50 to 1,000 and oligomer components having a weight average molecular weight of about 1,000 to 5,000, in addition to the polyphenylene ether compound, deteriorates, and it becomes difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0099] The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at a predetermined ratio, and generally pre-curing at 130° C. to 180° C. for 30 seconds to 500 seconds, and then post-curing at 150° C. to 200° C. for 2 hours to 15 hours, thereby allowing a sufficient curing reaction to obtain a 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 then cured after removing the solvent.

[0100] The curable resin composition of the present invention obtained in the above manner has moisture resistance, heat resistance, and high adhesion. 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 adhesion. Specifically, it can be effectively used as all materials for electrical and electronic parts such as insulating materials, laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), sealing materials, and resists. In addition to molding materials and composite materials, it can also be used in the fields of coating materials, adhesives, 3D printing, etc. In particular, in semiconductor sealing, solder reflow resistance is beneficial.

[0101] The semiconductor device has a device sealed with the curable resin composition of the present invention. Examples of the semiconductor device include dual in-line package (DIP), quad flat package (QFP), ball grid array (BGA), chip size package (CSP), small outline package (SOP), thin small outline package (TSOP), and thin quad flat package (TQFP).

[0102] The preparation method of the curable resin composition of the present invention is not particularly limited, and the components may be simply mixed uniformly, or prepolymerized. For example, the curable resin of the present invention may be heated in the presence or absence of a catalyst, in the presence or absence of a solvent, thereby prepolymerizing. Similarly, in addition to the curable resin of the present invention, curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenol resins, acid anhydride compounds, and other additives may be added to prepolymerize. For mixing or prepolymerizing the components, for example, an extruder, a kneader, a roller, etc. are used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.

[0103] As a method of uniform mixing, the resin composition can be uniformly mixed by mixing at a temperature in the range of 50°C to 100°C using a kneader, a roller, a planetary mixer or the like. The obtained resin composition can be crushed and then molded into a cylindrical ingot using a molding machine such as a tablet machine, or into a granular powder or a powdery molded body, or the composition can be melted on a surface support and molded into a sheet with a thickness of 0.05mm to 10mm to form a curable resin composition molded body. The obtained molded body is a non-sticky molded body at 0°C to 20°C, and the fluidity and curability are hardly reduced even if stored at -25°C to 0°C for more than 1 week.

[0104] The obtained molded body can be molded into a hardened product using a transfer molding machine or a compression molding machine.

[0105] An organic solvent may be added to the curable resin composition of the present invention to prepare a varnish-like composition (hereinafter referred to as varnish). The curable resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to prepare a varnish as needed, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heated and dried, and the obtained prepreg is hot-pressed to prepare a cured product of the curable resin composition of the present invention. The solvent used in this case is usually 10% to 70% by weight, preferably 15% to 70% by weight, in the mixture of the curable resin composition of the present invention and the solvent. In addition, if it is a liquid composition, a cured product of a curable resin containing carbon fibers may be obtained directly, for example, by resin transfer molding (RTM).

[0106] In addition, the curable composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is obtained by preparing the curable resin composition of the present invention into the curable resin composition varnish and applying it on a release film, removing the solvent under heating, and then performing B-stage, thereby obtaining a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate, etc.

[0107] The curable resin composition of the present invention can be heated and melted, reduced in viscosity, and impregnated into 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 inorganic fibers other than glass or polyparaphenyleneterephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited to these. The shape of the substrate is not particularly limited, and for example, woven fabrics, non-woven fabrics, rovings, chopped strand mats, etc. can be listed. In addition, as the weaving method of the woven fabric, plain weave, basket weave, twill weave, etc. are known, and can be appropriately selected from these existing weaving methods according to the target use or performance. In addition, glass woven fabrics that have been subjected to fiber opening treatment or surface treatment using a silane coupling agent or the like can be preferably used. The thickness of the substrate is not particularly limited, and is preferably about 0.01 mm to 0.4 mm. In addition, the prepreg can also be obtained by impregnating the varnish into the reinforcing fiber and heating and drying it.

[0108] The laminate of the present embodiment includes more than one prepreg. The laminate is not particularly limited as long as it is a laminate including more than one prepreg, and may also have any other layer. As a manufacturing method of the laminate, a generally existing method can be appropriately applied without particular limitation. For example, when forming a laminate with a metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used, and a laminate can be obtained by stacking the prepregs on each other and performing heating and pressurizing. At this time, the heating temperature is not particularly limited, preferably 65°C to 300°C, and more preferably 120°C to 270°C. In addition, the pressure of the pressurization is not particularly limited. If the pressure is too large, the solid content of the resin of the laminate is difficult to adjust, and the quality is unstable. In addition, if the pressure is too small, the air bubbles or the adhesion between the layers deteriorate, so it is preferably 2.0MPa to 5.0MPa, and more preferably 2.5MPa to 4.0MPa. The laminated plate of the present embodiment includes a layer having a metal foil, and can be preferably used as a metal foil clad laminated plate described later.

[0109] The prepreg is cut into a desired shape, and after being laminated with copper foil or the like as needed, the curable resin composition is heated and cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like, thereby obtaining an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0110] The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and coatings. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, and can therefore be preferably used in semiconductor element sealing materials, liquid crystal display element sealing materials, organic electroluminescence (EL) element sealing materials, printed wiring boards, build-up laminates and other electrical and electronic parts, or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

[0111] Example

[0112] Next, the present invention will be described in more detail by way of examples. Hereinafter, parts are parts by mass unless otherwise specified. In addition, the present invention is not limited to these examples.

[0113] Various analytical methods used in the Examples are described below.

[0114] <Weight average molecular weight (Mw), number average molecular weight (Mn)>

[0115] Calculate by polystyrene conversion using a polystyrene standard solution.

[0116] Gel permeation chromatograph (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0117] Column: Shodex KF-603, KF-602×2, KF-601×2

[0118] Linking eluent: tetrahydrofuran

[0119] Flow rate: 0.5ml / min.

[0120] Column temperature: 40℃

[0121] Detector: RI (differential refractometer)

[0122] [Example 1]

[0123] While nitrogen was flushed into a flask equipped with a thermometer, a cooling tube, a stirrer, and an aspirator (via an alkali trap), 100 parts of toluene, 20 parts of Septon HG252 (manufactured by Kuraray Co., Ltd., hydroxyl equivalent 40000 g / eq.), and 0.05 parts of methacrylic chloride were added, and the mixture was reacted at 25°C for 2 hours, at 60°C for 3 hours, and at 70°C for 12 hours while stirring to obtain a toluene solution of the target compound (S1: solid content 20 wt%). GPC of the toluene solution of the obtained compound was shown in Figure 1 The number average molecular weight Mn and weight average molecular weight Mw of the compound measured by GPC were 118709 and 131690, respectively.

[0124] [Example 2]

[0125] While nitrogen was flushed into a flask equipped with a thermometer, a cooling tube, and a stirrer, 100 parts of toluene, 20 parts of Septon HG252 (manufactured by Kuraray Co., Ltd., hydroxyl equivalent 40000 g / eq.), and 0.08 parts of Karenz MOI (manufactured by Showa Denko Co., Ltd.) were added, and the mixture was reacted at 80° C. for 3 hours while stirring to obtain a toluene solution of the target compound (S2: solid content 20 wt%). GPC of the toluene solution of the obtained compound is shown in Figure 2 The number average molecular weight Mn and weight average molecular weight Mw of the compound measured by GPC were 169,000 and 187,609, respectively.

[0126] [Example 3, Comparative Example 1-Comparative Example 2]

[0127] After each material was prepared in the ratio shown in Table 1, the resin solution was applied to a polyimide film (Kapton: manufactured by Toray Dupont), and then the solvent was dried at 120°C for 10 minutes. Then, it was cured at 250°C for 2 hours, and various tests were performed. In addition, for Comparative Example 2, it was prepared and kneaded in the ratio shown in Table 1, transfer-molded at 175°C, and then cured at 160°C for 2 hours and at 180°C for 6 hours.

[0128] <Dielectric constant test, dielectric loss tangent test>

[0129] The test was conducted using a 10 GHz cavity resonator manufactured by ATE Co., Ltd. using the cavity resonator perturbation method. The results are shown in Table 1.

[0130] [Table 1]

[0131]

[0132] ■SA-9000: terminal methacrylated polyphenylene ether (manufactured by Saudi Basic Industries Corporation (SABIC))

[0133] ■NC-3000-L: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)

[0134] ■GPH-65: Biphenyl aralkyl type phenol resin (manufactured by Nippon Kayaku Co., Ltd.)

[0135] ■2E4MZ: 2-ethyl-4-methylimidazole (hardening accelerator, manufactured by Shikoku Chemical Co., Ltd.)

[0136] ■DCP: dicumyl peroxide

[0137] From the results in Table 1, it was confirmed that Example 3 had excellent electrical characteristics.

[0138] [Example 4, Comparative Example 3 to Comparative Example 4]

[0139] In order to confirm that the copolymer of the present invention has thermosetting properties, an acetone solubility test of the cured film is performed. Generally speaking, thermosetting resins will generate insoluble and infusible cured materials after curing. After allocating each material in the proportion shown in Table 2, the resin solution is applied on a polyimide film (Kapton: manufactured by Toray Dupont), and then the solvent is dried at 120°C for 10 minutes. Then, it is heated at 250°C for 2 hours, and then it is confirmed whether the obtained film is dissolved in acetone. The case of insolubility in acetone is judged as ○, and the case of dissolution in acetone is judged as ×, and the results are shown in Table 2.

[0140] [Table 2]

[0141]

[0142]

[0143] From the results in Table 2, it was confirmed that Example 4 was cured under the prescribed curing conditions.

[0144] Industrial Applicability

[0145] The compounds, curable resin compositions and cured products thereof of the present invention are useful in applications such as insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.), laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.) or various composite materials represented by carbon fiber reinforced plastics (CFRP), coatings, 3D printing, and the like.

Claims

1. A curable resin composition for a printed wiring board, comprising a copolymer represented by the following formula (1) having a weight average molecular weight of 1,000 or more and less than 500,000 as measured by gel permeation chromatography, In formula (1), X represents any one of (A) to (E) described in formula (2) below, R represents a hydrogen atom or a methyl group; j, k, l, m, and n are average values ​​of the number of repetitions, and represent real numbers ranging from 1 to 100,000; the order of each repeating unit enclosed by k and l, or j, m, and n is not limited, and the bonding method may be any one of alternating, block, and random. 2 . The curable resin composition for a printed wiring board according to claim 1 , wherein in the formula (1), X is (A) described in the formula (2).

3. The curable resin composition for a printed wiring board according to claim 1, wherein the copolymer represented by the formula (1) is obtained by reacting a polystyrene-hydrogenated poly(butadiene / isoprene)-polystyrene copolymer having a hydroxyl group at one end with an acid chloride having a (meth)acryloyl group or an isocyanate having a (meth)acryloyl group. 4 . The curable resin composition for a printed wiring board according to claim 1 , further comprising a radical polymerization initiator. 5 . A cured product obtained by curing the curable resin composition for a printed wiring board according to claim 1 .

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