JP7570484B2 - Olefin compound, curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to an olefin compound, a curable resin composition, 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, as well as lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

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 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 problems such as large warping can 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 high Tg values 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 increasing need for low dielectric tangent materials, with a dielectric tangent of at least 0.005 or less at 1 GHz.

Furthermore, as computerization advances in the automotive field, precision electronic devices are sometimes placed near the engine drive, requiring higher levels of heat and moisture resistance. SiC semiconductors are beginning to be used in trains and air conditioners, and the encapsulation material for semiconductor elements is now required to have extremely high heat resistance, which is no longer possible with conventional epoxy resin encapsulation materials.

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 are not involved in the curing reaction remain, the electrical properties are not sufficient.

Japanese Patent Application Publication No. 04-359911

The present invention was made in consideration of these circumstances, and aims to provide an olefin compound, 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 the cured product of a curable resin composition containing a novel olefin compound 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 compound represented by the following formula (1):

(In formula (1), X represents any organic group, each R independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group, each m independently represents an integer of 0 to 3, and n represents 1≦n≦20, each Y independently exists and is one or more of (A) to (D), excluding cases where all are (D), * indicates the bonding position with the skeletal structure.)
[2]
The olefin compound according to the above item [1], wherein in the formula (1), X is any one or more of (a) to (j) represented by the following formula (2):

(In formula (2), * indicates the bonding position with the skeleton structure.)
[3]
The olefin compound according to the above item [2], wherein in the formula (2), X is represented by (b) or (d).
[4]
The olefin compound according to any one of the above items [1] to [3], wherein in the formula (1), Y is represented by only (A).
[5]
The olefin compound according to any one of the above items [1] to [3], wherein in the formula (1), Y is represented by only (C).
[6]
The olefin compound according to any one of items [1] to [3], wherein in the formula (1), Y has both (A) and (C) in one molecule.
[7]
The olefin compound according to any one of the above items [1] to [6], which is derived from a compound represented by the following formula (3):

(In formula (3), X represents any organic group, each R independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group, each m independently represents an integer of 0 to 3, and n represents 1≦n≦20.)
[8]
A curable resin composition comprising the olefin compound according to any one of items [1] to [7] above.
[9]
A cured product obtained by curing the curable resin composition described in the above item [8].
[10]
A compound represented by the following formula (3):

(In formula (3), X represents any organic group, and each R independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group. Each m independently represents an integer of 0 to 3, and n represents 1≦n≦20.)

The cured product of the olefin compound of the present invention has excellent properties such as high heat resistance and low dielectric properties. Therefore, it is useful for sealing electric and electronic components, circuit boards, carbon fiber composite materials, etc.

FIG. 1 shows a GPC chart of Example 1.
FIG. 2 shows the ¹ H-NMR chart of Example 1.

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

(In formula (1), X represents any organic group, and each R independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group. Each m independently represents an integer of 0 to 3, and n represents 1≦n≦20. Each Y independently exists and is one or more of (A) to (D), excluding cases where all are (D). * indicates the bonding position with the skeletal structure.)

In the formula (1), Y is usually at least one of (A) to (D), and from the viewpoint of curability, it is preferably at least one of (A) to (C), and more preferably (A) or (C) to further enhance the curability.

In the formula (1), m is preferably 0 to 2, and more preferably 0. n is preferably 1≦n≦10, and even more preferably 1≦n≦5. R is preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom. When R is a hydrocarbon group 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 addition, in the formula (1), X is preferably one or more of (a) to (j) in the following formula (2), more preferably one or more of (b) to (i), and particularly preferably (b) or (d).

(In formula (2), * indicates the bond position to the backbone structure.)

The olefin compound represented by formula (1) of the present invention is derived from a compound represented by formula (3) below.

(In formula (3), X represents any organic group, and each R independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group. m represents an integer of 0 to 3, and n represents 1≦n≦20.)

The preferred ranges for m, n, and R in formula (3) are the same as those in formula (1).

The olefin compound represented by formula (1) of the present invention is derived from the compound represented by formula (3), and specifically, is obtained by reacting the compound represented by formula (3) with a halogen compound having an unsaturated double bond in the presence of a catalyst. For example, the compound represented by formula (3) can be obtained by reacting allyl chloride, methallyl chloride, chloromethylstyrene, etc. in a solvent in the presence of a basic catalyst. Examples of the solvent to be used include aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone. In addition to the aprotic polar solvent, a non-water-soluble solvent can also be used in combination. Examples of the solvent include 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, but are not limited to these, and two or more of them may be used in combination. The catalyst is not particularly limited, and examples thereof include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. In addition, when the reaction is carried out in a non-water-soluble solvent in the presence of water, a phase transfer catalyst can also be used. Examples of the catalyst include quaternary ammonium salts, such as bromides, chlorides, iodides, hydrogen sulfates, and hydroxides of tetramethylammonium, trimethylethylammonium, dimethyldiethylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trioctylmethylammonium, tetraethylammonium, trimethylpropylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, stearyltrimethylammonium, cetyldimethylethylammonium, tetrapropylammonium, tetra-n-butylammonium, β-methylcholine, and phenyltrimethylammonium. The amount of the catalyst used is 0.001 to 400 parts by mass, preferably 0.005 to 300 parts by mass, based on 100 parts by mass of the total amount of the compound represented by the formula (3).

The method for producing the compound represented by formula (3) is not particularly limited. For example, a fluorene compound and a bis(halogenated methylaryl) compound may be reacted in the presence of an acid catalyst such as hydrochloric acid or activated clay, or a fluorene compound and a bis(hydroxymethylaryl) compound may be reacted in the presence of an acid catalyst such as hydrochloric acid or activated clay. When hydrochloric acid is used as a catalyst, the reaction is neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide, extracted with an aromatic hydrocarbon solvent such as toluene or xylene, washed with water until the wastewater becomes neutral, and the solvent is removed using an evaporator or the like to obtain an olefin compound having at least two or more fluorene structures in the target molecule.

Examples of fluorene-based compounds include fluorene, 1-methylfluorene, 2-methylfluorene, 3-methylfluorene, 4-methylfluorene, 1,6-dimethylfluorene, 1,7-dimethylfluorene, 1,8-dimethylfluorene, 2,3-dimethylfluorene, 2,5-dimethylfluorene, 2,6-dimethylfluorene, 2,7-dimethylfluorene, 3,6-dimethylfluorene, 4,5-dimethylfluorene, 1-ethylfluorene, 2-ethylfluorene, 3-ethylfluorene, 4-ethylfluorene, 1,6-diethylfluorene, 1,7-diethylfluorene, 1,8-diethylfluorene, 2,3-diethylfluorene, 2,5-diethylfluorene, 2,6-diethylfluorene, 2,7-diethylfluorene, 3,6-diethylfluorene, 4,5-diethylfluorene, and the like, but are not limited thereto. A larger number of carbon atoms improves solvent solubility but reduces heat resistance, 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.

Examples of bishalogenated methylaryl compounds include o-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, 4,4'-bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisiodomethylenebiphenyl, Examples of the compound include 2,4-diphenylphenyl, 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bisbromomethylenebiphenyl, 2,4-bisiodomethylenebiphenyl, 2,2'-bisfluoromethylenebiphenyl, 2,2'-bischloromethylenebiphenyl, 2,2'-bisbromomethylenebiphenyl, and 2,2'-bisiodomethylenebiphenyl. From the viewpoint of the reactivity of the raw materials during synthesis, chloride-based compounds, bromide-based compounds, and iodide-based compounds are preferred, and chloride-based compounds and bromide-based compounds are more preferred, but the compound is not limited thereto. Examples of the bishydroxymethylaryl compound include, but are not limited to, o-benzenedimethanol, m-benzenedimethanol, p-benzenedimethanol, 4,4'-bishydroxymethylbiphenyl, 2,4-bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, α,α,α',α'-tetramethyl-1,4-benzenedimethanol, α,α,α',α'-tetramethyl-1,3-benzenedimethanol, and α,α,α',α'-tetramethyl-1,2-benzenedimethanol. These may be used alone or in combination of two or more. The amount of these compounds used is usually 0.05 to 0.8% by weight, preferably 0.1 to 0.6% by weight, based on 1% by weight of the fluorene compound used.

When reacting a compound having a fluorene structure with a halogenated methylaryl compound, etc., a catalyst may be used as needed, such as 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, silica alumina, and other solid acids, and acidic ion exchange resins. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.1 to 0.8 moles, preferably 0.2 to 0.7 moles, per mole of the fluorene 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. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, or may be carried out without a solvent, as necessary. For example, after adding an acidic catalyst to a mixed solution of a fluorene compound, a halogenated methylaryl compound, and a solvent, if the catalyst contains water, the water is removed from the system by azeotropy. Then, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. The temperature is then raised to 80 to 300°C, preferably 80 to 250°C, more preferably 80°C to 200°C, while removing water and low molecular weight components generated in the system by azeotropic dehydration, and the reaction is carried out for 5 to 50 hours, preferably 5 to 30 hours. 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 washing with water is repeated until the wastewater becomes neutral.

The softening point of the compound represented by formula (3) is preferably 150°C or lower, more preferably 120°C or lower. If the softening point is higher than 150°C, the viscosity of the olefin resin becomes high, making it difficult to impregnate carbon fibers or glass fibers. If the viscosity is reduced by increasing the amount of dilution solvent, the resin may not adhere sufficiently to the fibrous material during the impregnation process.

The curable resin composition of the present invention may use any known material as a curable resin other than the olefin compound represented by the formula (1). 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. are mentioned, and it is preferable to contain epoxy resin, active alkene-containing resin, and cyanate ester resin from the balance of heat resistance, adhesion, and dielectric properties. By containing these curable resins, it is possible to improve the brittleness of the cured product and improve adhesion to metal, and it is possible to suppress cracks of the package during solder reflow and reliability tests such as thermal cycles. The curable resin other than the maleimide resin of the present invention may be used alone or in combination.
The amount of the curable resin used is usually 10 times by mass or less, preferably 5 times by mass or less, and more preferably 3 times by mass or less, relative to the olefin compound represented by formula (1). 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 more, the concentration of the olefin compound represented by formula (1) becomes low, and sufficient heat resistance and dielectric properties may not be obtained.

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, 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 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, 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 1,3-bis(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride), cyclopentane tetracarboxylic acid Dianhydrides, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-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(cyclo hexane-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 acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), polycondensation with 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

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 compound: A compound having one or more active ester groups in one molecule can be used as a curing agent for curable resins other than the compound represented by formula (1), such as epoxy resins, 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.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator in order to promote self-polymerization of radically polymerizable curable resins such as olefin resins and maleimide resins, 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.

The curable resin composition of the present invention may be used in combination with a curing accelerator (curing catalyst) as necessary. 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 is preferably an organic acid ion or hydroxide ion), and 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 0.001 to 5.0 parts by weight per 100 parts by mass of the curable resin composition, 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). 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, an antioxidant may be added to the curable resin composition of the present invention, if necessary. Usable antioxidants include phenol-based, sulfur-based, and phosphorus-based antioxidants. The antioxidants may be used alone or in combination of two or more. The amount of antioxidant 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 components in the curable resin composition of the present invention. Each of these antioxidants may be used alone, but two or more may be used in combination. In particular, phosphorus-based antioxidants are preferred in the present invention.

Specific examples of phenol-based antioxidants 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 antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

Specific examples of phosphorus-based antioxidants 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.

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-based 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 used is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin component, 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 can contain known additives as necessary. Specific examples of additives that can 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 where moisture resistance, heat resistance, and high adhesion are required. 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, etc. 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 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 multilayer substrates, 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]
A flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 100 parts of toluene, 41.6 parts of fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.3 parts of 4,4'-benzene dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.9 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and reacted at 110 ° C. for 3 hours. After cooling, 6.0 parts of 30 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes to perform neutralization. Subsequently, 100 parts of dimethyl sulfoxide, 5.0 parts of water, and 30 parts of sodium hydroxide were added, and 57.4 parts of allyl chloride were added dropwise over 1 hour so that the internal temperature did not exceed 30 ° C., and the reaction was performed at 40 ° C. for 8 hours. After cooling, 300 parts of toluene and 25 parts of methanol were added, and the organic layer was washed five times with 100 parts of water, and the solvent and excess allyl chloride were distilled off under heating and reduced pressure, to obtain 68.9 parts of olefin compound (O-1) as an orange liquid resin. The GPC chart of the obtained olefin resin at the completion of the reaction is shown in Figure 1. The molecular weight by GPC analysis was Mn: 506, Mw: 958. The ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in Figure 2. A signal derived from an allyl group was observed at 4.50-6.20 ppm in the ¹ H-NMR chart.

[Example 2]
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 100 parts of toluene, 41.6 parts of fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.3 parts of α,α,α',α'-tetramethylbenzene dimethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.9 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and reacted at 110 ° C. for 1 hour. After cooling, 6.0 parts of 30 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes to perform neutralization. Subsequently, 100 parts of dimethyl sulfoxide, 5.0 parts of water, and 30 parts of sodium hydroxide were added, and 57.4 parts of allyl chloride were added dropwise over 1 hour so that the internal temperature did not exceed 30 ° C., and the reaction was performed at 40 ° C. for 8 hours. After cooling, 300 parts of toluene and 25 parts of methanol were added, and the organic layer was washed five times with 100 parts of water. The solvent and excess allyl chloride were distilled off under heating and reduced pressure, obtaining 70.6 parts of olefin compound (O-2) as a yellow liquid resin.

[Example 3]
The olefin compound (O-1) obtained in Example 1, the thermosetting polyphenylene ether resin SA-9000-111 (manufactured by SABIC), and dicumyl peroxide were added to toluene to prepare a resin solution (S-1). S-1 was cast onto a commercially available imide film (Toray DuPont's "Kapton (registered trademark) 100H") using an applicator (wet film thickness 200 μm), and the applied resin film was heated and dried in a nitrogen atmosphere for 10 minutes with hot air at 120 ° C. and for 1 hour with hot air at 220 ° C. to remove the solvent, thereby obtaining a film-like cured product (film thickness 105 μm). The obtained film was cut to a length of 4 mm and a width of 3 mm and used for cured physical property evaluation. The measurement results are shown in Table 1.

[Comparative Example 1]
A biphenyl aralkyl type epoxy resin (NC-3000L manufactured by Nippon Kayaku Co., Ltd.), a biphenyl aralkyl type phenolic resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.), and 2-ethyl-4-methylimidazole (abbreviation: 2E-4MZ manufactured by Tokyo Kasei Co., Ltd.) as a curing accelerator were used and compounded in the ratios (parts by weight) shown in Table 1. The components were uniformly mixed and kneaded using a mixing roll, and after demolding, cured at 160°C for 2 hours and at 180°C for 6 hours to obtain a test piece for evaluation.

<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 AET Development Co., Ltd. using the cavity resonator perturbation method.

From the results in Table 1, it was confirmed that Example 3 has high heat resistance and excellent dielectric properties. In particular, the dielectric tangent of Example 3 is one order of magnitude lower than that of Comparative Example 1, and has extremely excellent properties.

Claims (1)

A compound represented by the following formula (3):
(In formula (3), X represents one or more of (b) to (j) in formula (2) below, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group, m each independently represents an integer of 0 to 3, and n represents 1≦n≦5.)

(In formula (2), * indicates the bonding position with the skeleton structure.)

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