JP7360981B2 - Olefin compounds, curable resin compositions and cured products thereof - Google Patents

Description

The present invention relates to an olefin compound, a curable resin composition, and a cured product thereof, and is used for electrical and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates, carbon fiber reinforced plastics, and glass fibers. Suitable for use in lightweight, high-strength materials such as reinforced plastics.

In recent years, the fields of use for laminates that carry electrical and electronic components have expanded, and the required characteristics have become broader and more sophisticated. 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 mounted on laminated boards made of polymer materials. It is increasingly being installed.

In particular, semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like are required to have thinner PKG substrates in order to meet the demands for smaller size, thinner profile, and higher density. When the PKG becomes thinner, its rigidity decreases, which causes problems such as large warping due to heating when the PKG is soldered to the motherboard (PCB). In order to reduce this, a PKG substrate material with a high Tg higher than the solder mounting temperature is required.

In addition, 5G, the fifth generation communication system whose development is currently accelerating, is expected to further increase capacity and speed. The need for low dielectric loss tangent materials is increasing, and a dielectric loss tangent of 0.005 or less is required at least at 1 GHz.

Furthermore, in the automotive field, computerization is progressing, and precision electronic equipment is sometimes placed near engine drive parts, so higher levels of heat and moisture resistance are required. SiC semiconductors are beginning to be used in trains, air conditioners, etc., and the encapsulating material for semiconductor elements is required to have extremely high heat resistance, so conventional epoxy resin encapsulating materials can no longer meet this demand.

Against this background, polymer materials that have both heat resistance and low dielectric loss tangent characteristics are being investigated. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenol resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain, the electrical properties cannot be said to be sufficient.

Japanese Patent Application Publication No. 04-359911

The present invention was made in view of these circumstances, and aims to provide an olefin compound, a curable resin composition, and a cured product thereof, which exhibits excellent heat resistance and electrical properties, and has good curability. purpose.

As a result of intensive research to solve the above problems, the present inventors discovered that a cured product of a curable resin composition containing a novel olefin compound has excellent heat resistance and low dielectric properties, and completed the present invention. reached.

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, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or a halogenated alkyl group. Represents an integer, and n represents 1≦n≦20.Y exists independently and is any one or more of (A) to (D), excluding those in which 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) described in 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 only by (A).
[5]
The olefin compound according to any one of the above items [1] to [3], wherein in the formula (1), Y is represented only by (C).
[6]
The olefin compound according to any one of the above 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, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or a halogenated alkyl group. represents an integer, and n represents 1≦n≦20.)
[8]
A curable resin composition containing the olefin compound according to any one of items [1] to [7] above.
[9]
A cured product obtained by curing the curable resin composition according to item [8].
[10]
A compound represented by the following formula (3).

(In formula (3), X represents any organic group, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or a halogenated alkyl group. represents an integer, 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 electrical and electronic parts, circuit boards, carbon fiber composite materials, etc.

FIG. 1: Shows the 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, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or a halogenated alkyl group. Represents an integer, and n represents 1≦n≦20.Y exists independently and is any one or more of (A) to (D), excluding those in which all are (D). .* indicates the bonding position with the skeletal structure.)

In the formula (1), Y is usually one or more of (A) to (D), and preferably one or more of (A) to (C) from the viewpoint of curability. is more preferably (A) or (C) in order to further improve curability.

In the formula (1), m is preferably 0 to 2, more preferably 0. It is preferable that n is 1≦n≦10, and more preferably that 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 number. When R is a hydrocarbon having 3 or less carbon atoms, it is difficult to cause molecular vibration when exposed to high frequency, so it has excellent electrical properties.

Further, in the above formula (1), it is preferable that X is any one or more of (a) to (j) described in the following formula (2), and any one of (b) to (i) It is more preferable that it is the above, and particularly preferable that it is (b) or (d).

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

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

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

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

The olefin compound represented by the above formula (1) of the present invention is derived from the compound represented by the above formula (3), and specifically, the olefin compound represented by the above formula (3) is a compound represented by the above formula (3). It is obtained by reacting a halogen compound having a saturated double bond in the presence of a catalyst. For example, it can be obtained by reacting the compound represented by the formula (3) with allyl chloride, methallyl chloride, chloromethylstyrene, etc. in a solvent in the presence of a basic catalyst. Examples of the solvent used include aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone. Moreover, in addition to the aprotic polar solvent, a water-insoluble solvent can also be used in combination. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, methyl isobutyl ketone, cyclopentanone, etc. Examples include, but are not limited to, ketone solvents, and two or more types may be used in combination. The catalyst is not particularly limited, but includes basic catalysts such as sodium hydroxide, potassium hydroxide, potassium carbonate, and the like. Furthermore, when the reaction is carried out in the coexistence of water in a water-insoluble solvent, a phase transfer catalyst can also be coexisting. Examples include quaternary ammonium salts such as 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, etc. Examples include chloride salts, chloride salts, iodide salts, hydrogen sulfates, and hydroxides. The amount used is 0.001 to 400 parts by weight, preferably 0.005 to 300 parts by weight, based on 100 parts by weight of the total amount of the compound represented by formula (3).

The method for producing the compound represented by formula (3) is not particularly limited. For example, a fluorene compound and a bishalogenated methylaryl compound may be reacted under an acid catalyst such as hydrochloric acid or activated clay, or a fluorene compound and a bishydroxymethylaryl compound may be reacted under an acid catalyst such as hydrochloric acid or activated clay. It's okay. When hydrochloric acid is used as a catalyst, it is neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide, extracted with an aromatic hydrocarbon solvent such as toluene or xylene, and then washed with water until the wastewater becomes neutral. By distilling off the solvent using , the desired olefin compound having at least two fluorene structures in its molecule can be obtained.

Examples of fluorene 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-diethyl Examples include, but are not limited to, fluorene, 2,7-diethylfluorene, 3,6-diethylfluorene, and 4,5-diethylfluorene. When the number of carbon atoms is large, solvent solubility improves, but heat resistance decreases, so it is preferable that the number of carbon atoms is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. It is more preferably substituted with a group, and most preferably unsubstituted or substituted with a methyl group.

Examples of bishalogenated methylaryl compounds include о-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, о-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, о- Xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, о-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, 4,4'-bisfluoromethylene biphenyl, 4,4 '-Bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisiodomethylenebiphenyl, 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bis Bromomethylene biphenyl, 2,4-bisiodomethylene biphenyl, 2,2'-bisfluoromethylene biphenyl, 2,2'-bischloromethylene biphenyl, 2,2'-bisbromo methylene biphenyl, 2,2'-biiodine Examples include methylene biphenyl, and from the viewpoint of reactivity of 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 are not limited thereto. It's not something you can do. Further, the bishydroxymethylaryl compounds include о-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, Examples include, but are not limited to, α, α, α', α'-tetramethyl-1,2-benzenedimethanol. These may be used alone or in combination of two or more. The amount of these 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., as a catalyst, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, or Lewis acid such as aluminum chloride or zinc chloride may be used as a catalyst. Examples include solid acids such as acids, activated clay, acid 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 the catalyst used is usually 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, per 1 mol of the fluorene compound used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult, while if it is too small, the progress of the reaction may be slowed down. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, xylene, etc., or without a solvent, if 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, water is removed from the system by azeotropy. Thereafter, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. Thereafter, the temperature is raised to 80 to 300°C, preferably 80 to 250°C, more preferably 5 to 50°C at 80 to 200°C while removing water and low molecular weight components generated in the system by azeotropic dehydration. The reaction is carried out for a period of time, preferably from 5 to 30 hours. After the reaction is completed, the acidic catalyst is neutralized with an aqueous alkali solution, a water-insoluble organic solvent is added to the oil layer, and water washing 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 olefin resin will have a high viscosity and will be difficult to impregnate into carbon fibers or glass fibers. If the viscosity is lowered by increasing the amount of diluting solvent, there is a possibility that the resin will not adhere sufficiently to the fibrous material during the impregnation process.

In the curable resin composition of the present invention, any known material may be used as the curable resin other than the olefin compound represented by formula (1). Specifically, phenolic resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, propenyl resins, methallyl resins, active ester resins, etc. From the viewpoint of balance of properties and dielectric properties, it is preferable to contain an epoxy resin, an active alkene-containing resin, and a cyanate ester resin. By containing these curable resins, the brittleness of the cured product can be improved and its adhesion to metal can be improved, and cracks in the package can be suppressed during reliability tests such as during solder reflow and cooling/heating cycles. The curable resins other than the maleimide resin of the present invention may be used alone or in combination.
The amount of the curable resin to be used is usually 10 times or less, preferably 5 times or less, more preferably 3 times or less by mass relative to the olefin compound represented by formula (1). Further, a preferable lower limit is 0.5 times by mass or more, more preferably 1 times by mass or more. When the amount is 10 times or more by mass, the concentration of the olefin compound represented by the formula (1) becomes low, and there is a possibility that sufficient heat resistance and dielectric properties cannot be obtained.

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

Phenol resin: Phenols (phenol, alkyl-substituted phenol, aromatic substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, Polycondensates of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, polymers with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) Polycondensates, phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted Phenol resins and bisphenols obtained by polycondensation with phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), etc. and polycondensates of various aldehydes, polyphenylene ether.

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

Amine resin: diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, naphthalene diamine, aniline novolak, orthoethylaniline novolac, aniline resin obtained by reaction of aniline and xylylene chloride, aniline and substituted biphenyl described in Patent No. 6429862 (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, 1,4-bis(hydroxymethyl)benzene, etc.).

Active alkene-containing resin: polycondensate of the above-mentioned phenolic resin and active alkene-containing halogen compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), active alkene-containing phenols (2- Allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4 - Bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), substituted or unsubstituted with epoxy resins or alcohols. Polycondensates of substituted 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'-diphenyl ether bismaleimide , 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene).

Isocyanate resin: p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc. Aromatic diisocyanates; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate; one or more types of isocyanate monomers A polyisocyanate such as a buret form or an isocyanate form obtained by trimerizing the above diisocyanate compound; A polyisocyanate obtained by a urethanization reaction between the above isocyanate compound and a polyol compound.

Polyamide resin: amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and diamines (ethylenediamine , trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine , heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane; cyclohexanediamine, bis-(4 -Alicyclic diamines such as aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, Aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and mixtures with dichloride). A polymer whose main raw material is one or more of:

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'-diphenylsulfone tetra Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic acid 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 Anhydride, 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-dicarboxyphenoxy)benzene dianhydride carboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, carboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis( 3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride), cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride Acid 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(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane) -1,2-dicarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R] -3-Oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-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 acid anhydride), 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 those obtained by converting the hydroxyl group of a phenol/dicyclopentadiene cocondensate into a cyanate group, but are not limited to these.
Furthermore, cyanate ester compounds whose synthesis method is described in JP-A No. 2005-264154 are particularly preferred as cyanate ester compounds because they have low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
The cyanate resin may optionally contain zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, or lead in order to trimerize the cyanate group to form a sym-triazine ring. Catalysts such as acetylacetonate and dibutyltin maleate can also be included. The catalyst is generally used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, based on 100 parts by weight of the total weight 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. . Active ester curing agents include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. preferable. The active ester curing agent is preferably one obtained by a condensation reaction between at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound are preferred. Agents are preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.
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 novolak, and a benzoylated product of phenol novolac. Examples include active ester compounds containing. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
Commercially available active ester curing agents include "EXB9451,""EXB9460,""EXB9460S,""HPC-8000-65T," and "HPC-" as active ester compounds containing a dicyclopentadiene diphenol structure. 8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure; acetylated product of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing phenol novolac; "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing benzoylated phenol novolac; acetylated phenol novolac Examples of the active ester curing agent include "DC808" (manufactured by Mitsubishi Chemical Corporation); and examples of the phosphorus atom-containing active ester curing agent include "EXB-9050L-62M" manufactured by DIC Corporation.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of the curable resin capable of radical polymerization such as olefin resin or maleimide resin or radical polymerization with other components. . Examples of radical polymerization initiators that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butyl peroxide). dialkyl peroxides such as isopropyl)-benzene, peroxyketals such as t-butylperoxybenzoate, 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peresters such as benzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butylperoxydicarbonate) Peroxycarbonates such as (oxycarbonyloxy)hexane, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide, azobisisobutyronitrile, etc. , 4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and other known curing accelerators for azo compounds, but are particularly limited to these. It's not a thing. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates and the like are preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, per 100 parts by weight of the curable resin composition. If the amount of radical polymerization initiator used is too large, the molecular weight will not be sufficiently extended during the polymerization reaction.

The curable resin composition of the present invention may contain a curing accelerator (curing catalyst) in combination, if necessary. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo[ Tertiary amines such as 5,4,0]undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen, (Organic acid ions, hydroxide ions, etc., although there are no particular specifications, organic acid ions and hydroxide ions are particularly preferred.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen Examples include transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid ester, zinc misty phosphate) and zinc phosphate ester (zinc octyl phosphate, zinc stearyl phosphate, etc.). The amount of the curing accelerator used is 0.001 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, if necessary.

The curable resin composition of the present invention can also contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, and 1,3-phenylene bis( Phosphate esters such as dixylylenyl phosphate), 1,4-phenylenebis(dixylylenyl phosphate), and 4,4'-biphenyl(dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the above phosphanes Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(dixylylenyl phosphate), 1 , 4-phenylenebis(dixylylenyl phosphate), 4,4'-biphenyl(dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably such that (phosphorus-containing compound)/(total curable resin) is in the range of 0.1 to 0.6 (mass ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, there is a concern that the hygroscopicity and dielectric properties of the cured product will be adversely affected.

Furthermore, an antioxidant may be added to the curable resin composition of the present invention, if necessary. Examples of antioxidants that can be used include phenolic, sulfur, and phosphorus antioxidants. Antioxidants can be used alone or in combination of two or more. The amount of antioxidant used is usually 0.008 to 1 part by mass, preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the resin component in the curable resin composition of the present invention. It is. Each of these antioxidants can be used alone, but two or more kinds may be used in combination. Particularly in the present invention, phosphorus-based antioxidants are preferred.

Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio) Monophenols such as -6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol; 2 , 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t- butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 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-hydroxy Benzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4, Bisphenols such as 8,10-tetraoxaspiro[5,5]undecane, bis(ethyl 3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium; 1,1,3-tris(2- Methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis- [Methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]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 Examples include polymeric phenols such as -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, distearyl-3,3'-thiodipropionate, etc. Ru.

Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t -butylphenyl) phosphite, cyclic neopentanetetryrubis(octadecyl)phosphite, cyclic neopentanetetryruby(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetryruby(2, 4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, etc. Class; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa Examples include oxaphosphaphenanthrene oxides such as -10-phosphaphenanthrene-10-oxide and 10-desyloxy-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, if necessary. As the light stabilizer, hindered amine light stabilizers, particularly HALS, etc. are suitable. HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2,2, 6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl -4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, a binder resin can be added to the curable resin composition of the present invention, if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin, etc. , but not limited to these. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by mass, preferably 0.05 parts by mass, based on 100 parts by mass of the curable resin component. ~20 parts by weight is used as needed.

Furthermore, the curable resin composition of the present invention may optionally contain fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia. Adding powders such as aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers made of these in spherical or crushed form. I can do it. In addition, especially when obtaining a curable resin composition for semiconductor encapsulation, the amount of the above-mentioned inorganic filler used is usually in the range of 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. be.

The curable resin composition of the present invention may contain known additives, if necessary. Specific examples of additives that can be used include fillers such as polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesins, silicone gels, silicone oils, and silane coupling agents. Examples include surface treatment agents for materials, mold release agents, and coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green. The blending amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

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

The curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, and high adhesiveness. Therefore, the curable resin composition of the present invention can be used in a wide range of fields where moisture resistance, heat resistance, and high adhesiveness are required. Specifically, it is useful as an insulating material, a laminated board (printed wiring board, BGA board, build-up board, etc.), a sealing material, a resist, and other materials for all electrical and electronic components. In addition to molding materials and composite materials, it can also be used in fields such as paint materials and adhesives. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.

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

The method for preparing the curable resin composition of the present invention is not particularly limited, but the components may be simply 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, curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate ester compounds, phenol resins, acid anhydride compounds, and other additives may be added to form a prepolymer. good. For mixing or prepolymerization of each component, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reaction vessel equipped with a stirring device, etc., is used in the presence of a solvent.

The method for uniformly mixing is to knead the resin composition using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100° C. to obtain a uniform resin composition. After the obtained resin composition is crushed, it is molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or it is made into a granular powder or a powder-like molded product, or the composition is molded onto a surface support. A curable resin composition molded product can also be obtained by melting and molding into a sheet having a thickness of 0.05 mm to 10 mm. The obtained molded product becomes a non-sticky molded product at 0 to 20°C, and its fluidity and hardenability hardly decrease even if it is stored at -25 to 0°C for one week or more.
The obtained molded product can be molded into a cured product using a transfer molding machine or a compression molding machine.

It is also possible to add an organic solvent to the curable resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish). The curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, etc. as necessary to form a varnish, which can be applied to glass fibers or carbon fibers. A cured product of the curable resin composition of the present invention can be obtained by hot press molding a prepreg obtained by impregnating a base material such as polyester fiber, polyamide fiber, alumina fiber, or paper and drying it by heating. . The amount of the solvent used in this case is usually 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition of the present invention and the solvent. Further, if the composition is a liquid composition, a cured resin containing carbon fibers can be obtained as it is, for example, by the RTM method.

Furthermore, 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 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 B-staging it. It is obtained as a sheet adhesive. This sheet adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

A prepreg can be obtained by heating and melting the curable resin composition of the present invention, reducing the viscosity, and impregnating it into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. 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, as well as inorganic fibers other than glass and polyester fibers. Paraphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Corporation), fully aromatic polyamide, polyester; and organic fibers such as polyparaphenylenebenzoxazole, polyimide, and carbon fiber, but are particularly limited to these. Not done. The shape of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, plain weaving, Nanako weaving, twill weaving, etc. are known as weaving methods of the woven fabric, and the weaving method can be appropriately selected from these known methods depending on the intended use and performance. In addition, woven fabrics subjected to opening treatment or glass woven fabrics whose surface is treated with a silane coupling agent or the like are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Further, a prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the impregnated fibers by heating.

The laminate of this embodiment includes one or more of the prepregs described above. The laminate is not particularly limited as long as it includes one or more prepregs, and may include any other layers. The method for manufacturing the laminate is not particularly limited, and any generally known method can be appropriately applied. For example, when molding a 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. Obtainable. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. The pressure to be applied is not particularly limited, but if the pressure is too high, it will be difficult to adjust the solids content of the resin in the laminate, and the quality will not be stable.If the pressure is too low, air bubbles and adhesion between the laminates may occur. 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminate of this embodiment can be suitably used as a metal foil-clad laminate, which will be described later, by including a layer made of metal foil.
After cutting the above prepreg into a desired shape and laminating it with copper foil etc. if necessary, the curable resin composition is heated and cured while applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, etc. Electrical and electronic laminates (printed wiring boards) and carbon fiber reinforced materials can be obtained.

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

Next, the present invention will be explained in more detail with reference to Examples. Hereinafter, parts are by weight unless otherwise specified. Note that 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)>
Calculated by polystyrene conversion using a polystyrene standard solution.
GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
Column: Shodex KF-603, KF-602x2, KF-601x2)
Coupling eluent: Tetrahydrofuran Flow rate: 0.5ml/min.
Column temperature: 40℃
Detection: RI (differential refraction detector)

[Example 1]
In a flask equipped with a thermometer, cooling tube, and stirrer, add 100 parts of toluene, 41.6 parts of fluorene (manufactured by Tokyo Kasei Co., Ltd.), 17.3 parts of 4,4'-benzenedimethanol (manufactured by Tokyo Kasei Co., Ltd.), and methanesulfone. 2.9 parts of acid (manufactured by Tokyo Kasei Co., Ltd.) was charged and reacted at 110°C for 3 hours. After cooling, 6.0 parts of a 30 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes to effect neutralization. Next, 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 was added dropwise over 1 hour so that the internal temperature did not exceed 30°C. The reaction was carried out for 8 hours. After cooling, 300 parts of toluene and 25 parts of methanol were added, the organic layer was washed 5 times with 100 parts of water, and the solvent and excess allyl chloride were distilled off under heating and reduced pressure to remove the olefin compound (O-1). 68.9 parts of orange liquid resin was obtained. A GPC chart of the obtained olefin resin upon completion of the reaction is shown in FIG. The molecular weight by GPC analysis was Mn: 506, Mw: 958. Furthermore, a ¹ H-NMR chart (CDCl ₃ ) of the obtained compound is shown in FIG. A signal derived from an allyl group was observed at 4.50-6.20 ppm on the ¹ H-NMR chart.

[Example 2]
In a flask equipped with a thermometer, cooling tube, and stirrer, 100 parts of toluene, 41.6 parts of fluorene (manufactured by Tokyo Kasei Co., Ltd.), α, α, α', α'-tetramethylbenzenedimethanol (Fuji Film Wako Pure Chemical Industries, Ltd.) 24.3 parts of methane sulfonic acid (manufactured by Tokyo Kasei Co., Ltd.) and 2.9 parts of methanesulfonic acid (manufactured by Tokyo Kasei Co., Ltd.) were added, and the mixture was reacted at 110°C for 1 hour. After cooling, 6.0 parts of a 30 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes to effect neutralization. Next, 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 was added dropwise over 1 hour so that the internal temperature did not exceed 30°C. The reaction was carried out for 8 hours. After cooling, 300 parts of toluene and 25 parts of methanol were added, the organic layer was washed 5 times with 100 parts of water, and the solvent and excess allyl chloride were distilled off under heating and reduced pressure to remove the olefin compound (O-2). 70.6 parts of yellow liquid resin was obtained.

[Example 3]
Add the olefin compound (O-1) obtained in Example 1, thermosetting polyphenylene ether resin SA-9000-111 (manufactured by SABIC), and dicumyl peroxide to toluene to prepare a resin solution (S-1). did. S-1 was cast onto a commercially available imide film (Kapton (registered trademark) 100H manufactured by DuPont Toray) using an applicator (WET film thickness 200 μm), and the applied resin film was heated at 120°C under a nitrogen atmosphere. The solvent was removed by heating and drying with hot air at 220° C. for 10 minutes and with hot air at 220° C. for 1 hour to obtain a cured product in the form of a film (thickness: 105 μm). The obtained film was cut to a length of 4 mm and a width of 3 mm, and used for evaluation of cured physical properties. The measurement results are shown in Table 1.

[Comparative example 1]
Biphenylaralkyl epoxy resin (NC-3000L manufactured by Nippon Kayaku Co., Ltd.), biphenylaralkyl type phenol resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.), and 2-ethyl-4-methylimidazole (abbreviation: 2E) as a curing accelerator. -4MZ (manufactured by Tokyo Kasei Co., Ltd.), were blended in the proportions (parts by weight) shown in Table 1, uniformly mixed and kneaded using a mixing roll, and after demolding, heated at 160°C for 2 hours and at 180°C for 6 hours. It was cured for a certain amount of time to obtain a test piece for evaluation.

<Heat resistance test>
-Glass transition temperature: measured by a dynamic viscoelasticity tester, the temperature when tan δ is at its maximum value.
Dynamic viscoelasticity measuring instrument: DMA-2980 manufactured by TA-instruments
Temperature rising rate: 2℃/min <dielectric constant test/dielectric loss tangent test>
・Tests were conducted using a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by AET Development Co., Ltd.

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

Claims (8)

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

(In formula (1), X represents any one or more of (a) to (j) described in formula (2) below , and R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or Represents a halogenated alkyl group. m each independently represents an integer of 0 to 3, n represents 1≦n≦20. Y exists independently, and any of (A) to (D) or one or more types, excluding those in which all are (D). * indicates the bonding position with the skeletal structure.)

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

(In formula (3), X represents any organic group, R each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or a halogenated alkyl group. represents an integer, and n represents 1≦n≦20.) A curable resin composition containing the olefin compound according to any one of claims 1 to 6 . A cured product obtained by curing the curable resin composition according to claim 7 .

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