JP2021143333A - Olefin resin, curable resin composition and cured product thereof - Google Patents

Abstract

To provide an olefin resin having excellent heat resistance, electric characteristics, and curability, a curable resin composition and a cured product thereof.SOLUTION: The present disclosure provides an olefin resin of a specific structure of formula (2). (l, m, n independently represent a real number of 0-20, and 1≤l+m+n≤20. R independently represent a hydrogen atom, a C1-10 hydrocarbon group, or a halogenated alkyl group. p is a real number of 0-4, and q is a real number of 0-3. (a), (b), (c) are bound to one another with *, and their repetition positions may be random.)SELECTED DRAWING: None

Description

The present invention relates to an olefin resin having a specific structure, a curable resin composition using the same, and a cured product thereof. Lightweight and high-strength materials such as fiber-reinforced plastics and glass fiber-reinforced plastics are suitably used for 3D printing applications.

In recent years, the required characteristics of laminated boards on which electrical and electronic components are mounted have become widespread and sophisticated due to the expansion of their fields of use. Conventional semiconductor chips are mainly mounted on metal lead frames, but semiconductor chips with high processing capacity such as central processing units (hereinafter referred to as CPUs) in recent years are laminated made of polymer materials. It is becoming more and more mounted on boards.

In particular, in semiconductor packages used for smartphones and the like (hereinafter referred to as PKG), in order to meet the demands for miniaturization, thinning and high density, thinning of the PKG substrate is required, but the PKG substrate is used. Since the rigidity decreases as the thickness becomes thinner, problems such as large warpage occur due to heating when the PKG is solder-mounted on the motherboard (PCB). In order to reduce this, a PKG substrate material having a high Tg equal to or higher than the solder mounting temperature is required.

In addition, in the 5th generation communication system "5G" whose development is currently accelerating, it is expected that the capacity will be further increased and high-speed communication will be promoted. Therefore, the need for a low dielectric loss tangent material is increasing more and more, and a dielectric loss tangent of 0.005 or less is required at least at 1 GHz, which cannot be met by a conventional epoxy resin encapsulant.

Against this background, polymer materials that can achieve both heat resistance and low dielectric loss tangent properties have been studied. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenol resin. However, on the other hand, since phenolic hydroxyl groups that are not involved in the reaction remain during the curing reaction, it cannot be said that the electrical characteristics are sufficient. Further, Patent Document 2 discloses an allyl ether resin in which a hydroxyl group is substituted with an allyl group. However, it has been shown that the Claisen rearrangement occurs at 190 ° C., and at 200 ° C., which is a general substrate molding temperature, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so that the electrical characteristics cannot be satisfied. No.

In recent years, 3D printing has been attracting attention as a three-dimensional modeling method, and this 3D printing method is applied in fields where reliability is required, such as aerospace, cars, and connectors for electronic components used in them. Is beginning to be done. In particular, photocurable and thermosetting resins are being studied for applications typified by stereolithography (SLA) and digital light processing (DLP). Therefore, in the conventional method of transferring from a mold, shape stability and accuracy are mainly required, but in 3D printing applications, heat resistance, mechanical properties, toughness, flame retardancy, and electrical properties are required. Various properties such as these are required, and the material development is underway. Further, when it is used for a structural member, a change in characteristics due to moisture absorption or the like has become an issue. Currently, acrylate resins and epoxy resins are applied in such applications, but their cured products contain a large number of ester bonds, ether bonds, and hydroxyl groups, and their properties in moisture absorption are not sufficient.

Japanese Unexamined Patent Publication No. 04-359911 International Publication 2016/002704

The present invention has been made in view of such a situation, and provides an olefin resin, a curable resin composition, and a cured product thereof, which exhibit excellent heat resistance and electrical properties and have good curability. The purpose.

As a result of diligent research to solve the above problems, the present inventors have found that a cured product containing a novel olefin resin is excellent in heat resistance and low dielectric properties, and have completed the present invention.

That is, the present invention relates to the following [1] to [10].
[1]
An olefin resin represented by the following formula (1).

(In equation (1), A is represented by equation (2).)

(In the formula (2), l, m, and n each independently represent a real number of 0 to 20, and 1 ≦ l + m + n ≦ 20, respectively. R is a hydrogen atom and a hydrocarbon having 1 to 10 carbon atoms, respectively. Represents a group or an alkyl halide group. P represents a real number from 0 to 4, q represents a real number from 0 to 3. (a), (b), and (c) are each bonded by * and a repeating position. May be random. It is also attached with * to the isopropenyl group of the formula (1).)
[2]
The olefin resin according to the previous item [1], wherein in the formula (2), 1.1 ≦ l + m + n ≦ 20.
[3]
The olefin resin according to the previous item [1] or [2], wherein R is a hydrogen atom in the above formula (2).
[4]
The olefin resin according to any one of the above items [1] to [3], which is derived from a diisopropenylbenzene compound.
[5]
The olefin resin according to any one of the above items [1] to [3], which is derived from 1,3-diisopropenylbenzene.
[6]
The olefin resin according to any one of the above items [1] to [5], wherein the weight average molecular weight determined by the measurement of gel permeation chromatography is 200 or more and less than 5000.
[7]
A curable resin composition containing the olefin resin according to any one of the above items [1] to [6] and a polymerization inhibitor.
[8]
A curable resin composition containing the olefin resin according to any one of the above items [1] to [6] and a curable resin other than the olefin resin.
[9]
The curable resin composition according to the above item [7] or [8], which further contains a curing accelerator.
[10]
A cured product obtained by curing the olefin resin according to any one of the preceding items [1] to [6] and the curable resin composition according to any one of the preceding items [7] to [9].

The olefin resin of the present invention has excellent curability, and the cured product has excellent properties of high heat resistance and low dielectric properties. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, and the like.
Further, since the olefin resin of the present invention has excellent reactivity, it is one of the preferable embodiments to cure it alone.

The GPC chart of Example 1 is shown. The 1 ¹ H-NMR chart of Example 1 is shown. The GPC chart of Example 2 is shown. ^{The 1 1} H-NMR chart of Example 2 is shown. The GPC chart of Example 3 is shown. The GPC chart of Example 4 is shown.

The olefin compound of the present invention is represented by the following formula (1).

(In equation (1), A is represented by equation (2).)

(In the formula (2), l, m, and n each independently represent a real number of 0 to 20, and 1 ≦ l + m + n ≦ 20, respectively. R is a hydrogen atom and a hydrocarbon having 1 to 10 carbon atoms, respectively. Represents a group or an alkyl halide group. P represents a real number from 0 to 4, q represents a real number from 0 to 3. (a), (b), and (c) are each bonded by * and a repeating position. May be random. It is also attached with * to the isopropenyl group of the formula (1).)

In the formula (2), p is usually a real number from 0 to 4, preferably 0 to 3, and more preferably 0. q is usually a real number from 0 to 3, preferably 0 to 2, and even more preferably 0.
R is usually a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkyl halide group, preferably a hydrogen atom, or a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a hydrogen atom. It is a hydrocarbon group having 1 to 3 carbon atoms. When R is a hydrogen atom or a hydrocarbon having 3 or less carbon atoms, molecular vibration is unlikely to occur when exposed to a high frequency, so that the electrical characteristics are excellent.

In the above formula (2), l, m, and n are independent real numbers, usually 0 to 20, and satisfy 1 ≦ l + m + n ≦ 20. The sum of l, m, and n is preferably 1.1 ≦ l + m + n ≦ 20, more preferably 1.1 ≦ l + m + n ≦ 10, and particularly preferably 1.1 ≦ l + m + n ≦ 5. Therefore, the olefin resin of the present invention may be a polymer having a single structure of only one of (a), (b), and (c).

The olefin resin of the present invention preferably has a weight average molecular weight (Mw) of 200 or more and less than 5000, and preferably 300 or more and less than 3000, as determined by gel permeation chromatography (GPC) measurement. It is more preferable, and it is particularly preferable that it is 400 or more and less than 2000. If the weight average molecular weight is less than 5000, purification by washing with water becomes easy, and if it is 200 or more, the target compound does not volatilize in the solvent distillation step.

The olefin resin of the present invention can be represented by, for example, the following formula (3).

In formula (3), l, m, n, R, p, and q are the same as in formula (2). Although each repeating unit is shown in a specific order for convenience of description, each repeating unit exists in no particular order, and those in no particular order are also included in the present application. Specifically, the structure of each repeating unit may be random copolymerized or block copolymerized. Further, it may be a polymer having a single structure having only one of the structures of each repeating unit.

The method for producing the olefin resin of the present invention is not particularly limited, but it can be obtained by reacting a diisopropenylbenzene-based compound in the presence of an acidic catalyst. Examples of the solvent that can be used in the reaction include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, and ester solvents such as ethyl acetate and butyl acetate. Examples thereof include water-insoluble solvents such as ketone solvents such as methylisobutylketone and cyclopentanone, but the present invention is not limited to these, and two or more kinds may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent can also be used in combination. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like can be mentioned, and two or more of them may be used in combination. The catalyst is not particularly limited, but the catalyst includes hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acidic clay, white carbon, zeolite, and the like. A solid acid such as silica-alumina, an acidic ion exchange resin, or the like can be used. These may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.0001 to 0.8 mol, preferably 0.0002 to 0.7 mol, based on 1 mol of the diisopropenylbenzene compound used. If the amount of the catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult, and if it is too small, the progress of the reaction may be slowed down and the raw material monomer may remain. The polymerization reaction temperature is −50 to 180 ° C., preferably 0 to 100 ° C. for 0.5 to 60 hours, and more preferably 1 to 30 hours. By carrying out the polymerization reaction in the above range, the amount of the raw material monomer can be reduced below the GPC (gel permeation chromatography: RI) detection limit at the time of the polymerization reaction. Since the raw material monomer does not remain, the production operation such as distillation and reprecipitation becomes unnecessary, which is preferable from the viewpoint of simplifying the manufacturing process and reducing waste, and the generation of volatile matter can be suppressed when producing the cured product. , Can create void-free cured products. After completion of the reaction, the acidic catalyst is neutralized with an alkaline aqueous solution, a water-insoluble organic solvent is added to the oil layer, and washing with water is repeated until the wastewater becomes neutral.

Examples of the diisopropenylbenzene compound include 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and the like, as well as 1,2-bis (α-hydroxyisopropyl). It is also possible to use benzene, 1,3-bis (α-hydroxyisopropyl) benzene, or diisopropenylbenzene obtained by dehydrating 1,4-bis (α-hydroxyisopropyl) benzene, but these can be used. It is not limited. As the substitution position, it is preferable that it is substituted at the 1,4-position or the 1,3-position, and it is more preferable that it is substituted at the 1,3-position. When substituted at the 1,2-position, the intermolecular reaction is less likely to occur. Further, it may have a substituent on the aromatic ring of the above-mentioned compound, and it is preferable that the substituent is substituted with an alkyl group or an alkyl halide group. If the substituent has a large number of carbon atoms, the solvent solubility is improved. However, since the heat resistance is lowered, it is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, and more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms. Most preferably, it is unsubstituted or substituted with a methyl group.

The curable resin composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor that can be used include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based polymerization inhibitors. The polymerization inhibitor may be added at the time of synthesizing the olefin resin of the present invention or may 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 part by weight, based on 100 parts by weight of the resin component. Each of these polymerization inhibitors can be used alone, but two or more of them may be used in combination. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferable.

Specific examples of the phenolic polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β- (. 3,5-Di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) Monophenols such as -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2 , 2'-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t- Butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy) -Hydrosinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxy Benzyl Phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2-{β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4 Bisphenols such as 8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl) calcium; 1,1,3-tris (2-) Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [Methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methan, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) ) Butyric acid] Glycol ester, Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -a Socianurate, 1,3,5-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol Such as high molecular weight phenols are exemplified.

Specific examples of the sulfur-based polymerization inhibitor include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyll-3,3'-thiodipropionate and the like. NS.

Specific examples of the phosphorus-based polymerization inhibitor include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, and tris (2,4-di-t). -Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2, Phenyl phosphite such as 4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Class: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa Examples thereof include oxaphosphaphenanthrene oxides such as -10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Specific examples of the hindered amine-based polymerization inhibitor include Adecastab LA-40MP, Adecastab LA-40Si, Adecastab LA-402AF, Adecastab LA-87, Decastab LA-82, Decastab LA-81, Adecastab LA-77Y, and Adecastab LA. -77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, Adekastab LA-57, ADK STAB LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB etc. Is exemplified, but the present invention is not limited to this.

Specific examples of the nitroso-based polymerization inhibitor include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cuperon) and the like, and ammonium of N-nitrosophenylhydroxyamine is preferable. It is salt (cuperon).

Specific examples of the nitroxyl radical-based polymerization inhibitor include, but are not limited to, TEMPO-free radicals, 4-hydroxy-TEMPO-free radicals, and the like.

As the curable resin composition of the present invention, any known material can be used as a curable resin other than the olefin resin of the present invention. Specific examples thereof include phenol resin, epoxy resin, amine resin, active arcene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, metallicyl resin, and active ester resin, and are used as one type. However, a plurality of them may be used in combination. Further, from the viewpoint of the balance of heat resistance, adhesion and dielectric properties, it is preferable to contain an epoxy resin, an active alkene-containing resin, and a cyanate ester resin. By containing these curable resins, it is possible to improve the brittleness of the cured product and the adhesion to the metal, and it is possible to suppress cracks in the package during reliability tests such as solder reflow and thermal cycling.
The amount of the curable resin used is preferably in the mass range of 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less with respect to the olefin resin of the present invention. Further, the preferable lower limit value 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 olefin resin of the present invention can be utilized.

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

Phenolic resin: Phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, hydroquinone, resorcin, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, etc.) Polycondensate with benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, etc.) Polymers of norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., and phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.) Polycondensate, phenols and substituted biphenyls (4,54'-bis (chloromethyl) -1,1'-biphenyl and 4,4'-bis (methoxymethyl) -1,1'-biphenyl, etc.) or substitutions Phenolic resins and bisphenols obtained by polycondensation with phenyls (1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, etc.) and the like. Polyphenylene ether, a polycondensate of various aldehydes.

Epoxy resin: Glysidyl ether-based epoxy resin obtained by glycidylizing the above-mentioned phenol resin, alcohols, etc., 4-vinyl-1-cyclohexene epoxide, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, etc. Typical alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol.

Amin resin: diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resin obtained by the reaction of aniline with xylylene chloride, and aniline described in Japanese Patent No. 6429862. Substituted biphenyls (4,4'-bis (chlormethyl) -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.).

Active alkene-containing resin: A polycondensate of the above-mentioned phenol resin and a halogen-based compound containing active alkene (chloromethylstyrene, allyl chloride, metallyl chloride, acrylic acid chloride, allyl chloride, etc.), active alkene-containing phenols (2- Allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,5'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 -Bis (chloromethyl) benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanul chloride, etc.) polycondensate, epoxy resin or alcohols substituted or non-substituted Polycondensate of substituted acrylates (acrylate, methacrylate, etc.), maleimide resin (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis [4- (4- (4- (4- (4- (4- (4-) 4-) Maleimide phenoxy) 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'-Diphenylsulphonbis maleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene).

Isocyanate resin: p-phenylene diisocyanate, m-phenylenedi isocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc. Aromatic diisocyanates of Polyisocyanate such as a burette of the above or an isocyanate compound obtained by quantifying the diisocyanate compound; a polyisocyanate obtained by a urethanization reaction between the isocyanate compound and a polyol compound.

Polyamide resin: amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, etc.), lactam (ε-caprolactam, ω-undecantham, ω-laurolactam) and "diamine (ethylenediamine) , Trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine , Heptadecandiamine, octadecanediamine, nonadecandiamine, eikosandiamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane and other aliphatic diamines; cyclohexanediamine, bis- (4) Alicyclic diamines such as −aminocyclohexyl) methane and bis (3-methyl-4-aminocyclohexyl) methane; aromatic diamines such as xylylenediamine and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, etc. Aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Selected from a mixture with aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkylesters of these dicarboxylic acids, and dichloride). A polymer using at least one type as the main raw material.

Polygonide resin: Diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- Cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride , 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetra Carboxyl dianhydride, 2,2', 3,3'-biphenyltetracarboxylic hydride, methylene-4,4'-diphthalic hydride, 1,1-ethylidene-4,4'-diphthalic acid Dianhydride, 2,2'-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'- Diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic hydride, 1,5-pentamethylene-4,4'-diphthalic hydride, 4,4'-oxydiphthalic hydride Anhydride, thio-4,4'-diphthalic hydride, sulfonyl-4,4'-diphthalic hydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1, 3-Bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-di) Carboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenyl) Carboxyphenoxy) 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 acid dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-na Phthylenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthranetetracarboxylic dianhydride, 1,2,7,8-phenanthrene Tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), cyclopentane Tetetracarboxylic 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) Dianide, 1,2-ethylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) Acid) dianhydride, 2,2-propyridene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dihydride, 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-spirio-3'-( tetrahydrofuran-2', 5'-dione), 4- (2,5-dioxotetraki-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic dianhydride, ethylene glycol-bis- (3,4-dicarboxylic dianhydride phenyl) ether, 4,4'-biphenylbis (trimellitic acid monoesteric dianhydride), 9,9 Polycondensate with'-bis (3,4-dicarboxyphenyl) fluorene dianhydride).

Cyanate ester resin: A cyanate ester compound obtained by reacting a phenolic resin with cyanate halide. Specific examples thereof include disianate benzene, tricyanate benzene, disianato naphthalene, disianato biphenyl, 2, 2 '-Bis (4-cyanate phenyl) propane, bis (4-cyanate phenyl) methane, bis (3,5-dimethyl-4-cyanate phenyl) methane, 2,2'-bis (3,5-dimethyl) -4-Cyanatephenyl) propane, 2,2'-bis (4-cyanatephenyl) ethane, 2,2'-bis (4-cyanatephenyl) hexafluoropropane, bis (4-cyanatephenyl) sulfone , Bis (4-cyanatephenyl) thioether, phenol novolac cyanate, phenol-dicyclopentadiene cocondensate obtained by converting the hydroxyl group into a cyanate group, and the like, but are not limited thereto.
Further, the cyanate ester compound whose synthesis method is described in JP-A-2005-264154 is particularly preferable as the cyanate ester compound because it is excellent in low hygroscopicity, flame retardancy and dielectric properties.
The cyanate resin contains zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, and lead in order to tritrate the cyanate group to form a sym-triazine ring, if necessary. It can also contain a catalyst such as acetylacetonate or dibutyltin maleate. The catalyst is usually 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.

Active ester resin: A compound having one or more active ester groups in one molecule can be used as a curing agent for the curable resin, such as an epoxy resin, if necessary. Examples of the active ester-based curing agent include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between at least one compound of a carboxylic acid compound and a thiocarboxylic acid compound and at least one compound of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from at least one compound of the carboxylic acid compound, the phenol compound and the naphthol compound is preferable. Agents are preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl compound of phenol novolac. Examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.
Commercially available products of the active ester-based curing agent include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure; acetylated product of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing Examples of the active ester-based curing agent are "DC808" (manufactured by Mitsubishi Chemical Corporation); and "EXB-9050L-62M" manufactured by DIC Co., Ltd. as a phosphorus atom-containing active ester-based curing agent.

The curable resin composition of the present invention can also be used in combination with a curing accelerator (curing catalyst) to improve curability. As a specific example of the curing accelerator that can be used, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of a radically polymerizable curable resin such as an olefin resin or a maleimide resin or radical polymerization with other components. .. Examples of the 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, dicumyl peroxide, and 1,3-bis- (t-butylperoxy). Dialkyl peroxides such as isopropyl) -benzene, t-butylperoxybenzoate, peroxyketals such as 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peroxides such as benzoate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis (t-butylper) Oxycarbonyloxy) Peroxy carbonates such as hexane, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctate, lauroyl peroxide and azobisisobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) and other known curing accelerators for azo compounds can be mentioned, but are particularly limited thereto. It's not a thing. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxides, percarbonates and the like are preferable, and dialkyl peroxides are more preferable. 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 with respect to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight does not sufficiently extend during the polymerization reaction.

Further, if necessary, a curing accelerator other than the radical polymerization initiator may be added or used in combination. Specific examples of the curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diazabicyclo ( 5,4,0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl A quaternary ammonium salt such as ammonium hydroxide, a quaternary phosphonium salt such as a triphenylbenzylphosphonium salt, a triphenylethylphosphonium salt, a tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen, Organic acid ions, hydroxide ions, etc. are not particularly specified, but organic acid ions and hydroxide ions are particularly preferable), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen). Examples thereof include transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid acid (zinc acid, zinc mistylate) and zinc phosphate ester (zinc octyl phosphate, zinc stearyl phosphate, etc.). The amount of the curing accelerator to be blended is 0.01 to 5.0 parts by weight with respect to 100 of the total curable resin component, if necessary.

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 the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixilylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, and 1,3-phenylenebis (. Phosphoric acid esters such as dixilylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4'-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenantrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenantren-10-oxide; epoxy resin and active hydrogen of the phosphanes Phosphorus-containing epoxy compounds obtained by reacting with, red phosphorus and the like can be mentioned, but phosphoric acid esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1 , 4-Phenylenebis (dixylyleneyl phosphate), 4,4'-biphenyl (dixylyleneyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably in the range of 0.1 to 0.6 (weight ratio) of (phosphorus-containing compound) / (total curable resin component). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Further, a light stabilizer may be added to the curable resin composition of the present invention, if necessary. As the light stabilizer, a hindered amine-based light stabilizer, particularly HALS and the like, is suitable. The HALS is not particularly limited, but typical ones are dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-). Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -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-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-Pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] Butylmalonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Examples thereof include 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6-pentamethyl-4-piperidyl). Only one type of HALS may be used, or two or more types may be used in combination.

Further, a binder resin can be added to the curable resin composition of the present invention, if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin and the like. , Not limited to these. The blending amount of the binder resin is preferably in 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 with respect to 100 parts by mass of the total curable resin component. More preferably, 0.05 to 20 parts by mass is used as needed.

Further, the curable resin composition of the present invention contains, if necessary, molten silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia. , Aluminum nitride, graphite, forsterite, steatite, spinel, mulite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or an inorganic filler obtained by spheroidizing or crushing these powders. Can be done. Further, particularly when a curable resin composition for encapsulating a semiconductor is obtained, the amount of the above-mentioned inorganic filler used is usually in the range of 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. be.

Known additives can be added to the curable resin composition of the present invention, if necessary. Specific examples of the additives that can be used include fillings such as polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ethers, polystyrenes, polyethylenes, polyimides, fluororesins, silicone gels, silicone oils, and silane coupling agents. Examples thereof include surface treatment agents for materials, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The blending amount of these additives is preferably in the range of 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention is obtained by uniformly mixing each of the above components at a predetermined ratio, and is usually pre-cured at 130 to 180 ° C. for 30 to 500 seconds, and further, 150 to 200 ° C. After curing for 2 to 15 hours, a sufficient curing reaction proceeds, and the cured product of the present invention is obtained. It is also possible to uniformly disperse or dissolve the components of the curable resin composition in a solvent or the like, remove the solvent, and then cure.

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 in which moisture resistance, heat resistance, and high adhesiveness are required. Specifically, it is useful as an insulating material, a laminated board (printed wiring board, BGA board, build-up board, etc.), a sealing material, a resist, and other materials for all electrical and electronic components. In addition to molding materials and composite materials, it can also be used in fields such as paint materials, adhesives, and 3D printing. Especially in semiconductor encapsulation, solder reflow resistance is beneficial.

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

The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be uniformly mixed or prepolymerized. For example, the curable resin of the present invention is prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, in addition to the curable resin of the present invention, a curing agent such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives may be added to prepolymerize. good. For mixing or prepolymerizing each component, for example, an extruder, kneader, roll or the like is used in the absence of a solvent, and a reaction kettle with a stirrer is used in the presence of a solvent.

As a method of uniformly mixing, the mixture is kneaded at a temperature in the range of 50 to 100 ° C. using a device such as a kneader, a roll, or a planetary mixer to obtain a uniform resin composition. After pulverizing the obtained resin composition, it is molded into a cylindrical tablet shape by a molding machine such as a tablet machine, or a granular powder or a powder-like molded product, or these compositions are placed on a surface support. It can also be melted and molded into a sheet having a thickness of 0.05 mm to 10 mm to obtain a curable resin composition molded body. The obtained molded product becomes a non-sticky molded product at 0 to 20 ° C., and even if it is stored at 25 to 0 ° C. for 1 week or more, its fluidity and curability are hardly deteriorated.
The obtained molded body can be molded into a cured product by a transfer molding machine or a compression molding machine.

It is also possible to add an organic solvent 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 a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to form a varnish, and glass fibers and carbon fibers are prepared. , Polyester fiber, Polyamide fiber, Alumina fiber, Paper, etc. can be obtained as a cured product of the curable resin composition of the present invention by hot-press molding the prepreg obtained by impregnating it with a base material such as paper and heating and drying it. .. 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. Further, if it is a liquid composition, for example, a curable resin cured product containing carbon fibers can be obtained as it is by the RTM method.

Further, 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 and the like in the B-stage. In such a film-type resin composition, the curable resin composition of the present invention is applied as the curable resin composition varnish on a release film, the solvent is removed under heating, and then B-stage is performed. Is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in 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 fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber 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 inorganic fibers and polys other than glass. Paraphenylene terephthalamide (Kevlar®, manufactured by DuPont Co., Ltd.), all aromatic polyamides, polyesters; and organic fibers such as polyparaphenylene benzoxazole, polyimide and carbon fibers, but are particularly limited. Not done. The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, and chopped strand mats. Further, as a weaving method of the woven fabric, plain weave, Nanako weave, twill weave and the like are known, and it is possible to appropriately select and use from these known ones according to the intended use and performance. Further, a woven fabric that has been subjected to fiber opening treatment or a glass woven fabric that has been surface-treated with a silane coupling agent or the like is preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating the reinforcing fibers with the varnish and heating and drying the varnish.

The laminated board of this embodiment includes one or more of the above prepregs. The laminated board is not particularly limited as long as it includes one or more prepregs, and may have any other layer. As a method for producing the laminated board, a generally known method can be appropriately applied, and the method is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when forming a metal foil-clad laminate, and the laminate is formed by laminating the above prepregs and forming them under heat and pressure. Obtainable. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, more preferably 120 to 270 ° C. Further, the pressure to pressurize is not particularly limited, but if the pressurization is too large, it is difficult to adjust the solid content of the resin of the laminated board and the quality is not stable, and if the pressure is too small, air bubbles and adhesion between the laminates are deteriorated. 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable because it becomes worse. The laminated board of the present embodiment can be suitably used as a metal foil-clad laminated board described later by providing a layer made of a metal foil.
The prepreg is cut into a desired shape, laminated with copper foil or the like if necessary, and then the curable resin composition is heat-cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. Laminated boards for electrical and electronic use (printed wiring boards) and carbon fiber reinforced materials can be obtained.

The cured product of the present invention can be used for various purposes such as molding materials, adhesives, composite materials, and paints. Since the cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, it is a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, a sealing material for organic EL elements, and a printed wiring substrate. , It is suitably used for electric / electronic parts such as build-up laminates and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

Next, the present invention will be described in more detail with reference to Examples. Hereinafter, unless otherwise specified, the parts are parts by weight. The present invention is not limited to these examples.
The various analytical methods used in the examples are described below.
<Number average molecular weight (Mn), weight average molecular weight (Mw)>
It was calculated by polystyrene conversion using a polystyrene standard solution.
GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
Columns: Shodex KF-603, KF-602x2, KF-601x2)
Linked eluent: tetrahydrofuran Flow rate: 0.5 ml / min.
Column temperature: 40 ° C
Detection: RI (Differential Refractometer)

[Example 1]
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 125 parts of 1,3-diisopropenylbenzene (manufactured by Tokyo Kasei Co., Ltd.), 125 parts of toluene, and 12.5 parts of activated clay are charged, and the internal temperature is raised to 30 ° C. After warming and reacting for 2 hours, the reaction was carried out at 45 ° C. for 1 hour, 60 ° C. for 1 hour, 70 ° C. for 1 hour, and 80 ° C. for 10 hours. At this time, it was confirmed by GPC analysis that no residual monomer was contained. After allowing to cool, the active clay was removed by filtration, and the solvent was distilled off under heating and reduced pressure to remove 80 parts of the olefin resin (O-1) into a solid resin (softening point: 101 ° C., ICI viscosity (150 ° C.): 4. 2 Pa · s) (Mn: 1197, Mw: 2288). The GPC chart of the obtained compound is shown in FIG. In addition, a ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in FIG. ¹ A signal derived from the isopropenyl group was observed at 4.70-5.40 ppm on the 1 H-NMR chart.

[Example 2]
A flask equipped with a thermometer, a cooling tube, and a stirrer is charged with 125 parts of 1,3-diisopropenylbenzene (manufactured by Tokyo Kasei Co., Ltd.), 125 parts of toluene, and 6.3 parts of p-toluenesulfonic acid, and the internal temperature is 60. The temperature was raised to ° C. and the reaction was carried out for 18 hours. At this time, it was confirmed by GPC analysis that no residual monomer was contained. After allowing to cool, 100 parts of water was added and the mixture was repeatedly washed with 100 parts of water until the waste liquid became neutral. By distilling off the solvent under heating and reduced pressure, 115 parts of the olefin resin (O-2) was obtained as a white solid (ICI viscosity (150 ° C.): 0.02 Pa · s) (Mn: 371, Mw: 403). The GPC chart of the obtained compound is shown in FIG. In addition, a ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in FIG. ¹ A signal derived from the isopropenyl group was observed at 4.70-5.40 ppm on the 1 H-NMR chart.

[Example 3]
160 parts of 1,3-bis (α-hydroxyisopropyl) benzene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 80 parts of toluene, 0.08 parts of p-toluenesulfonic acid in a flask equipped with a thermometer, a cooling tube, and a stirrer. , 0.19 parts of water was charged, the internal temperature was raised to 120 ° C., and the reaction was carried out for 3 hours to generate 1,3-diisopropenylbenzene in the system by dehydration reaction (dehydration amount was 29.7 parts). It was almost the same as the theoretical amount.) After allowing to cool, 6.4 parts of p-toluenesulfonic acid and 3.6 parts of water were charged, the internal temperature was raised to 60 ° C., and the reaction was carried out for 16 hours. At this time, it was confirmed by GPC analysis that no residual monomer was contained. After allowing to cool, 150 parts of toluene and 100 parts of water were added, and the mixture was repeatedly washed with 100 parts of water until the waste liquid became neutral. By distilling off the solvent under heating and reduced pressure, 122 parts of the olefin resin (О-3) was obtained as a white solid (Mn: 367, Mw: 411). The GPC chart of the obtained compound is shown in FIG.

[Example 4]
A flask equipped with a thermometer, a cooling tube, and a stirrer is charged with 160 parts of 1,3-bis (α-hydroxyisopropyl) benzene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 80 parts of toluene, and 0.08 parts of methanesulfonic acid. The internal temperature was raised to 120 ° C. and reacted for 2 hours to generate 1,3-diisopropenylbenzene in the system by dehydration reaction (the amount of dehydration was 29.5 parts, which was almost the same as the theoretical amount. there were.). After allowing to cool, 1.6 parts of methanesulfonic acid was charged, the internal temperature was raised to 60 ° C., and the reaction was carried out for 18 hours. At this time, it was confirmed by GPC analysis that no residual monomer was contained. After allowing to cool, 150 parts of toluene and 100 parts of water were added, and the mixture was repeatedly washed with 100 parts of water until the waste liquid became neutral. By distilling off the solvent under heating and reduced pressure, 120 parts of the olefin resin (O-4) was obtained as a white solid (ICI viscosity (150 ° C.): 0.75 Pa · s, Mn: 861, Mw: 1766). The GPC chart at the end of the reaction is shown in FIG.

[Example 5]
A resin solution containing the compound (O-1) obtained in Example 1 and the maleimide resin (M2) described in Example 4 of JP2009-001783A was solidified by distilling off the solvent under reduced pressure. Dikmyl peroxide (DCP, manufactured by Tokyo Kasei Co., Ltd.) was blended in the ratio (parts by mass) shown in Table 1 as a curing accelerator, heated, melted and mixed in a metal container, poured into a mold as it was, and at 220 ° C. Allowed to cure for 2 hours. The evaluation results are shown in Table 1.

[Comparative Example 1]
A resin solution containing diallyl bisphenol A (manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the maleimide resin (M2) described in Example 4 of JP-A-2009-001783, solidified by distilling off the solvent under reduced pressure, and Dicumyl peroxide (DCP, manufactured by Tokyo Kasei Co., Ltd.) is blended as a curing accelerator at the ratio (parts by mass) shown in Table 1, heated, melted and mixed in a metal container, poured into a mold as it is, and cured at 220 ° C. for 2 hours. However, the test piece could not be taken out because it did not reach a sufficient degree of curing.
Therefore, after pouring into a mold, the mixture was cured at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 230 ° C. for 2 hours, and 250 ° C. for 2 hours. The evaluation results are shown in Table 1.

<Heat resistance test>
-Glass transition temperature: The temperature when tan δ is the maximum value measured by a dynamic viscoelasticity tester.
Dynamic viscoelasticity measuring instrument: DMA-2980 manufactured by TA-instruments
Temperature rise rate: 2 ° C / min <Dielectric constant test / dielectric loss tangent test>
-The test was performed by the cavity resonator perturbation method using a 1 GHz hollow resonator manufactured by ATE.

表中、〇は硬化したこと、×は硬化不十分で試験片が取り出せないことを示す。

In the table, ◯ indicates that the test piece has been cured, and × indicates that the test piece cannot be taken out due to insufficient curing.

From Table 1, it was confirmed that Example 5 had good curability, high heat resistance, and excellent dielectric properties. In particular, the dielectric loss tangent of Example 5 is one order lower than that of Comparative Example 1, and has extremely excellent characteristics. On the other hand, Comparative Example 1 does not cure under the curing conditions of 220 ° C. for 2 hours, and has problems in curability and dielectric properties.

[Example 6]
The compound (O-3) obtained in Example 3, a dicyclopentadiene dimethanol type acrylate resin (KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd.), and dicumyl peroxide (DCP, Tokyo Kasei Co., Ltd.) as a curing accelerator. (Manufactured) was blended in the proportions (parts by mass) shown in Table 2 to obtain a curable resin composition. The obtained curable resin composition was applied to an imide film (Kapton: manufactured by Toray DuPont) using an applicator (thickness 250 μm), cured at 200 ° C. for 30 minutes, and then cut into a length of 4 mm and a width of 3 mm. Then, the cured physical properties were evaluated. The evaluation results are shown in Table 2.

表中、〇は硬化したこと、×は硬化不十分で試験片が取り出せないことを示す。

In the table, ◯ indicates that the test piece has been cured, and × indicates that the test piece cannot be taken out due to insufficient curing.

From Table 2, it was confirmed that Example 6 had good curability, high heat resistance, and excellent dielectric properties. In particular, Example 6 showed excellent curability that it could be cured even in a short time of 200 ° C. for 30 minutes.

The olefin resin of the present invention is an insulating material for electrical and electronic parts (highly reliable semiconductor encapsulation material, etc.), a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), and an adhesive (conductive adhesive, etc.). It is useful for various composite materials such as CFRP, paints, and 3D printing.

Claims (10)

An olefin resin represented by the following formula (1).

(In equation (1), A is represented by equation (2).)

(In the formula (2), l, m, and n each independently represent a real number of 0 to 20, and 1 ≦ l + m + n ≦ 20, respectively. R is a hydrogen atom and a hydrocarbon having 1 to 10 carbon atoms, respectively. Represents a group or an alkyl halide group. P represents a real number from 0 to 4, q represents a real number from 0 to 3. (a), (b), and (c) are each bonded by * and a repeating position. Can be random.) The olefin resin according to claim 1, wherein in the formula (2), 1.1 ≦ l + m + n ≦ 20. The olefin resin according to claim 1 or 2, wherein R is a hydrogen atom in the formula (2). The olefin resin according to any one of claims 1 to 3, which is derived from a diisopropenylbenzene-based compound. The olefin resin according to any one of claims 1 to 3, which is derived from 1,3-diisopropenylbenzene. The olefin resin according to any one of the above items [1] to [5], wherein the weight average molecular weight determined by the measurement of gel permeation chromatography is 200 or more and less than 5000. A curable resin composition containing the olefin resin according to any one of claims 1 to 6 and a polymerization inhibitor. A curable resin composition containing the olefin resin according to any one of claims 1 to 6 and a curable resin other than the olefin resin. The curable resin composition according to claim 7 or 8, further comprising a curing accelerator. A cured product obtained by curing the olefin resin according to any one of claims 1 to 6 and the curable resin composition according to any one of claims 7 to 9.

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