JP7360345B2 - Olefin resin, curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to an olefin resin having a specific structure, a curable resin composition using the same, and a cured product thereof, and relates to electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates, Suitable for use in lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber 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 in recent years, semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are mounted on laminates made of polymer materials. It is increasingly being installed in

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. As the PKG becomes thinner, its rigidity decreases, causing 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. Therefore, 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, which cannot be met by conventional epoxy resin encapsulants.

Against this background, polymer materials that can 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, since phenolic hydroxyl groups that do not participate in the curing reaction remain, the electrical properties cannot be said to be sufficient. Further, Patent Document 2 discloses an allyl ether resin in which the hydroxyl group is substituted with an allyl group. However, it has been shown that Claisen rearrangement occurs at 190°C, and at 200°C, which is the general molding temperature for substrates, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so electrical properties cannot be satisfied. do not have.

In recent years, 3D printing has attracted attention as a three-dimensional modeling method, and 3D printing methods are being applied in fields that require reliability, such as aerospace, cars, and connectors for electronic components used in these. It's starting. In particular, photocuring and thermosetting resins are being studied for applications typified by stereolithography (SLA) and digital light processing (DLP). Therefore, in the conventional method of transferring from a mold, stability and accuracy of shape are mainly required, but in 3D printing applications, heat resistance, mechanical properties, toughness, flame retardance, and even electrical properties are required. A variety of properties are required, and the development of materials for these properties is progressing. Furthermore, when used in structural members, changes in characteristics due to moisture absorption, etc. are a problem. Currently, acrylate resins and epoxy resins are used in such applications, but their cured products contain many ester bonds, ether bonds, and even hydroxyl groups, and do not have sufficient properties such as hygroscopicity. Not.

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

The present invention was made in view of these circumstances, and aims to provide an olefin resin, 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 new olefin resin 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 [4].
[1] Olefin resin having repeating units of the following formulas (a) and (b).

(In the above formula, m and n each independently represent a real number from 1 to 20. R represents a substituent bonded to the norbornene structure in formula (a) or the norbornene structure in formula (b) , and Represents a hydrocarbon group or a halogenated alkyl group of numbers 1 to 18. p represents a real number of 0 to 9, and q represents a real number of 0 to 11. (a) and (b) are each bonded with *, and repeat (The position may be random.)
[2]
Among the olefin resins described in the preceding item [1], p and q are 0.
[3]
A curable resin composition containing the olefin resin described in the preceding item [1] or [2].
[4]
A cured product obtained by curing the curable resin composition described in the preceding item [3].

The olefin resin of the present invention has excellent heat resistance and dielectric properties. Therefore, it is useful for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, 3D printing, etc.

1 shows a GPC chart of the reaction solution of Example 1. A ¹ H-NMR chart of Example 1 is shown.

The olefin resin according to the present invention is represented by the following formula (1).

(In the above formula, m and n each independently represent a real number from 1 to 20. R represents a substituent bonded to the norbornene structure in formula (a) or the norbornene structure in formula (b) , and Represents a hydrocarbon group or a halogenated alkyl group of numbers 1 to 18. p represents a real number of 0 to 9, and q represents a real number of 0 to 11. (a) and (b) are each bonded with *, and repeat (The position may be random.)

In the above formula, m and n are each independently preferably from 1.1 to 20, more preferably from 1.1 to 10, particularly preferably from 2 to 5. p and q are preferably 0 to 6, more preferably 0 to 3, and particularly preferably 0. R is preferably unsubstituted or a hydrocarbon group having 1 to 3 carbon atoms, more preferably unsubstituted or a hydrocarbon group having 1 to 2 carbon atoms, and is unsubstituted or has 1 carbon number. is more preferred, and unsubstituted is particularly preferred. When p and q are small, or when the number of carbon atoms in R is small, molecular vibrations are less likely to occur when exposed to high frequencies, resulting in good electrical properties.

The method for producing the olefin resin of the present invention is not particularly limited. For example, a compound having a 5-vinyl-2-norbornene structure can be reacted in the presence of an acid catalyst such as boron trifluoride diethyl ether complex, aluminum chloride, hydrochloric acid, sulfuric acid, methanesulfonic acid, activated clay, or the like. When using boron trifluoride diethyl ether complex as a catalyst, add water to the reaction solution to stop the reaction, extract with an aromatic hydrocarbon solvent such as toluene or xylene, and wash with water until the waste water becomes neutral. The olefin resin of the present invention can be obtained by distilling off the solvent using an evaporator or the like.

Examples of the compound having a 5-vinyl-2-norbornene structure include 5-vinyl-2-norbornene, which may be used alone or in combination with other compounds having a norbornene structure or cationically polymerizable compounds. You may.
Examples of the cationic polymerizable compound include, but are not limited to, styrene, α-methylstyrene, β-methylstyrene, indene, benzofulvene, and dibenzofulvene. The substituent of the compound having a norbornene structure used as a raw material is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. It is preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, even more preferably unsubstituted or substituted with a methyl group, and particularly preferably unsubstituted. .
When a cationically polymerizable compound is used, the amount used is preferably 0.001 to 0.9% by weight, and 0.01 to 0. More preferably, it is .8% by weight.

When synthesizing the olefin resin of the present invention, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, Lewis acids such as aluminum chloride, zinc chloride, and boron trifluoride, activated clay, Catalysts such as acid clay, white carbon, zeolite, solid acids such as silica alumina, and acidic ion exchange resins can be used. These may be used alone or in combination of two or more. The amount of the catalyst used is generally 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, per 1 mol of the compound having a 5-vinyl-2-norbornene structure. 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 compound having a 5-vinyl-2-norbornene structure and a solvent, the reaction is carried out at 0 to 120°C, preferably 10 to 100°C for 0.5 to 20 hours. After the reaction is complete, a water-insoluble organic solvent is added to the oil layer and water washing is repeated until the waste water becomes neutral.

The softening point of the olefin resin of the present invention is preferably 160°C or lower, more preferably 150°C or lower. When the softening point is higher than 160°C, the viscosity of the olefin resin increases, making it difficult to impregnate carbon fibers and glass fibers. Although the viscosity can be lowered by increasing the amount of diluting solvent, the resin may not adhere well to the fibrous material during the impregnation step.

The curable resin composition of the present invention may use any known material as the curable resin other than the olefin resin of the present invention. 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. These 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 resin of the present invention. 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 resin of the present invention becomes low, and there is a possibility that sufficient heat resistance and dielectric properties cannot be obtained.

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 novolak, aniline resin obtained by reaction of aniline with xylylene chloride, aniline and aniline described in Japanese Patent No. 6429862. 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, 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 phenolic resin with a cyanide 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 usually used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by 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 essential components described in the present invention, 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 novolak. 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 be used in combination with a curing accelerator, 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( 5,4,0) Tertiary amines such as 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 curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, 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 epoxy resin) is in the range of 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, there is a 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 weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. 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, the curable resin composition of the present invention can also contain a binder resin, 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 to 20 parts by mass, per 100 parts by mass of the resin component. Parts by mass are used as appropriate.

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, 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 can be added. can. 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 weight, preferably 15 to 70% by weight 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.
<Weight average molecular weight (Mw), number average molecular weight (Mn)>
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]
24.4 parts of 5-vinyl-2-norbornene (manufactured by Tokyo Kasei Co., Ltd.) and 25 parts of toluene were added to a flask equipped with a thermometer, cooling tube, and stirrer, and stirring was started. 0.43 parts of boron trifluoride diethyl ether complex (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was reacted at room temperature for 6 hours, at 45°C for 1 hour, and at 70°C for 6 hours. 1 part of sodium hydrogen sulfate and 100 parts of water were added to stop the reaction. Extraction was performed with 100 parts of toluene, and the organic layer was washed five times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 21 parts of olefin resin (VN-1) was obtained as a solid resin (Mn: 972, Mw: 7672). A GPC chart of the reaction solution upon completion of the reaction is shown in FIG. Furthermore, a ¹ H-NMR chart (CDCl3) of the obtained compound is shown in FIG. A signal derived from vinyl groups was observed at 4.60-6.10 ppm on the ¹ H-NMR chart.

[Example 2]
The compound (VN-1) obtained in Example 1 was solidified by distilling off the solvent under reduced pressure from the resin solution containing the maleimide resin (M2) described in Example 4 of JP-A-2009-001783. , and dicumyl peroxide (DCP, manufactured by Tokyo Kasei Co., Ltd.) as a curing accelerator in the proportions (parts by mass) shown in Table 1, heated and melted in a metal container, poured into a mold, and heated to 220°C. Allowed to cure for hours. The evaluation results are shown in Table 1.

[Comparative example 1]
Biphenylaralkyl type epoxy resin (NC-3000L manufactured by Nippon Kayaku Co., Ltd.), biphenylaralkyl type phenol resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.), curing accelerator 2-ethyl-4-methylimidazole (2E-4MZ, Tokyo (manufactured by Kasei Co., Ltd.), blended in the proportions (parts by weight) shown in Table 1, mixed and kneaded uniformly using a mixing roll, and after demolding, conditions of 2 hours at 160 ° C. and 6 hours at 180 ° C. hardened with. The evaluation results are shown in Table 1.

<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 Kanto Denshi Application Development Co., Ltd.

From the results in Table 1, it was confirmed that Example 2 had high heat resistance and excellent dielectric properties. In particular, the dielectric loss tangent of Example 2 is one order of magnitude lower than that of Comparative Example 1, and has extremely excellent characteristics.

Claims (4)

An olefin resin consisting only of repeating units of the following formula (a) and repeating units of the following formula (b) .

(In the above formula, m and n each independently represent a real number from 1 to 20. R represents a substituent bonded to the norbornene structure in formula (a) or the norbornene structure in formula (b) , and Represents a hydrocarbon group or a halogenated alkyl group of numbers 1 to 18. p represents a real number of 0 to 9, and q represents a real number of 0 to 11. (a) and (b) are each bonded with *, and repeat (The position may be random.) The olefin resin according to claim 1, wherein p and q are 0. A curable resin composition containing the olefin resin according to claim 1 or 2. A cured product obtained by curing the curable resin composition according to claim 3.

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