JPWO2019131413A1 - Thermosetting composition, thermosetting resin modifier, cured product thereof, semiconductor encapsulant material, prepreg, circuit board and build-up film - Google Patents

Abstract

An object of the present invention is a thermosetting composition, a thermosetting resin modifier, which can achieve good copper foil adhesion, elastic modulus, heat resistance and toughness in a well-balanced manner in the obtained cured product. The present invention is to provide a cured product, a semiconductor encapsulating material, a prepreg, a circuit board, and a build-up film. The present invention is a thermosetting composition containing a thermosetting resin, a thermosetting agent and a modified resin, wherein the modified resin has at least one selected from the group consisting of hydroxyl groups and carboxy groups. A thermosetting resin, characterized in that the glass transition temperature of the modified resin is −100 ° C. or higher and 50 ° C. or lower, and the number average molecular weight of the modified resin is 600 or higher and 50,000 or lower. Use the composition.

Description

The present invention relates to a thermosetting composition, a thermosetting resin modifier, a cured product thereof, and a semiconductor encapsulating material, a prepreg, a circuit board, and a build-up film using the same.

Thermosetting resins are used as sealing materials to protect semiconductor elements such as capacitors, diodes, transistors and thyristors, and integrated circuits such as ICs and LSIs. Along with the miniaturization and thinning of electronic components, the density and high integration of printed wiring boards are required, and along with this, the semiconductor encapsulant material is required to have low thermal expansion.

As the semiconductor encapsulating material, a thermosetting resin composition containing an aromatic amine compound, an aliphatic amine compound, a siloxane compound, and a maleimide compound has been proposed (see, for example, Patent Document 1). Further, a resin composition containing a cyanate ester resin and a naphthylene ether type epoxy resin has been proposed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2017-178991 Japanese Unexamined Patent Publication No. 2016-006187

However, according to the studies by the present inventors, the cured product formed from the conventional thermosetting resin composition has good low thermal expansion property, but has good copper foil adhesion, elastic modulus, heat resistance and heat resistance. The toughness could not be achieved with a sufficiently satisfactory balance.

An object of the present invention is a thermosetting composition, a thermosetting resin modifier, which can achieve good copper foil adhesion, elastic modulus, heat resistance and toughness in a well-balanced manner in the obtained cured product. The present invention is to provide a cured product, a semiconductor encapsulating material, a prepreg, a circuit board, and a build-up film.

The present invention is a thermosetting composition containing a thermosetting resin, a thermosetting agent and a modified resin, wherein the modified resin has at least one selected from the group consisting of hydroxyl groups and carboxy groups. A thermosetting resin, characterized in that the glass transition temperature of the modified resin is −100 ° C. or higher and 50 ° C. or lower, and the number average molecular weight of the modified resin is 600 or higher and 50,000 or lower. Use the composition.

According to the thermosetting composition of the present invention, it is possible to exhibit excellent heat resistance, copper foil adhesion, and toughness in the obtained cured product.

FIG. 1 is an atomic force microscope image of a fracture surface of the cured product of Example 1. FIG. 2 is an atomic force microscope image of a fracture surface of the cured product of Example 2. FIG. 3 is an atomic force microscope image of the fracture surface of the cured product of Example 3. FIG. 4 is an atomic force microscope image of the fracture surface of the cured product of Example 4. FIG. 5 is an atomic force microscope image of the fracture surface of the cured product of Comparative Example 1. FIG. 6 is an atomic force microscope image of the fracture surface of the cured product of Comparative Example 2.

The thermosetting composition of the present invention contains a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C). The thermosetting composition may contain an inorganic filler (D), and may further contain a flame retardant (E) and the like.

Examples of the thermosetting resin (A) include epoxy resins, benzoxazine structure-containing resins, maleimide resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic acid anhydride, and the like, and include at least epoxy resins. Is preferable.

As the epoxy resin, one type or two or more types can be used, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, and a diglycidyloxynaphthalene compound ( 1,6-Diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type Epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy Resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl novolac type epoxy resin, naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, various of these Examples thereof include a phosphorus-modified epoxy resin in which a phosphorus atom is introduced into the epoxy resin of.

Among them, the epoxy resins include cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin containing a naphthalene skeleton, naphthol aralkyl type epoxy resin, and naphthol-phenol co-condensed novolac. Type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xantene type epoxy resin, and alkoxy group-containing aromatic ring-modified novolac type epoxy resin (glycidyl with formaldehyde) A group-containing aromatic ring and a compound in which an epoxy group-containing aromatic ring is linked) are particularly preferable because a cured product having excellent heat resistance can be obtained.

The content of the epoxy resin in the thermosetting resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and the upper limit is 100% by mass.

As the maleimide resin, one type or two or more types can be used, and examples thereof include resins represented by any of the following structural formulas.

[In the formula (1), R ¹ represents an a1-valent organic group, and R ² and R ³ are independent hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms or 6 to 6 carbon atoms, respectively. It represents 20 aryl groups, and a1 represents an integer of 1 or more. ]

[In formula (2), R ⁴ , R ⁵ and R ⁶ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and 7 to 20 carbon atoms, respectively. Represents an aralkyl group, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, and L ¹ and L ² are independently saturated hydrocarbon groups having 1 to 5 carbon atoms and 6 to 10 carbon atoms, respectively. Represents a group having 6 to 15 carbon atoms, which is a combination of an aromatic hydrocarbon group or a saturated hydrocarbon group and an aromatic hydrocarbon group. a3, a4 and a5 each independently represent an integer of 1 to 3, and n represents an integer of 0 to 10. ]

The content of the thermosetting resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 90% by mass or more, in the non-volatile content of the thermosetting composition. Is 99% by mass or less, more preferably 98% by mass or less.

The thermosetting agent (B) may be any compound that can react with the thermosetting resin (A) by heating to cure the thermosetting composition, and one kind or two or more kinds can be used. , Amine compound, amide compound, active ester resin, acid anhydride, phenol resin, cyanate ester resin and the like. Among them, the thermosetting agent (B) preferably contains at least one selected from an active ester resin, a phenol resin and a cyanate resin.

Examples of the amine compounds, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophoronediamine, imidazo - Le, BF ₃ - amine complex, guanidine derivatives and the like.

Examples of the amide compound include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine.

The active ester resin is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferable. More preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like, or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenol phthalein, 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, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin , Benzintriol, dicyclopentadiene-phenol-added resin and the like.

Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Acids and the like can be mentioned.

Examples of the phenol resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and triphenylol methane resin. Tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nuclei are linked by bismethylene groups), naphthalene Skeletal-containing phenolic resin, biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenolic nuclei are linked by bismethylene groups), aminotriazine-modified phenolic resin (polyvalent phenolic hydroxyl group-containing compound in which phenolic nuclei are linked by melamine, benzoguanamine, etc.) And an alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenolic hydroxyl group-containing compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde), a polyphenolic hydroxyl group-containing resin, and a bisphenol such as bisphenol A and bisphenol F. Compounds, biphenyl compounds such as biphenyl and tetramethylbiphenyl; triphenylolmethane, tetraphenylolethane; dicyclopentadiene-phenol addition reaction type resins, phosphorus-modified phenol compounds in which a phosphorus atom is introduced into these various phenol hydroxyl group-containing compounds, etc. Can be mentioned.

As the cyanate ester resin, one type or two or more types can be used, for example, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol. Sulfide-type cyanate ester resin, phenylene ether-type cyanate ester resin, naphthylene ether-type cyanate ester resin, biphenyl-type cyanate ester resin, tetramethylbiphenyl-type cyanate ester resin, polyhydroxynaphthalene-type cyanate ester resin, phenol novolac-type cyanate ester resin, Cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol Aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolak type cyanate ester resin, Anthracene-type cyanate ester resin and the like can be mentioned.

Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, and polyhydroxynaphthalene type cyanate ester resin are particularly effective in obtaining a cured product having excellent heat resistance. , Naftylene ether type cyanate ester resin and novolak type cyanate ester resin are preferably used, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

The thermosetting composition of the present invention may further contain a curing accelerator (B1). As the curing accelerator (B1), one kind or two or more kinds can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. .. Especially when used as a semiconductor encapsulant material, triphenylphosphine is used as a phosphorus compound and 1,8-diazabicyclo- is used as a tertiary amine because of its excellent curability, heat resistance, electrical properties, moisture resistance and reliability. [5.4.0] -Undesen (DBU) is preferred.

The thermosetting composition of the present invention may further contain a maleimide compound (B2). However, the maleimide compound (B2) is different from the maleimide resin. As the maleimide compound (B2), one type or two or more types can be used, for example, N-cyclohexylmaleimide, N-methylmaleimide, Nn-butylmaleimide, N-hexylmaleimide, N-tert-butyl. N-aliphatic maleimide such as maleimide; N-aromatic maleimide such as N-phenylmaleimide, N- (P-methylphenyl) maleimide, N-benzylmaleimide; 4,4'-diphenylmethanebismaleimide, 4,4'- Diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimidephenyl) methane, bis (3,5-dimethyl-4-maleimidephenyl) Examples thereof include bismaleimides such as methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane and bis (3,5-diethyl-4-maleimidephenyl) methane.

Among them, as the maleimide compound (B2), bismaleimides are preferable from the viewpoint of improving the heat resistance of the cured product, and particularly 4,4'-diphenylmethane bismaleimide and bis (3,5-dimethyl-4-maleimide). Preferable are phenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane and bis (3,5-diethyl-4-maleimidephenyl) methane.

When the maleimide compound (B2) is used, the amine compound, the phenol compound, the acid anhydride compound, the imidazole compound, the organic metal salt and the like may be contained, if necessary.

The modified resin (C) is a thermoplastic resin having at least one selected from the group consisting of a hydroxyl group and a carboxy group, and preferably has a hydroxyl group.
The hydroxyl value of the modified resin (C) is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 18 mgKOH / g or more, preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g. Below, it is more preferably 120 mgKOH / g or less.

The number of at least one type (preferably hydroxyl group) selected from the group consisting of hydroxyl groups and carboxy groups contained in the modified resin (C) is preferably 2 or more, preferably 6 or less, per molecule. It is more preferably 4 or less, further preferably 3 or less, and particularly preferably 2 or less.

The modified resin (C) is preferably at least one selected from the group consisting of polyester resin and polyurethane resin, and more preferably polyester resin.

As the polyester resin, one kind or two or more kinds can be used. For example, a polyester resin obtained by reacting a polyol with a polycarboxylic acid; a polyester resin obtained by a ring-opening polymerization reaction of a cyclic ester compound. ; Examples include polyester resins obtained by copolymerizing these.

As the polyol used in the production of the polyester resin, one kind or two or more kinds can be used, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol. , 1,3-Butandiol and the like; aliphatic polyols such as cyclohexanedimethanol and the like; polyols having an alicyclic structure such as bisphenol A and bisphenol F; and the polyols having the aromatic structures as alkylene oxides. Examples include modified polyols.
Among them, a polyol having the alicyclic structure, a polyol having the aromatic structure, and a polyol obtained by modifying the polyol having the aromatic structure with alkylene oxide are preferable, and a polyol obtained by modifying the polyol having the aromatic structure with alkylene oxide is more preferable. preferable.

The molecular weight of the polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, still more preferably 700 or less.
In the present specification, the number average molecular weight shall mean a value calculated based on the hydroxyl value.

Examples of the alkylene oxide used for the modification of the polyol having an aromatic structure include alkylene oxides having 2 or more and 4 or less carbon atoms (preferably 2 or more and 3 or less) such as ethylene oxide and propylene oxide. The number of moles of the alkylene oxide added is preferably 2 mol or more, more preferably 4 mol or more, preferably 20 mol or less, and more preferably 16 mol or less, relative to 1 mol of the polyol having the aromatic structure. is there.

As the polycarboxylic acid, one kind or two or more kinds can be used, and for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, Aromatic polycarboxylic acids such as naphthalenedicarboxylic acids; their anhydrides or esterifieds and the like.
Above all, it is preferable to contain an aliphatic polycarboxylic acid. The content of the aliphatic polycarboxylic acid is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 100 mol% or less in the total of the polycarboxylic acids.
It is also a preferred embodiment that the polycarboxylic acid contains an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid. The content ratio of the aromatic polycarboxylic acid to the aliphatic polycarboxylic acid is preferably 1/99 or more, more preferably 30/70 or more, still more preferably 50/50 or more, and preferably 99 on a molar basis. It is 1/1 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

The content ratio (polypoly / polycarboxylic acid) of the polyol used in the production of the polyester resin to the polycarboxylic acid is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40 on a mass basis. It is / 60 or more, preferably 99/1 or less, more preferably 90/10 or less, and further preferably 85/15 or less.

As the cyclic ester compound, one type or two or more types can be used, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε. Examples include -propylcaprolactone, 3-penten-4-olid, 12-dodecanolide, and γ-dodecanolactone.

The content of the oxyalkylene unit having 4 or more carbon atoms contained in the polyester resin is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Is.

The polyester resin can be produced, for example, by reacting the polyol with the polycarboxylic acid. The reaction temperature is preferably 190 ° C. or higher, more preferably 200 ° C. or higher, preferably 250 ° C. or lower, and more preferably 240 ° C. or lower. The reaction time is preferably 1 hour or more and 100 hours or less.

A catalyst may coexist in the reaction. As the catalyst, one kind or two or more kinds can be used, for example, a titanium-based catalyst such as tetraisopropyl titanate and tetrabutyl titanate; a tin-based catalyst such as dibutyltin oxide; and an organic sulfone such as p-toluenesulfonic acid. Examples include acid catalysts.
The amount of the catalyst is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and preferably 0.01 parts by mass with respect to 100 parts by mass of the total of the polyol and the polycarboxylic acid. Hereinafter, it is more preferably 0.005 part by mass or less.

The polyurethane resin is a reaction product of a polyol and a polyisocyanate, and has a hydroxy group at the terminal.

Examples of the polyol used for producing the polyurethane resin include polyether polyols, polyester polyols, polycarbonate polyols and the like.

Examples of the polyether polyol include those obtained by addition polymerization (ring-opening polymerization) of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Linear diols such as: neopentyl glycol, 1,2-propanediol, branched chain diols such as 1,3-butanediol; triols such as glycerin, trimethylolethane, trimethylolpropane, pyrogallol; sorbitol, Polyols such as citrus sugar and aconit sugar; tricarboxylic acids such as aconitic acid, trimellitic acid and hemmellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1 , 2,3-Propanetriol and the like.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

As the polyether polyol, polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran to the initiator is preferable.

The polyester polyol is, for example, a polyester polyol obtained by esterifying a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 300 or less) and a polycarboxylic acid; and ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. Polyester polyols obtained by reaction; examples thereof include these copolymerized polyester polyols.

As the low molecular weight polyol, a polyol having a molecular weight of about 50 or more and 300 or less can be used, and for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol can be used. , 3-Methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol and other aliphatic polyols having 2 to 6 carbon atoms; 1,4-cyclohexanediol, cyclohexane Alicyclic structure-containing polyols such as dimethanol; bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof can be mentioned.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecandicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; and the fat. Examples thereof include anhydrides or ester-forming derivatives of group polycarboxylic acids and aromatic polycarboxylic acids.

Examples of the polycarbonate polyol include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.

Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

Examples of the polyol capable of reacting with the carbonic acid ester include the polyol exemplified as the low molecular weight polyol; the high molecular weight polyol (number) such as a polyether polyol (polyethylene glycol, polypropylene glycol, etc.) and a polyester polyol (polyhexamethylene adipate, etc.). (Average molecular weight of 500 or more and 5,000 or less) and the like.

The number average molecular weight of the polyol used in the production of the polyurethane resin is preferably 500 or more, more preferably 700 or more, preferably 3,000 or less, and more preferably 2,000 or less.

As the polyisocyanate, one type or two or more types can be used, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylenediisocyanate, trienediisocyanate. , Naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and other aromatic polyisocyanates; hexamethylene diisocyanate, lysine diisocyanate and other aliphatic polyisocyanates; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and the like Examples thereof include polyisocyanates containing an alicyclic structure.

The equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol used in the production of the urethane resin to the isocyanate group of the polyisocyanate is preferably 0.1 or more, more preferably 0.2 or more on a molar basis. Yes, preferably 0.9 or less, more preferably 0.7 or less.

A polyurethane resin can be produced by reacting a polyol used for producing the polyurethane resin with a polyisocyanate. When the terminal of the obtained polyurethane resin is an isocyanate group, a chain extender having a hydroxy group may be further reacted.

As the chain extender having a hydroxy group, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol. , 1,4-Butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol and other glycol compounds; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy Phenol compounds such as diphenylsulfone, hydrogenated bisphenol A, and hydroquinone; water and the like can be mentioned.

The solubility parameter of the modified resin (C) is preferably 9.0 (cal / cm ³ ) ^0.5 or more, more preferably 9.7 (cal / cm ³ ) ^0.5 or more, and preferably 10.5 (cal / cm ³ ) or more. / Cm ³ ) ^0.5 or less, more preferably 10.3 (cal / cm ³ ) ^0.5 or less.

The difference in solubility parameters between the mixture of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) (the mixture-modified resin (C)) is preferably -2 (cal). / Cm ³ ) ^0.5 or more, more preferably -1.5 (cal / cm ³ ) ^0.5 or more, still more preferably -1 (cal / cm ³ ) ^0.5 or more, even more preferably 0 (cal / cm ³ ) ^0.5 or more. Especially preferably 0.2 (cal / cm ³ ) ^0.5 or more, preferably 2 (cal / cm ³ ) ^0.5 or less, more preferably 1.5 (cal / cm ³ ) ^0.5 or less, still more preferably 0. 8 (cal / cm ³ ) ^0.5 or less. When the difference in solubility parameters between the mixture and the modified resin (C) is within an appropriate range, it is possible to be compatible before thermosetting, and thermosetting (that is, thermosetting resin (A) and heat). The compatibility between the mixture (including those in the reaction process) and the modified resin (C) decreases with the reaction with the curing agent (B), and after thermosetting, the thermosetting resin (A) and heat It is considered that the reactant of the curing agent (B) and the modified resin (C) can be phase-separated.

The solubility parameter of the mixture is the solubility of each compound contained in the curable resin (A) and the thermosetting agent (B) based on the method of Fedors (Polymer Engineering and Science, 1974, vol.14, No. 2). The parameter can be calculated and obtained as a weighted average value based on the mass-based ratio of each compound. For the solubility parameter of the modified resin (C), the solubility parameter of the unit derived from each compound used as the raw material of the modified resin (C) is calculated based on the method of Means, and the mass of the unit derived from each compound is calculated. It can be calculated as a weighted average value based on the reference ratio.

The glass transition temperature of the modified resin (C) is −100 ° C. or higher, preferably −80 ° C. or higher, more preferably −70 ° C. or higher, 50 ° C. or lower, preferably 40 ° C. or lower, and more. It is preferably 30 ° C. or lower.

The number average molecular weight of the modified resin (C) is 500 or more, preferably 1,000 or more, more preferably 1,500 or more, 50,000 or less, preferably 30,000 or less, and more. It is preferably 20,000 or less, more preferably 15,000 or less.
The number average molecular weight of the modified resin (C) can be calculated based on the functional group value.

The modified resin (C) (epoxy resin modifier) is at least one resin selected from the group consisting of polyester resin and polyurethane resin, has a hydroxyl group, and has a glass transition temperature of −100 ° C. It is preferably 50 ° C. or lower and the number average molecular weight is 600 or more and 50,000 or less.

The thermosetting composition is in a compatible state before the thermosetting reaction, but the thermosetting resin (A) and the modified resin (C) are phase-separated after the thermosetting reaction. preferable. In the phase-separated state after the thermosetting reaction, the reactants of the thermosetting resin (A) and the thermosetting agent (B) form a sea part, and the modified resin (C) forms an island part. It is preferable to form a phase-separated structure. The reaction product of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) may form a co-continuous structure. By being in a compatible state before the thermosetting reaction, the modified resin (C) can be uniformly dispersed in the mixture of the thermosetting resin (A) and the thermosetting agent (B), while the heat After the curing reaction, the reaction product of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) are phase-separated to improve the chemical and mechanical properties of the modified resin (C) itself. Since it can be maintained, the domain of the modified resin (C) can be uniformly dispersed in the reaction products of the thermosetting resin (A) and the thermosetting agent (B) in the obtained cured product. Therefore, it is considered that it becomes possible to provide a cured product having more excellent heat resistance, copper foil adhesion, and toughness.

The presence or absence of phase separation in the cured product can be confirmed by the presence or absence of cloudiness of the cured product and the presence of sea and island parts when observing the fracture surface of the cured product with an atomic force microscope (AFM).

The content of the modified resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of the thermosetting resin (A). It is preferably 60 parts by mass or less, and more preferably 45 parts by mass or less. Further, it may be 35 parts by mass or less, further 15 parts by mass or less, particularly 10 parts by mass or less.

The thermosetting composition of the present invention may further contain an inorganic filler (D). By including the inorganic filler (D), the coefficient of thermal expansion of the insulating layer can be further reduced. As the inorganic filler, one type or two or more types can be used, for example, silica (molten silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, hydroxide. Examples thereof include aluminum, magnesium hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide and the like, and silica is preferable, and molten silica is more preferable. Further, the shape of the silica may be either crushed or spherical, and is preferably spherical from the viewpoint of suppressing the melt viscosity of the thermosetting composition while increasing the blending amount.
In particular, when the thermosetting composition of the present invention is used as a semiconductor encapsulant (preferably a power transistor or a high thermal conductive semiconductor encapsulant for a power IC), silica (molten silica, crystalline silica is preferable, and crystalline silica is preferable). ), Alumina and silicon nitride are preferable.

The content of the inorganic filler is preferably 0.2% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, still more preferably 70% by mass or more in the thermosetting composition. It is particularly preferably 80% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less. By increasing the content of the inorganic filler, it is easy to increase the flame retardancy, moisture heat resistance, and solder crack resistance, and reduce the coefficient of thermal expansion.

The thermosetting composition of the present invention may further contain a flame retardant (E). The flame retardant (E) is preferably a non-halogen type that does not substantially contain a halogen atom. As the flame retardant (E), one kind or two or more kinds can be used. For example, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an inorganic flame retardant, an organometallic salt-based flame retardant, etc. Can be mentioned.

As the phosphorus-based flame retardant, one kind or two or more kinds can be used, for example, ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate. Inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amides and other inorganic nitrogen-containing phosphorus compounds; general-purpose organic compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, and organic nitrogen-containing phosphorus compounds. In addition to phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-Oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-Oxa-10-phosphaphenanthrene = 10-oxide and other cyclic organophosphorus compounds, and compounds such as epoxy resins and phenolic resins Examples thereof include organic phosphorus compounds such as reacted derivatives.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boring compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated charcoal and the like may be used in combination with the phosphorus-based flame retardant. ..

The red phosphorus is preferably surface-treated, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, and bismuth hydroxide. Method of coating with an inorganic compound such as bismuth nitrate or a mixture thereof, (ii) a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin such as a phenol resin. (Iii) A method of double coating with a thermosetting resin such as phenol resin on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. Can be mentioned.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine compounds and the like, and triazine compounds, cyanuric acid compounds and isocyanuric acid compounds are preferable. When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melamine, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine and the like, and for example, (i) guanyl melamine sulfate, melem sulfate, sulfuric acid. A cocondensate of aminotriazine sulfate compounds such as melam, (ii) phenols, cresols, xylenol, butylphenols, nonylphenols and other phenols with melamines such as melamine, benzoguanamine, acetguanamine and formguanamine and formaldehyde, (iii). Examples thereof include a mixture of the cocondensate of (ii) and phenolic resins such as phenol formaldehyde condensate, and (iv) the above (ii) and (iii) further modified with tung oil, isomerized melamine oil and the like. ..

Specific examples of the cyanuric acid compound include cyanuric acid and melamine cyanuric acid.

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the thermosetting composition, and the desired degree of flame retardancy, and is, for example, an epoxy resin. It is preferable to blend in the range of 0.05 to 10 parts by mass in 100 parts by mass of the thermosetting composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives, and particularly 0. It is preferable to mix in the range of 1 to 5 parts by mass.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

As the inorganic flame retardant, one kind or two or more kinds can be used, and for example, metals such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zinc oxide. Hydroxide; zinc molybdenum, molybdenum trioxide, zinc tinate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, oxidation Metal oxides such as nickel, copper oxide, tungsten oxide; metal carbonate compounds such as zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate; aluminum, Metal powders such as iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten and tin; boron compounds such as zinc borate, zinc metaborate, barium metaborate, boric acid and borosand; Shipley (Boxy Brown), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ series, ZnO-P ₂ O _5- MgO series, P ₂ O _5- B ₂ O _3- PbO- Examples thereof include low melting point glass such as MgO-based, P-Sn-OF-based, PbO-V ₂ O _5- TeO _2- based, Al _2- O _3- H ₂ O-based, and lead borosilicate-based.

Examples of the organometallic salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound, or a heterocyclic compound. Examples thereof include a coordination-bonded compound.

The thermosetting composition of the present invention may further contain an organic solvent (F). When the thermosetting composition contains the organic solvent (F), the viscosity can be lowered, which makes it particularly suitable for manufacturing a printed circuit board.

As the organic solvent (F), one kind or two or more kinds can be used, for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; an ether solvent such as propylene glycol monomethyl ether; ethyl acetate and butyl acetate. , Acetic acid ester solvents such as cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate, carbitol acetate; carbitol solvents such as cellosolve, methyl cellosolve, butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethyl Examples thereof include amide solvents such as formamide, dimethylacetamide, and N-methylpyrrolidone.

In particular, when the thermosetting composition of the present invention is used for a printed wiring substrate, the organic solvent (F) includes a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and an ether solvent such as propylene glycol monomethyl ether. Acetic acid ester solvents such as propylene glycol monomethyl ether acetate and ethyl diglycol acetate; carbitol solvents such as methyl cellosolve; amide solvents such as dimethylformamide are preferable.

When the thermosetting composition of the present invention is used for a build-up film, the organic solvent (F) is a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate. , Acetic acid ester solvent such as carbitol acetate; carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvent such as toluene and xylene; amide solvent such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone are preferable.

When the organic solvent (F) is contained, the content thereof in the thermosetting composition is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass. % Or less, more preferably 70% by mass or less.

The thermosetting composition of the present invention may further contain conductive particles. By containing the conductive particles, it can be used as a conductive paste and is suitable for an anisotropic conductive material.

The thermosetting composition of the present invention may further contain rubber, a filler and the like. By including rubber, filler, etc., it becomes suitable for build-up film.

The thermosetting composition of the present invention may further contain various additives such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier.

The thermosetting composition of the present invention can be obtained by mixing each of the above components and can be made into a cured product by thermosetting. Examples of the shape of the cured product include a laminate, a cast product, an adhesive layer, a coating film, and a film.

Applications of the thermosetting composition of the present invention include semiconductor encapsulation materials, printed wiring board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, adhesive films for build-up, and the like. Among the above applications, in insulating materials for printed wiring boards and electronic circuit boards, and adhesive films for build-up, passive components such as capacitors and active components such as IC chips are embedded in the substrate, so-called substrates for built-in electronic components. It can be used as an insulating material. Among these, it is preferable to use it as a printed wiring board material or an adhesive film for build-up because of its characteristics such as high heat resistance, low thermal expansion, and solvent solubility.

As a method for preparing a semiconductor encapsulating material from the thermosetting composition of the present invention, the thermosetting resin (A), the thermosetting agent (B) and the modified resin (C) and each component used as necessary Can be sufficiently melt-mixed with an extruder, a feeder, a roll or the like until uniform, if necessary.

When the thermosetting composition of the present invention is used as a semiconductor encapsulating material, it can be molded into a semiconductor package. Specifically, the composition is cast or molded using a transfer molding machine, an injection molding machine, or the like. Then, the semiconductor device which is a molded product can be obtained by further heating at 50 to 200 ° C. for 2 to 10 hours.

Further, in order to manufacture a printed circuit board using the thermosetting composition of the present invention, a method of impregnating a reinforcing base material with a curable composition and superimposing a copper foil on the reinforcing base material to be heat-bonded can be mentioned. Examples of the reinforcing base material include paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, first, the thermosetting composition is heated (preferably 50 to 170 ° C. depending on the type of the organic solvent (F)) to obtain a cured prepreg. The content of the resin in the prepreg is preferably 20% by mass or more and 60% by mass or less. Next, the desired printed circuit board can be obtained by laminating the prepreg, stacking copper foils, and heat-pressing the prepreg at 170 to 300 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

When the thermosetting composition of the present invention is used as a conductive paste, for example, conductive particles (fine conductive particles) are dispersed in the thermosetting composition to obtain an anisotropic conductive film composition. Examples thereof include a paste resin composition for circuit connection which is liquid at room temperature and a method of using an anisotropic conductive adhesive.

As a method for obtaining an interlayer insulating material for a build-up substrate from a thermosetting product of the present invention, for example, a thermosetting composition is applied to a wiring board on which a circuit is formed by a spray coating method, a curtain coating method, or the like. After that, it is cured. Then, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities and a metal such as copper is plated. As the plating method, electroless plating and electrolytic plating treatment are preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. A build-up substrate can be obtained by alternately repeating such an operation as desired to alternately build up and form a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, the through-hole portion is drilled after the resin insulating layer of the outermost layer is formed. Further, a roughened surface is formed and plated by heat-pressing a resin-containing copper foil obtained by semi-curing the thermosetting composition on the copper foil on a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to manufacture a build-up substrate by omitting the processing step.

The method for producing a build-up film from the thermosetting composition of the present invention is, for example, a method for applying the thermosetting composition of the present invention on a support film to form a resin composition layer for a multilayer printed wiring board. A method of making a build-up film can be mentioned.

When the thermosetting composition of the present invention is used as a build-up film, the film is softened under the temperature conditions of lamination (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and is applied to the circuit board at the same time as laminating the circuit board. It is important to show fluidity (resin flow) capable of filling the existing via hole or through hole with resin, and it is preferable to blend each of the above components so as to exhibit such characteristics.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range. When laminating both sides of a circuit board, it is desirable to fill about 1/2 of the through holes.

Specifically, the method for producing the above-mentioned adhesive film is to prepare a varnish-like thermosetting composition of the present invention, and then apply the varnish-like composition to the surface of the support film (Y). Further, it can be produced by drying an organic solvent by heating, blowing hot air, or the like to form a layer (X) of a thermosetting composition.

The thickness of the formed layer (X) is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

The layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further release. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.

The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent dust and the like from adhering in the curing step. When peeling off after curing, the support film is usually subjected to a mold release treatment in advance.

Next, in a method of manufacturing a multilayer printed wiring board using the adhesive film obtained as described above, for example, when the layer (X) is protected by a protective film, the layers (X) are peeled off and then the layer ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be preheated if necessary before laminating.

The laminating conditions are such that the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., the crimping pressure is preferably 1 to 11 kgf / cm ² (9.8 × 104 to 107.9 × 104 N / m ² ), and the air pressure is 20 mmHg. It is preferable to laminate under a reduced pressure of (26.7 hPa) or less.

The method for obtaining the cured product of the present invention may be based on a general method for curing a thermosetting composition, but for example, the heating temperature conditions may be appropriately selected depending on the type and application of the curing agent to be combined. However, the composition obtained by the above method may be heated in a temperature range of about 20 to 300 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1] In a synthetic reaction apparatus for polyester resin A, 779.1 parts by mass of bisphenol A type glycol ether (trademark; manufactured by DIC Corporation, "Hyplox MDB-561") and isophthalic acid (hereinafter, "iPA") are added. 132.9 parts by mass and 40.4 parts by mass of sebacic acid (hereinafter referred to as "SebA") were charged, and temperature raising and stirring were started.
Next, after raising the internal temperature to 230 ° C., 0.10 parts by mass of TiPT was charged and reacted at 230 ° C. for 24 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 36.9, a number average molecular weight of 3,040, and a glass transition temperature of −14 ° C.

[Synthesis Example 2] Ethylene glycol (395.6 parts by mass) and adipic acid (838.8 parts by mass) were charged into a synthetic reaction apparatus for polyester resin B, and temperature raising and stirring were started.
Next, after raising the internal temperature to 220 ° C., 0.03 parts by mass of TiPT was charged and subjected to a condensation reaction at 220 ° C. for 24 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 56.2, a number average molecular weight of 2,000, and a glass transition temperature.

[Synthesis Example 3] 1000.0 parts by mass of polytetramethylene glycol (trademark; manufactured by Mitsubishi Chemical Corporation, “PTMG-1000”) is added to a synthetic reaction apparatus for urethane resin A, and tolylene diisocyanate (trademark; Mitsui Chemicals Co., Ltd.) SKC Polyurethane Co., Ltd., "Cosmonate T-80") 128.8 parts by mass was charged. Then, after raising the outside temperature to 80 ° C., the reaction was continued for 10 hours to synthesize urethane resin A.
The obtained urethane resin had a hydroxyl value of 28.0, a number average molecular weight of 4,010, and a glass transition temperature of −22 ° C.

[Example 1]
80 parts of orthocresol novolac type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON N-680") and bisphenol A type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON 850-S") in a mixing container. ), 50 parts of novolak type phenol resin (trademark; manufactured by DIC Co., Ltd., "Phenolite TD-2131") as a curing agent, and 30 parts of both terminal OH group polyesters obtained in Synthesis Example 1. The mixture was stirred at an internal temperature of 130 ° C. until they became compatible. A part of triphenylphosphine was added as a curing accelerator, and the mixture was stirred for 20 seconds and then vacuum defoamed to obtain an epoxy resin composition (X1) which is a thermosetting composition of the present invention.

[Examples 2 and 3]
In the same manner as in Example 1, 45 parts by mass (Example 2) and 60 parts by mass (Example 3) of both terminal OH group polyesters (polyester resin A) obtained in Synthesis Example 1 were used. Epoxy resin compositions (X2) and (X3), which are thermosetting compositions of the present invention, were obtained.

[Example 4]
Except that 30 parts by mass of both-terminal OH-based polyurethane (urethane resin A) obtained in Synthesis Example 3 was used instead of 30 parts by mass of both-terminal OH-based polyester (polyester resin A) obtained in Synthesis Example 1. , An epoxy resin composition (X4), which is a thermosetting composition of the present invention, was obtained in the same manner as in Example 1.

[Comparative Example 1]
80 parts of orthocresol novolac type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON N-680") and bisphenol A type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON 850-S") in a mixing container. ), And 50 parts of a novolak type phenol resin (trademark; manufactured by DIC Co., Ltd., "Phenolite TD-2131") as a curing agent were mixed, and the mixture was stirred at an internal temperature of 130 ° C. until they were compatible. A part of triphenylphosphine was added as a curing accelerator, and the mixture was stirred for 20 seconds and then vacuum defoamed to obtain the epoxy resin composition of the present invention (Y1).

[Comparative Example 2]
Except that 30 parts by mass of both-terminal OH-based polyester (polyester resin B) obtained in Synthesis Example 2 was used instead of 30 parts by mass of both-terminal OH-based polyester (polyester resin A) obtained in Synthesis Example 1. , An epoxy resin composition (Y2) was obtained in the same manner as in Example 1.

The obtained epoxy resin compositions (X1) to (X4), (Y1), and (Y2) were evaluated as follows. The results are shown in Table 1 together with the solubility parameter of the modified resin (C) used for each epoxy resin composition.

[Evaluation method of copper foil adhesion]
The epoxy resin compositions obtained in Examples and Comparative Examples were poured into a casting plate sandwiched between glass plates having a 2 mm thick rubber spacer on one side at 130 ° C. and heat-cured at 175 ° C. for 5 hours. It was. The obtained cured product was cut into a size of 10 mm in width × 60 mm in length, and the 90 ° peel strength was measured using a peeling tester.

Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation)
Model: AG-1
Test speed: 50 mm / m

[Evaluation method of glass transition temperature (Tg) and storage elastic modulus (E')]
The epoxy resin compositions obtained in Examples and Comparative Examples were poured into a casting plate having a 2 mm thick rubber spacer sandwiched between glass plates at 130 ° C. and heat-cured at 175 ° C. for 5 hours. The obtained cured product was cut into a size of 5 mm in width and 55 mm in length, and the storage elastic modulus (E') and the loss elastic modulus (E ") were measured under the following conditions.
When E'/ E ”is tan δ, the temperature at which tan δ is maximized is defined as the glass transition temperature (Tg, unit; ° C.), and measurement is performed.
In addition, the storage elastic modulus (E') at 25 ° C. was measured.
Measuring equipment: Dynamic viscoelasticity measuring machine (manufactured by SII Nanotechnology Co., Ltd.)
Model: DMA6100
Measurement temperature range: 0 ° C to 300 ° C
Temperature rise rate: 5 ° C / min Frequency: 1Hz
Measurement mode: Bending

[Evaluation method of fracture toughness]
The epoxy resin compositions obtained in Examples and Comparative Examples were poured into a casting plate having a 4 mm thick rubber spacer sandwiched between glass plates at 130 ° C. and heat-cured at 175 ° C. for 5 hours.
The obtained cured product is cut into a size of 13 mm in width × 80 mm in length × 4 mm in thickness, processed as a test piece according to ASTM D5045-93 (ISO 13586), and the fracture toughness (unit: MPa · m ^0.5 ) is measured. Was done.
The notch (notch) in the test piece before the test was made by applying the razor blade to the test piece and giving an impact to the razor blade with a hammer.
When the resin composition of the present invention is used as a semiconductor encapsulating material, it is often required to improve the microscopic fracture toughness, and the macroscopic fracture toughness as evaluated by the present evaluation method is not required. In some cases, the toughness improving effect may be exhibited at a content smaller than the content of the modified resin (C) in this example.
Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation)
Model: AG-X plus
Test speed: 10 mm / min Distance between marked lines: 50 mm

The epoxy resin compositions (X1) to (X4) of Examples 1 to 4 are thermosetting compositions of the present invention, and exhibit excellent heat resistance, copper foil adhesion, and toughness in the obtained cured product. did. On the other hand, Comparative Example 1 was an example in which the modified resin (C) was not contained, and was inferior in copper foil adhesion and toughness. Comparative Example 2 was an example in which a resin having no glass transition temperature was used, and was inferior in all of copper foil adhesion, heat resistance, and toughness.

Claims (11)

A thermosetting composition containing a thermosetting resin, a thermosetting agent, and a modified resin.
The modified resin is a thermoplastic resin having at least one selected from the group consisting of hydroxyl groups and carboxy groups.
The glass transition temperature of the modified resin is −100 ° C. or higher and 50 ° C. or lower.
A thermosetting composition characterized in that the number average molecular weight of the modified resin is 600 or more and 50,000 or less. The thermosetting composition according to claim 1, wherein the modified resin is at least one selected from the group consisting of polyester resin and polyurethane resin. The thermosetting composition according to claim 1 or 2, wherein the modified resin has a hydroxyl value of 2 mgKOH / g or more and 350 mgKOH / g or less. The thermosetting composition according to any one of claims 1 to 3, wherein the content of the modified resin is 0.1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the thermosetting resin. .. The thermosetting composition according to any one of claims 1 to 4, wherein the solubility parameter of the modified resin is 9.0 (cal / cm ³ ) ^0.5 or more and 10.5 (cal / cm ³ ) ^0.5 or less. .. Epoxy resin modifier
At least one resin selected from the group consisting of polyester resin and polyurethane resin.
It has a hydroxyl group and
The glass transition temperature is -100 ° C or higher and 50 ° C or lower.
An epoxy resin modifier having a number average molecular weight of 600 or more and 50,000 or less. A cured product of the thermosetting composition according to any one of claims 1 to 5. A semiconductor encapsulating material comprising the thermosetting composition according to any one of claims 1 to 5. A prepreg that is a semi-cured product of an impregnated base material having the thermosetting composition according to any one of claims 1 to 5 and a reinforcing base material. A circuit board containing a plate-shaped excipient of the thermosetting composition according to any one of claims 1 to 5 and a copper foil. A build-up film containing a cured product of the thermosetting composition according to any one of claims 1 to 5 and a base film.

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