JP7586738B2 - Olefin resin, curable resin composition and cured product thereof - Google Patents

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, which are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.

In recent years, the required characteristics of laminates for mounting electric and electronic components have become more extensive and sophisticated due to the expansion of fields of use. Conventional semiconductor chips were mainly mounted on metal lead frames, but in recent years, semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are increasingly being mounted on laminates made of polymer materials.

In particular, semiconductor packages (hereafter referred to as PKGs) used in smartphones and other devices require thinner PKG substrates to meet the demand for smaller size, thinner thickness, and higher density. However, as the PKG substrate becomes thinner, its rigidity decreases, and defects such as large warping occur when the PKG is heated during solder mounting to the motherboard (PCB). To reduce this, there is a demand for PKG substrate materials with a high Tg above the solder mounting temperature.

In addition, the development of the fifth-generation communication system "5G" is currently accelerating, and it is expected that even greater capacity and faster communication will be achieved. This will lead to an ever-increasing need for low dielectric tangent materials, with a dielectric tangent of at least 0.005 or less at 1 GHz, which is no longer possible with conventional epoxy resin encapsulants.

In light of this background, polymeric materials that can achieve both heat resistance and low dielectric tangent characteristics are being studied. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain during the curing reaction, the electrical properties are not sufficient. Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are replaced with allyl groups. However, it has been shown that Claisen rearrangement occurs at 190°C, and at 200°C, which is the molding temperature for general substrates, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties are not satisfactory.

In recent years, 3D printing has been attracting attention as a method for three-dimensional modeling, and this 3D printing method is beginning to be applied in fields that require reliability, such as aerospace, automobiles, and connectors for electronic components used in these fields. In particular, photocurable and thermosetting resins are being studied for applications such as stereolithography (SLA) and digital light processing (DLP). Therefore, while the conventional method of transferring from a mold mainly requires shape stability and accuracy, 3D printing applications require various properties such as heat resistance, mechanical properties, toughness, flame retardancy, and even electrical properties, and material development is being promoted. In addition, when used in structural components, changes in properties due to moisture absorption, etc. are an issue. Currently, acrylate resins and epoxy resins are used in such applications, but the cured products of both contain many ester bonds, ether bonds, and even hydroxyl groups, and their moisture absorption properties are insufficient.

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

The present invention was made in consideration of these circumstances, and aims to provide an olefin resin, a curable resin composition, and a cured product thereof that exhibit excellent heat resistance and electrical properties and have good curability.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that a cured product containing a novel olefin resin has excellent heat resistance and low dielectric properties, which led to the completion of 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 formula (1), A is represented by formula (2).)

(In formula (2), l, m, and n each independently represent a real number from 0 to 20, with 1≦l+m+n≦20. Each R independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group. p represents a real number from 0 to 4, and q represents a real number from 0 to 3. (a), (b), and (c) are each bonded with an *, and the repeating positions may be random. They are also bonded to the isopropenyl group in formula (1) with an *.)
[2]
The olefin resin according to the above item [1], wherein, in the formula (2), 1.1≦l+m+n≦20.
[3]
The olefin resin according to the above item [1] or [2], wherein in the formula (2), R is a hydrogen atom.
[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 items [1] to [3] above, which is derived from 1,3-diisopropenylbenzene.
[6]
The olefin resin according to any one of the above items [1] to [5], having a weight average molecular weight of 200 or more and less than 5,000 as determined by gel permeation chromatography.
[7]
A curable resin composition comprising the olefin resin according to any one of the above items [1] to [6] and a polymerization inhibitor.
[8]
A curable resin composition comprising the olefin resin according to any one of items [1] to [6] above, and a curable resin other than the olefin resin.
[9]
The curable resin composition according to item [7] or [8], further comprising a curing accelerator.
[10]
A cured product obtained by curing the olefin resin according to any one of the above items [1] to [6] or the curable resin composition according to any one of the above items [7] to [9].

The olefin resin of the present invention has excellent curing properties, and the cured product thereof has excellent properties such as high heat resistance and low dielectric properties, and is therefore useful as a material for sealing electric and electronic parts, circuit boards, carbon fiber composite materials, etc.
In addition, since the olefin resin of the present invention has excellent reactivity, it is also one of the preferred embodiments to cure the resin alone.

1 shows a GPC chart of Example 1. 1 shows a ¹ H-NMR chart of Example 1. 1 shows a GPC chart of Example 2. 1 shows a ¹ H-NMR chart of Example 2. 1 shows a GPC chart of Example 3. 1 shows a GPC chart of Example 4.

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

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

(In formula (2), l, m, and n each independently represent a real number between 0 and 20, with 1≦l+m+n≦20. Each R independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group. p represents a real number between 0 and 4, and q represents a real number between 0 and 3. (a), (b), and (c) are each bonded with an *, and the repeating positions may be random. They are also bonded to the isopropenyl group in formula (1) with an *.)

In the formula (2), p is usually a real number of 0 to 4, preferably 0 to 3, and more preferably 0. q is usually a real number of 0 to 3, preferably 0 to 2, and more preferably 0.
R is usually a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. When R is a hydrogen atom or a hydrocarbon having 3 or less carbon atoms, it is less likely to undergo molecular vibration when exposed to high frequency waves, and therefore has excellent electrical properties.

In the formula (2), l, m, and n are each independently a real number usually ranging from 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) determined by gel permeation chromatography (GPC) of 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 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 during the solvent distillation step.

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

In formula (3), l, m, n, R, p, and q are the same as in formula (2). Although the repeating units are shown in a specific order for convenience of description, the repeating units may be present in any order, and the present application also includes repeating units in any order. Specifically, the structure of each repeating unit may be randomly copolymerized or block copolymerized. Also, the polymer may be a single structure polymer of only one of the repeating unit structures.

The method for producing the olefin resin of the present invention is not particularly limited, but it can be obtained by reacting a diisopropenylbenzene compound in the presence of an acid catalyst. Examples of solvents that can be used in the reaction include, but are not limited to, non-water-soluble solvents such as 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, and ketone solvents such as methyl isobutyl ketone and cyclopentanone. Two or more of these may be used in combination. In addition to the non-water-soluble solvent, aprotic 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 used in combination. Two or more of these may also be used in combination. The catalyst is not particularly limited, and examples of the catalyst that can be used include 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 silica alumina, and acidic ion exchange resins. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.0001 to 0.8 mol, preferably 0.0002 to 0.7 mol, per mol of the diisopropenylbenzene compound used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high, making stirring difficult, and if the amount is too small, the reaction may proceed slowly and raw material monomers may remain. The polymerization reaction temperature is -50 to 180°C, preferably 0 to 100°C, and the reaction is carried out for 0.5 to 60 hours, more preferably 1 to 30 hours. By carrying out the polymerization reaction within the above range, the raw material monomers can be reduced to below the detection limit of GPC (gel permeation chromatography: RI) at the time of the polymerization reaction. Since no raw monomer remains, production operations such as distillation and reprecipitation are not necessary, which is preferable from the viewpoint of simplifying the manufacturing process and reducing waste. When creating a cured product, the generation of volatile matter can be suppressed, making it possible to create a cured product without voids. After the reaction is completed, the acid catalyst is neutralized with an alkaline aqueous solution, and then a water-insoluble organic solvent is added to the oil layer and repeated washing with water is performed until the wastewater becomes neutral.

Diisopropenylbenzene compounds include, but are not limited to, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, etc., as well as 1,2-bis(α-hydroxyisopropyl)benzene, 1,3-bis(α-hydroxyisopropyl)benzene, and diisopropenylbenzene obtained by dehydrating 1,4-bis(α-hydroxyisopropyl)benzene. The substitution positions are preferably 1,4-positions or 1,3-positions, and more preferably 1,3-positions. Substitution at the 1,2-positions makes it difficult for intermolecular reactions to occur. The aromatic ring of the above-mentioned compound may have a substituent, and is preferably substituted with an alkyl group or a halogenated alkyl group. If the substituent has a large number of carbon atoms, the solvent solubility improves, but the heat resistance decreases, so it is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, and most preferably unsubstituted or substituted with a methyl group.

The curable resin composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors 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 when synthesizing the olefin resin of the present invention, or after synthesis. The polymerization inhibitor may be used alone or in combination of two or more kinds. 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, per 100 parts by weight of the resin component. Each of these polymerization inhibitors may be used alone, but may also be used in combination of two or more kinds. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred.

Specific examples of phenol-based polymerization inhibitors include monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, 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)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; -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), triethylene glycol-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-hydrocinnamamide), 2,2-thio-diethylenebis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl)calcium bisphenols; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, Examples include polymeric phenols such as 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

Specific examples of sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

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

Specific examples of hindered amine polymerization inhibitors include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, DEKA STAB LA-82, DEKA STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB Examples include, but are not limited to, 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.

Specific examples of nitroso-based polymerization inhibitors include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cupferron), etc., with the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) being preferred.

Specific examples of nitroxyl radical polymerization inhibitors include, but are not limited to, TEMPO free radical, 4-hydroxy-TEMPO free radical, etc.

The curable resin composition of the present invention may use any known material as a curable resin other than the olefin resin of the present invention. Specifically, phenolic resin, epoxy resin, amine resin, active alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, methallyl resin, active ester resin, etc. may be used alone or in combination. In addition, it is preferable to contain an epoxy resin, an active alkene-containing resin, or a cyanate ester resin from the perspective of the balance of heat resistance, adhesion, and dielectric properties. By containing these curable resins, the brittleness of the cured product and adhesion to metals can be improved, and cracks in the package during solder reflow and reliability tests such as thermal cycles can be suppressed.
The amount of the curable resin used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the olefin resin of the present invention. The preferred lower limit is 0.5 times by mass or more, and more preferably 1 time by mass or more. If the amount is 10 times by mass or less, the effects of the heat resistance and dielectric properties of the olefin resin of the present invention can be utilized.

Examples of phenolic resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins that can be used include the following:

Phenolic resins: Polycondensates of phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydrofuran, etc.) Polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenolic resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.), polycondensates of bisphenols and various aldehydes, polyphenylene ether.

Epoxy resins: glycidyl ether epoxy resins obtained by glycidylating the above-mentioned phenolic resins and alcohols, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidyl amine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins.

Amine resins: diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resins obtained by reacting aniline with xylylene chloride, aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.) described in Japanese Patent No. 6429862.

Active alkene-containing resins: Polycondensates of the above-mentioned phenolic resins and halogen-based compounds containing active alkenes (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), polycondensates of active alkene-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based 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.), epoxy resins Or polycondensates of alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene).

Isocyanate resins: Aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by the urethane reaction of the above isocyanate compounds with polyol compounds.

Polyamide resin: Amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and aliphatic diamines such as 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. Polymers made from one or more of the following main raw materials: alicyclic diamines such as cyclohexanediamine, bis-(4-aminocyclohexyl)methane, and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine, and mixtures 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, and 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, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and dichlorides).

Polyimide resin: The above diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride) Anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-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 Acid dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 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-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride benzene dianhydride, 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 water, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 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), cyclo Pentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic 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-ethylidene-4, 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-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'-biphenylbis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride) polycondensate.

Cyanate ester resin: a cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto.
Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
The cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate, etc., in order to trimerize the cyanate group to form a sym-triazine ring, if necessary. 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, per 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. As the active ester curing agent, a compound 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, is preferred. The active ester curing agent is preferably one 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and at least one compound of a phenol compound and a naphthol compound is preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, etc. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
Preferred specific examples of the active ester 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 an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
Commercially available active ester curing agents include, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation); and phenolic Examples of active ester compounds containing an acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing a benzoylated phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is a phosphorus atom-containing active ester curing agent.

The curable resin composition of the present invention can also be improved in curability by using a curing accelerator (curing catalyst) in combination. As a specific example of a 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, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butylperoxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-3,5,5-trimethylhexanoate. peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide; and known curing accelerators such as azo compounds such as azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). However, the curing accelerator is not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, with dialkyl peroxides being more preferred. The amount of radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If a large amount of radical polymerization initiator is used, the molecular weight does not extend sufficiently during the polymerization reaction.

If necessary, a curing accelerator other than the radical polymerization initiator may be added or used in combination. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide, Examples of the transition metal compounds include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt may be a halogen, an organic acid ion, a hydroxide ion, or the like, but is not particularly specified, and organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as zinc compounds such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate), and zinc phosphate ester (zinc octylphosphate, zinc stearylphosphate, etc.). The amount of the curing accelerator to be used is 0.01 to 5.0 parts by weight per 100 of the total curable resin components, as necessary.

The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of phosphorus-containing compounds include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5- Phosphanes such as dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc. are included, but phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixylyl phosphate), 1,4-phenylenebis(dixylyl phosphate), 4,4'-biphenyl(dixylyl 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) (phosphorus-containing compound)/(total curable resin components). 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 it may have an adverse effect on the moisture absorption and dielectric properties of the cured product.

Furthermore, a light stabilizer may be added to the curable resin composition of the present invention as necessary. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferred. Although there is no particular limitation on the HALS, representative ones include a polycondensate 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 polycondensate of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 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) bis(1,2,2,6,6-pentamethyl-4-piperidyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butyl malonate, 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, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), and the like. Only one type of HALS may be used, or two or more types may be used in combination.

Furthermore, the curable resin composition of the present invention can also contain a binder resin as needed. Examples of binder resins include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. The amount of binder resin to be added 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, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the total curable resin components, as needed.

Furthermore, to the curable resin composition of the present invention, powders such as fused 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, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers in the form of spherical or crushed powders thereof, can be added as necessary. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass, in the curable resin composition.

The curable resin composition of the present invention may contain known additives as necessary. Specific examples of additives that may be used 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, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components in a predetermined ratio, and is usually pre-cured at 130 to 180°C for 30 to 500 seconds, and then post-cured at 150 to 200°C for 2 to 15 hours to allow the curing reaction to proceed sufficiently and obtain the cured product of the present invention. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and cured after removing the solvent.

The curable resin composition of the present invention thus obtained 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 that require moisture resistance, heat resistance, and high adhesion. Specifically, it is useful as an insulating material, a laminate (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, a resist, and other materials for all electrical and electronic components. It can also be used in fields such as molding materials, composite materials, paint materials, adhesives, and 3D printing. In particular, solder reflow resistance is beneficial in semiconductor sealing.

The semiconductor device is encapsulated 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), TSOP (thin small outline package), TQFP (thin quad flat package), etc.

The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be 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 phenolic resin, or an acid anhydride compound and other additives may be added to prepolymerize. For mixing or prepolymerization of each component, for example, an extruder, kneader, or roll 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 uniform mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet having a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced.
The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

An organic solvent can be added to the curable resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish). The curable resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as necessary to form a varnish, which can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg, which can then be hot-press molded to form a cured product of the curable resin composition of the present invention. The solvent used in this case usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of the present invention and the solvent. If the composition is in a liquid form, a cured product of the curable resin containing carbon fiber can be obtained as is, for example, by the RTM method.

The curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of the present invention as the curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate, etc.

The curable resin composition of the present invention can be heated and melted to reduce the 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 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, inorganic fibers other than glass, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), fully aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not limited to these. The shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, plain weave, sash weave, twill weave, and the like are known as weaving methods for woven fabrics, and these known methods can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. Prepregs can also be obtained by impregnating reinforcing fibers with the varnish and drying them by heating.

The laminate of this embodiment comprises one or more of the prepregs. The laminate is not particularly limited as long as it comprises one or more prepregs, and may have any other layer. The method for producing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, when forming the metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminate of this embodiment comprises a layer made of metal foil, and can be suitably used as a metal foil-clad laminate described later.
The prepreg is cut into a desired shape and laminated with copper foil or the like as necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and coating materials. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, printed wiring boards, and build-up laminates, as well as composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by weight. However, the present invention is not limited to these examples.
Various analytical methods used in the examples are described below.
<Number average molecular weight (Mn), weight average molecular weight (Mw)>
Calculations were made in terms of polystyrene 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)
Column: Shodex KF-603, KF-602x2, KF-601x2)
Eluent for coupling: tetrahydrofuran Flow rate: 0.5 ml/min.
Column temperature: 40°C
Detection: RI (Differential Refraction Detector)

[Example 1]
In a flask equipped with a thermometer, a condenser, and a stirrer, 125 parts of 1,3-diisopropenylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts of toluene, and 12.5 parts of activated clay were charged, the internal temperature was raised to 30°C, and the reaction was carried out for 2 hours, followed by reaction 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 cooling, the activated clay was removed by filtration, and the solvent was distilled off under heating and reduced pressure to obtain 80 parts of olefin resin (O-1) as 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 Figure 1. Also, the ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in Figure 2. A signal derived from an isopropenyl group was observed at 4.70-5.40 ppm in the ¹ H-NMR chart.

[Example 2]
In a flask equipped with a thermometer, a condenser, and a stirrer, 125 parts of 1,3-diisopropenylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts of toluene, and 6.3 parts of p-toluenesulfonic acid were charged, and the internal temperature was raised to 60° C. and reacted for 18 hours. At this time, it was confirmed by GPC analysis that no residual monomer was contained. After cooling, 100 parts of water was added and the waste liquid was repeatedly washed with 100 parts of water until it became neutral. The solvent was distilled off under heating and reduced pressure to obtain 115 parts of olefin resin (O-2) 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. 3. Also, the ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in FIG. 4. A signal derived from an isopropenyl group was observed at 4.70-5.40 ppm in the ¹ H-NMR chart.

[Example 3]
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 160 parts of 1,3-bis(α-hydroxyisopropyl)benzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 80 parts of toluene, 0.08 parts of p-toluenesulfonic acid, and 0.19 parts of water were charged, the internal temperature was raised to 120°C, and the reaction was carried out for 3 hours, and 1,3-diisopropenylbenzene was generated in the system by a dehydration reaction (the amount of dehydration was 29.7 parts, which was almost the theoretical amount.). After cooling, 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 cooling, 150 parts of toluene and 100 parts of water were added, and the waste liquid was repeatedly washed with 100 parts of water until it became neutral. The solvent was distilled off under heating and reduced pressure to obtain 122 parts of olefin resin (O-3) as a white solid (Mn: 367, Mw: 411). The GPC chart of the obtained compound is shown in FIG.

[Example 4]
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 160 parts of 1,3-bis(α-hydroxyisopropyl)benzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 80 parts of toluene, and 0.08 parts of methanesulfonic acid were charged, the internal temperature was raised to 120°C, and the reaction was carried out for 2 hours, and 1,3-diisopropenylbenzene was generated in the system by a dehydration reaction (the amount of dehydration was 29.5 parts, which was almost the theoretical amount.). After cooling, 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 cooling, 150 parts of toluene and 100 parts of water were added, and the waste liquid was repeatedly washed with 100 parts of water until it became neutral. The solvent was distilled off under heating and reduced pressure to obtain 120 parts of olefin resin (O-4) 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 JP-A-2009-001783 was solidified by distilling off the solvent under reduced pressure, and dicumyl peroxide (DCP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator was mixed in the ratio (parts by mass) shown in Table 1, melted and mixed by heating in a metal container, and then poured directly into a mold and cured at 220° C. for 2 hours. The evaluation results are shown in Table 1.

[Comparative Example 1]
A resin solution containing diallyl bisphenol A (manufactured by Daiwa Chemical Industry Co., Ltd.) and the maleimide resin (M2) described in Example 4 of JP2009-001783A was solidified by distilling off the solvent under reduced pressure, and dicumyl peroxide (DCP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator was blended in the ratio (parts by mass) shown in Table 1, heated and melted and mixed in a metal container, and then poured directly into a mold and cured at 220°C for 2 hours. However, a sufficient degree of curing was not achieved, and a test piece could not be removed.
Therefore, after pouring into a mold, the composition was cured for 2 hours at 160° C., 2 hours at 180° C., 2 hours at 200° C., 2 hours at 230° C., and 2 hours at 250° C. The evaluation results are shown in Table 1.

<Heat resistance test>
Glass transition temperature: The temperature at which tan δ is maximum as measured by a dynamic viscoelasticity tester.
Dynamic viscoelasticity measuring instrument: TA-instruments DMA-2980
Heating rate: 2°C/min. <Dielectric constant test/Dielectric tangent test>
A test was performed using a 1 GHz cavity resonator manufactured by ATE Corporation using the cavity resonator perturbation method.

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 material was cured, and × indicates that the material was insufficiently cured and the test piece could not be removed.

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

[Example 6]
A curable resin composition was obtained by mixing 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, manufactured by Tokyo Kasei Co., Ltd.) as a curing accelerator in the ratio (parts by mass) shown in Table 2. The obtained curable resin composition was applied to an imide film (Kapton: manufactured by Toray DuPont Co., Ltd.) using an applicator (film thickness 250 μm), cured at 200° C. for 30 minutes, and then cut to a length of 4 mm and a width of 3 mm to evaluate the cured physical properties. 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 material was cured, and × indicates that the material was insufficiently cured and the test piece could not be removed.

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

The olefin resin of the present invention is useful for applications such as insulating materials for electric and electronic components (high-reliability semiconductor encapsulation materials, etc.), laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.), and various composite materials including CFRP, paints, and 3D printing.

Claims (6)

A curable resin composition comprising an olefin resin represented by the following formula (1) and at least one selected from a curable resin other than an olefin resin, a curing accelerator, and a polymerization inhibitor:

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

(In formula (2), l, m, and n each independently represent a real number from 0 to 20, with 1≦l+m+n≦20. Each R independently represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents a real number from 0 to 4, and q represents a real number from 0 to 3. (a), (b), and (c) are each bonded with *, the repeating positions may be random, and at least one structure represented by (b) is contained in the molecule.) The curable resin composition according to claim 1, wherein in formula (2), 1.1≦l+m+n≦20. 3. The curable resin composition according to claim 1, which is derived from a diisopropenylbenzene compound. The curable resin composition according to claim 1 or 2, which is derived from 1,3-diisopropenylbenzene. The curable resin composition according to any one of claims 1 to 4, having a weight average molecular weight determined by gel permeation chromatography of 200 or more and less than 5,000. A cured product obtained by curing the curable resin composition according to claim 1 .

Images