TW202319459A - Thermosetting composition, cured product thereof, semiconductor encapsulation material, prepreg, circuit board and build-up film capable of achieving both excellent copper foil adhesion and heat resistance - Google Patents

Abstract

The problem to be solved by the present invention is to provide a thermosetting composition capable of achieving both excellent copper foil adhesion and heat resistance. The present invention provides a thermosetting composition, comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), wherein the thermosetting composition is characterized in that the modified resin (C) is urethane resin made of polyol (c1) and polyisocyanate (c2) as raw materials having isocyanate group content of 0 mol/kg; the glass transition temperature of the modified resin (C) is -100 DEG C to 50 DEG C, the number average molecular weight of the modified resin (C) is 4,000 to 100,000, and the content of the modified resin (C) is 0.1 to 60 parts by mass based on 100 parts by mass of the thermosetting resin (A).

Description

Thermosetting composition, cured product thereof, semiconductor sealing material, prepreg, circuit board, and buildup film

The present invention relates to a thermosetting composition, its cured product, a semiconductor sealing material, a prepreg, a circuit board, and a buildup film.

In recent years, demands for miniaturization, weight reduction, and higher speed of electronic equipment have increased, and higher densification of printed wiring boards has progressed. Therefore, it is required to further reduce the wiring width or wiring interval, and in order to keep the wiring width small, sufficient adhesion between the metal layer (metal film) forming the wiring and the resin base material is required.

However, in conventional printed wiring boards, the adhesion between the metal layer and the resin mainly depends on roughened metal foil roughness, physical roughening such as plasma treatment on the resin surface, or permanganate etching. The anchoring effect due to the unevenness of the surface obtained by chemical roughening becomes the cause of signal attenuation (transmission loss) due to processing of high-frequency signals when used in printed wiring boards for high-frequency applications such as large servers and antennas. Therefore, it is required to improve adhesion independently of the anchoring effect.

In order to improve adhesiveness, thermosetting compositions containing polyester-based additives have been proposed (for example, refer to Patent Document 1 and Patent Document 2). [Prior art literature] [Patent Document]

Patent Document 1: International Publication No. 19/131413 Patent Document 2: Japanese Patent Laid-Open No. 2021-107493

[Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide a thermosetting composition capable of achieving both excellent copper foil adhesion and heat resistance. [Means to solve the problem]

The present invention provides a thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C). The thermosetting composition is characterized in that the modified resin ( C) Urethane resin with polyol (c1) and polyisocyanate (c2) as raw materials and an isocyanate group content of 0 mol/kg, the glass transition temperature of the modified resin (C) is -100 ° C to 50 ° C, the number average molecular weight of the modified resin (C) is 4,000 to 100,000, and the modified resin (C) is Content is 0.1 mass part or more and 60 mass parts or less.

In addition, the present invention provides a cured product, a semiconductor sealing material, a prepreg, a circuit board, and a buildup film characterized by being formed from the thermosetting composition. [Effect of the invention]

According to the thermosetting composition of the present invention, excellent copper foil adhesion and heat resistance can be achieved in the obtained cured product.

The thermosetting composition of the present invention contains a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C) as essential components.

The glass transition temperature (intermediate glass transition temperature (Tmg)) of the thermosetting composition is preferably 180°C or higher, more preferably 190°C or higher, still more preferably 200°C or higher, and the upper limit is 400°C. In addition, in this specification, the measuring method of a glass transition temperature is described in the Example mentioned later.

In addition, as in the present invention, if a urethane resin is added as the modified resin (C), it is generally feared that the heat resistance will be greatly reduced. However, in the present invention, by adding a specific urethane resin, Excellent copper foil adhesion and heat resistance can be achieved at the same time.

The glass transition temperature (intermediate point glass transition temperature (Tmg)) of the thermosetting composition without adding the modified resin (C) is preferably 180°C or higher, more preferably 190°C or higher, More preferably, it is 200°C or higher, and the upper limit is 400°C.

The difference between the glass transition temperature of the thermosetting composition and the glass transition temperature of the thermosetting composition without adding the modified resin (C) (the glass transition temperature of the thermosetting composition temperature - the glass transition temperature of the thermosetting composition without adding the modified resin (C)) is preferably -30°C or higher, more preferably -20°C or higher, and still more preferably -10°C or higher , with an upper limit of 30°C.

Examples of the thermosetting resin (A) include epoxy resins, resins containing a benzoxazine structure, maleimide resins, polyphenylene ether resins, vinyl benzyl compounds, acrylic compounds, styrene and Copolymers of maleic anhydride and the like preferably contain at least an epoxy resin.

As the epoxy resin, one kind or two or more kinds can be used, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc. Resin, diglycidyloxynaphthalene compound (1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc.), phenol novolak type epoxy resin, cresol novolak type epoxy resin , bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type Epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol novolac type epoxy resin, naphthol-cresol novolak type epoxy resin, Naphthylene ether type epoxy resin, 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane and other polyhydroxynaphthalene type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type Epoxy resins, biphenyl novolak-type epoxy resins, phosphorus-modified epoxy resins in which phosphorus atoms have been introduced into the above-mentioned various epoxy resins, and the like.

Among them, as the epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene- Phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl novolak type epoxy resin, or naphthol novolac type epoxy resin containing naphthalene skeleton, naphthol aralkyl type epoxy resin , naphthol-phenol co-decalized novolak type epoxy resin, naphthol-cresol co-decalized novolak type epoxy resin; naphthylene ether type epoxy resin, polyhydroxynaphthalene type epoxy resin, or crystalline link Benzene-type epoxy resin, tetramethylbiphenyl-type epoxy resin, xanthene-type epoxy resin, or alkoxy-containing aromatic ring-modified novolak-type epoxy resin (use formaldehyde to contain glycidyl aromatic ring A compound formed by linking with an aromatic ring containing an alkoxy group), etc.

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

As the maleimide resin, one kind or two or more kinds can be used, for example, resins represented by any one of the following structural formulas are mentioned.

[chemical 1]

[In formula (1), ^R1 represents an organic group with a1 valence, ^R2 and ^R3 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms , a1 represents an integer greater than 1]

[Chem 2]

[In formula (2), R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aromatic group with 7 to 20 carbon atoms. An alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group with 1 to 20 carbon atoms, ^L1 and ^L2 independently represent a saturated hydrocarbon group with 1 to 5 carbon atoms, an aromatic hydrocarbon group with 6 to 10 carbon atoms, or A group having 6 to 15 carbon atoms composed of a combination of 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 It is 99% by mass or less, more preferably 98% by mass or less.

The thermosetting agent (B) can be used as long as it is a compound capable of curing the thermosetting composition by reacting with the thermosetting resin (A) by heating, and one or more types can be used. Examples thereof include: amine compounds , Amide compounds, active ester resins, acid anhydrides, phenolic resins, cyanate ester resins, etc. Among them, as the thermosetting agent (B), it is preferable to contain at least one selected from the group consisting of active ester resins and phenol resins.

Examples of the amine compound include: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ - Amine complexes, guanidine derivatives, etc.

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

The active ester resins are not particularly limited, and usually preferably use phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have more than two highly reactive compounds in one molecule. ester-based compounds. The active ester resin is preferably obtained through a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester resins obtained from carboxylic acid compounds or their halides and hydroxyl compounds are preferred, and active ester resins obtained from carboxylic acid compounds or their halides and phenol compounds and/or naphthol compounds are more preferred. active ester resins. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or their halides . Examples of the phenol compound or the naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, and methylated bisphenol A. Methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, glucinol (Benzenetriol), dicyclopentadiene-phenol addition type resin, etc.

Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic anhydride. , Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

Examples of the phenol resin include: phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylock ) resins), naphthol aralkyl resins, triphenol-based methane resins, tetraphenol-based ethane resins, naphthol novolac resins, naphthol-phenol co-denatured novolac resins, naphthol-cresol co-diphenolized novolak resins , Biphenyl-modified phenol resin (a compound containing polyhydric phenolic hydroxyl group with a phenol core linked by a double methylene group), a phenol resin containing a naphthalene skeleton, a biphenyl-modified naphthol resin (a phenolic hydroxyl compound linked by a double-methylene group) polyhydric naphthol compound with nucleus), aminotriazine modified phenolic resin (compound containing polyphenolic hydroxyl group with phenolic nucleus linked by melamine, benzoguanamine, etc.) or alkoxy-containing aromatic ring modified novolac Resins (polyphenolic hydroxyl-containing compounds in which a phenol core and an alkoxy-containing aromatic ring are linked by formaldehyde) and other polyphenolic hydroxyl-containing resins, bisphenol compounds such as bisphenol A and bisphenol F, biphenyl, tetra Biphenyl compounds such as methyl biphenyl; triphenolyl methane, tetraphenolyl ethane; dicyclopentadiene-phenol addition reaction type resins, phosphorus-modified compounds in which phosphorus atoms are introduced into the various phenolic hydroxyl-containing compounds phenolic compounds, etc.

As the cyanate resin, one kind or two or more kinds can be used, for example, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S Type cyanate resin, bisphenol sulfide type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type Cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolak type cyanate resin, cresol novolak type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin Ester resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol novolac type cyanate resin, naphthol aralkyl type cyanate resin , naphthol-phenol novolac-type cyanate ester resin, naphthol-cresol novolac-type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin-type cyanate ester resin, biphenyl modified phenolic resin Varnish type cyanate resin, anthracene type cyanate resin, etc.

Among the above-mentioned cyanate resins, bisphenol A type cyanate resins, bisphenol F type cyanate resins, bisphenol E type cyanate resins, and bisphenol E type cyanate resins are preferably used from the viewpoint of obtaining a hardened product having excellent heat resistance. Resin, polyhydroxynaphthalene-type cyanate resin, naphthylene ether-type cyanate resin, novolak-type cyanate resin, dicyclopentadiene is preferable in terms of obtaining a cured product excellent in dielectric properties -Phenol addition reaction type cyanate ester resin.

The thermosetting composition of the present invention may further contain a curing accelerator (B1). As the hardening 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. In particular, when used as a sealing material for semiconductors, triphenylphosphine is preferred among phosphorus-based compounds, and triphenylphosphine is preferred among tertiary amines in terms of excellent curability, heat resistance, electrical properties, and moisture-resistant reliability. It is 1,8-diazabicyclo-[5.4.0]-undecene (1,8-diazabicyclo[5,4,0]-undecene, DBU).

The thermosetting composition of the present invention may further contain a maleimide compound (B2). However, the maleimide compound (B2) is different from the above maleimide resin. As the maleimide compound (B2), one kind or two or more kinds can be used, for example, N-cyclohexylmaleimide, N-methylmaleimide, N-n-butyl Maleimide, N-hexylmaleimide, N-tert-butylmaleimide, etc. N-aliphatic maleimide; N-phenylmaleimide, N-(P -Methylphenyl)maleimide, N-benzylmaleimide and other N-aromatic maleimides; 4,4'-diphenylmethanebismaleimide, 4, 4'-diphenylbismaleimide, m-phenylene bismaleimide, bis(3-methyl-4-maleimidephenyl)methane, bis(3-ethyl -4-maleimide phenyl) methane, bis(3,5-dimethyl-4-maleimide phenyl) methane, bis(3-ethyl-5-methyl-4-maleimide Bismaleimides such as phenylimide phenyl)methane and bis(3,5-diethyl-4-maleimide phenyl)methane.

Among them, as the maleimide compound (B2), bismaleimides are preferable in terms of improving the heat resistance of the cured product, and 4,4'-diphenylmethane bismaleimide is particularly preferable. Laimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane , Bis(3,5-diethyl-4-maleimidophenyl)methane.

When the maleimide compound (B2) is used, the amine compound, the phenol compound, the acid anhydride compound, the imidazole compound, the organometallic salt, and the like may be included as necessary.

The modified resin (C) is a urethane resin with an isocyanate group content of 0 mol/kg made from polyol (c1) and polyisocyanate (c2) as raw materials.

As a polyol (c1) used for manufacture of the said urethane resin, a polyester polyol, a polyether polyol, a polycarbonate polyol etc. are mentioned. Among these, it is preferable to contain polyester polyol and/or polycarbonate polyol from the point which acquires more excellent copper foil adhesiveness and heat resistance.

As the polyester polyol, one kind or two or more kinds can be used, for example, polyester polyol obtained by reacting polyol and polycarboxylic acid; polyol obtained by ring-opening polymerization of cyclic ester compound; ester polyols; polyester polyols obtained by copolymerizing them, and the like.

As the polyol used in the production of the polyester polyol, one kind or two or more kinds can be used, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-deca Diethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3- Propylene glycol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl- 1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol and other aliphatic polyols; Polyols with an alicyclic structure such as hexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and their alkylene oxide adducts; polyols with an aromatic structure such as bisphenol A and bisphenol F; Polyols obtained by modifying the above-mentioned polyols having an aromatic structure with alkylene oxide, etc. Among them, it is preferable to include the above-mentioned aliphatic polyhydric alcohol from the point of obtaining more excellent copper foil adhesiveness and heat resistance.

The molecular weight of the polyol is preferably 50 or more, and is preferably 1,500 or less, more preferably 1,000 or less, and still more preferably 700 or less. In addition, in this specification, the number average molecular weight shows the value calculated based on the hydroxyl value in accordance with the potentiometric titration method of Japanese Industrial Standards (Japanese Industrial Standards, JIS) K0070:1992.

Examples of the alkylene oxide used for modifying the polyol having an aromatic structure include rings 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. oxane. The number of added moles of the alkylene oxide is preferably 2 moles or more, more preferably 4 moles or more, and preferably 20 moles or less, with respect to 1 mole of the polyol having an aromatic structure, and more preferably Preferably it is 16 mol or less.

As the polycarboxylic acid, one kind or two or more kinds can be used, for example: aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, etc. Aromatic polycarboxylic acids such as phthalic acid, phthalic acid, and naphthalene dicarboxylic acid; their anhydrides or esters, etc.

The content ratio (polyol/polycarboxylic acid) of the polyol used in the manufacture of the polyester polyol to the polycarboxylic acid is preferably 20/80 or more, more preferably 30/70 or more, and further Preferably it is 40/60 or more, and preferably 99/1 or less, more preferably 99/10 or less, still more preferably 85/15 or less.

As the cyclic ester compound, one kind or two or more kinds can be used, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone Esters, ε-ethylcaprolactone, ε-propylcaprolactone, 3-penten-4-olide (3-penten-4-olide), 12-dodecanolide (12-dodecanolide), γ -Lauryl lactone.

The polyester polyol 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, and preferably 250°C or lower, more preferably 240°C or lower. The reaction time is preferably not less than 1 hour and not more than 100 hours.

When carrying out the reaction, a catalyst may also be allowed to coexist. As the catalyst, one type or two or more types can be used, for example: titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; organic sulfonic acid such as p-toluenesulfonic acid; acid catalysts, etc. 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 or less, more preferably 0.005 parts by mass relative to the total of 100 parts by mass of the polyol and the polycarboxylic acid. Parts by mass or less.

As the polyether polyol, polyether polyols obtained by addition polymerization (ring-opening polymerization) of alkylene oxide using one or more than two compounds having two or more active hydrogen atoms as initiators can be cited. Alcohol etc.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. Alcohol, 1,6-hexanediol and other straight-chain diols; Neopentyl glycol, 1,2-propanediol, 1,3-butanediol and other branched-chain diols; Glycerin, trimethylolethane, Triols such as trimethylolpropane and pyrogallol; polyols such as sorbitol, sucrose, and aconite sugar; triols such as aconitic acid, trimellitic acid, and 1,2,3-trimellitic acid Carboxylic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetrithiol, etc. .

As said alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran etc. are mentioned, for example.

As said polycarbonate polyol, the reaction product of carbonate ester and polyol; the reaction product of phosgene (phosgene) and bisphenol A etc. are mentioned, for example.

As said carbonate, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, etc. are mentioned, for example.

Examples of polyols capable of reacting with the carbonate ester include: polyols exemplified as polyols used in the manufacture of the polyester polyol; polyether polyols (polyethylene glycol, polypropylene glycol, Polyoxytetramethylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.), high molecular weight polyols (number average molecular weight 500 to 5,000), etc.

The polyol (c1) used in the production of the urethane resin has a number average molecular weight of preferably 500 or more, more preferably 700 or more, and preferably 20,000 or less, more preferably 15,000 or less.

As the polyisocyanate (c2), one kind or two or more kinds can be used, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide modified Aromatic polyisocyanates such as permanent diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as methyl diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and other aliphatic polyisocyanates Polyisocyanate, etc.

The hydroxyl value of the urethane resin of the modified resin (C) is preferably 1 mgKOH/g or more, more preferably 1.5 mgKOH/g or more, still more preferably 2 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less, still more preferably 25 mgKOH/g or less.

The number of hydroxyl groups contained in the urethane resin of the modified resin (C) is preferably one or more per molecule, and preferably six or less, more preferably four or less, and still more preferably Three or less, particularly preferably two.

The equivalent ratio [isocyanate group/hydroxyl group] of the hydroxyl group of the polyol (c1) used in the production of the urethane resin to the isocyanate group of the polyisocyanate (c2) is on a molar basis, It is preferably 0.1 or more, more preferably 0.2 or more, and is preferably 0.95 or less, more preferably 0.9 or less.

The modified resin (C) may contain other additives as necessary.

As the other additives, for example, curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, thermoplastic resins and the like can be used. These additives may be used alone or in combination of two or more.

The solubility parameter of the modified resin (C) is preferably 9.7 (cal/cm ³ ) ^0.5 or more, more preferably 10.0 (cal/cm ³ ) ^0.5 or more, and preferably 12.0 (cal/cm ³ ) ^0.5 or less, more preferably Preferably it is 11.7 (cal/cm ³ ) ^0.5 or less.

The difference in solubility parameter between the cured product of 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, still more preferably 0 (cal/cm ³ ) ^0.5 or more, Particularly 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 the following. It is considered that by making the difference in the solubility parameters of the cured product and the modified resin (C) within an appropriate range, it is possible to be compatible before thermosetting, and accompanied by thermosetting (that is, thermosetting resin (A) and thermosetting agent (B) reaction), the compatibility of the mixture (including the substances in the reaction process) and the modified resin (C) is reduced, and the thermosetting resin (A) and the thermosetting agent ( The reaction product of B) and the modified resin (C) undergo phase separation.

Regarding the solubility parameter of the cured product, the curable resin (A) and The solubility parameter of each compound contained in the cured product of the mixture of the thermosetting agent (B) is obtained as a weighted average based on the ratio of each compound on a mass basis. In addition, regarding the solubility parameter of the modified resin (C), the solubility parameter of units derived from each compound used as a raw material for the modified resin (C) can be calculated based on the method of Fedors, and based on the source The ratio based on the mass of the unit of each compound was calculated|required as a weighted average value.

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

The modified resin (C) has a number average molecular weight of 3,000 or more, preferably 4,000 or more, more preferably 5,000 or more, and 100,000 or less, preferably 80,000 or less, more preferably 60,000 or less, and still more preferably 50,000 or less. The number average molecular weight of the modified resin (C) represents a value calculated based on the hydroxyl value according to the potentiometric titration method of JIS K 0070:1992.

The thermosetting composition is preferably in a compatible state before the thermosetting reaction, but the thermosetting resin (A) and the modified resin (C) undergo phase separation after the thermosetting reaction. In the phase-separated state after the thermosetting reaction, it is preferable that the reaction product of the thermosetting resin (A) and the thermosetting agent (B) forms a sea portion, and the modified resin (C) forms an island portion, thereby forming a sea-island type phase. separate structure. The reaction product of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) may also form a co-continuous structure. It is considered that the modified resin (C) can be uniformly dispersed in the mixture of the thermosetting resin (A) and the thermosetting agent (B) by being in a compatible state before the thermosetting reaction. After the reaction, the reaction product of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) undergo phase separation, which can maintain the chemical and mechanical properties of the modified resin (C), so the obtained In the cured product, the domains of the modified resin (C) can be uniformly dispersed in the reaction product of the thermosetting resin (A) and the thermosetting agent (B), thereby providing more excellent heat resistance And a hardened product of copper foil adhesion.

The presence or absence of phase separation in the hardened product can be confirmed by whether the hardened product is cloudy or not, and the existence of sea and island parts when the fracture surface of the hardened product is observed with an atomic force microscope (AFM).

With respect to 100 parts by mass of the thermosetting resin (A), the content of the modified resin (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably It is 60 mass parts or less, More preferably, it is 45 mass parts or less. In addition, it may be 35 parts by mass or less, further 15 parts by mass or less, especially 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 thermal expansion coefficient of the insulating layer can be further reduced. As the inorganic filler, one kind or two or more kinds can be used, for example, silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.) , mica powder, aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc., preferably silicon dioxide, more preferably fused silicon dioxide. In addition, 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 compounding amount. In particular, when the thermosetting composition of the present invention is used for a semiconductor sealing material (preferably a high thermal conductivity semiconductor sealing material for a power transistor or a power integrated circuit (integrated circuit, IC), silicon dioxide (which can be Examples include fused silica, crystalline silica, preferably crystalline silica), alumina, silicon nitride.

The content of the inorganic filler (D) in the thermosetting composition 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, It is particularly preferably at least 80% by mass, and preferably at most 95% by mass, more preferably at most 90% by mass. When the content rate of the inorganic filler is increased, it is easy to improve the flame retardancy, heat and humidity resistance, and resistance to solder cracking, and it is easy to 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 system that does not substantially contain a halogen atom. As the above-mentioned flame retardant (E), one or more kinds can be used, for example, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, organometallic salts, etc. Department of flame retardants, etc.

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, ammonium polyphosphate, and inorganic systems such as amide phosphate. Nitrogen-containing phosphorus compounds; common organophosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, in addition: 9,10-dihydro- 9-oxa-10-phosphaphenanthrene=10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene=10-oxide, 10-( 2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene=10-oxide and other cyclic organophosphorus compounds, and reacting them with compounds such as epoxy resin or phenol resin Derivatives such as organophosphorus compounds, etc.

In the case of using the phosphorus-based flame retardant, hydrotalcite, magnesium hydroxide, boron compound, zirconia, black dye, calcium carbonate, zeolite, zinc molybdate, active carbon etc.

The red phosphorus is preferably subjected to surface treatment. As a surface treatment method, for example: (i) using magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or A method of coating with an inorganic compound such as a mixture thereof; (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide and a thermosetting resin such as a phenol resin; (iii) A method of double-coating a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide with a thermosetting resin such as a phenol resin.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine compounds, and are preferably triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds. compound. 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, mellon, melam, succinylguanamine, and ethylene bis-melamine. (ethylene dimelamine), melamine polyphosphate, triguanamine, etc., and, for example, (i) aminotriazine sulfate compounds such as amidinomelamine sulfate, melem sulfate, and melam sulfate; (ii) phenol, Co-condensates of phenols such as cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, and formaldehyde, and formaldehyde; (iii) ( ii) A mixture of phenolic resins such as cocondensates and phenol-formaldehyde condensates; (iv) Those obtained by further modifying the above (ii) and (iii) with tung oil, isomerized linseed oil, etc.

Specific examples of the cyanuric acid compound include cyanuric acid, melamine cyanurate, and the like.

As the blending amount of the nitrogen-based flame retardant, it is appropriately selected according to the type of nitrogen-based flame retardant, other components of the thermosetting composition, and the degree of desired flame retardancy. For example, when an epoxy resin is blended , curing agent, non-halogen-based flame retardant, and other fillers or additives, etc., are preferably blended in the range of 0.05 parts by mass to 10 parts by mass, particularly preferably in the range of 100 parts by mass of the thermosetting composition. It is prepared within the range of 0.1 parts by mass to 5 parts by mass.

As the silicone-based flame retardant, any organic compound containing a silicon atom can be used without particular limitation, 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, for example, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc. Zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, Copper oxide, tungsten oxide and other metal oxides; zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate and other metal carbonate compounds; aluminum, iron, titanium, Metal powders of manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.; boron compounds such as zinc borate, zinc metaborate, barium metaborate, boric acid, borax, etc.; Brown (Bokusui Brown Company), 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-MgO Low melting point glass such as P-Sn-OF system, PbO-V ₂ O ₅ -TeO ₂ system, Al ₂ O ₃ -H ₂ O system, lead borosilicate system, etc.

Examples of the organic metal salt-based flame retardant include ferrocene, acetylpyruvate metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, metal atoms and aromatic Compounds or heterocyclic compounds that are ionically bonded or coordinate bonded, etc.

The thermosetting composition of the present invention may further contain an organic solvent (F). When a thermosetting composition contains an organic solvent (F), viscosity can be made low, and it is especially suitable for manufacture of a printed wiring board.

As the organic solvent (F), one kind or two or more kinds can be used. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propylene glycol monomethyl ether; acetic acid Ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate, carbitol acetate and other acetate solvents; cellosolve, methyl solvent Carbitol solvents such as fiber agent and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc.

In particular, when the thermosetting composition of the present invention is used for printed wiring boards, the organic solvent (F) is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclic Ketone solvents such as hexanone; ether solvents such as propylene glycol monomethyl ether; acetate solvents such as propylene glycol monomethyl ether acetate and ethyl diglycol acetate; carbitol solvents such as methyl cellosolve; dimethyl Amide solvents such as formamide, etc.

In addition, when the thermosetting composition of the present invention is used for a buildup film, the organic solvent (F) is preferably a ketone solvent such as acetone, methyl ethyl ketone, or cyclohexanone; ethyl acetate; acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other acetate solvents; cellosolve, butyl carbitol and other carbitol solvents; toluene, Aromatic hydrocarbon solvents such as xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc.

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

The thermosetting composition of this invention may contain electroconductive particle further. By containing electroconductive particles, it can be used as an electroconductive paste, and is suitable for an anisotropic electroconductive material.

The thermosetting composition of the present invention may further contain rubber, fillers, and the like. Suitable for build-up films by including rubber, fillers, etc.

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

The thermosetting composition of the present invention is obtained by mixing the above components, and can be cured 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.

Examples of applications of the thermosetting composition of the present invention include semiconductor sealing materials, printed wiring board materials, resin casting materials, adhesives, interlayer insulating materials for buildup substrates, and adhesive films for buildup. Among the above-mentioned applications, it can be used as a so-called built-in electronic component for embedding passive components such as capacitors or active components such as IC chips in substrates in the application of insulating materials for printed wiring boards or electronic circuit boards, and adhesive films for build-up layers. Insulating materials for substrates. Among these, it is preferable to use for a printed wiring board material or the adhesive film for buildups from the characteristics, such as high heat resistance and solvent solubility.

As a method for preparing a semiconductor sealing material from the thermosetting composition of the present invention, the thermosetting resin (A), thermosetting agent (B) and modified resin may be mixed using an extruder, kneader, roll, etc. (C) and each component used as needed are fully melt-mixed until they become uniform.

When the thermosetting composition of the present invention is used as a semiconductor encapsulant, semiconductor encapsulation molding can be carried out. Specifically, by casting the composition, or using a transfer molding machine, an injection molding machine, etc., the resulting The above composition is molded, and further heated at 50° C. to 200° C. for 2 hours to 10 hours to obtain a semiconductor device as a molded product.

Moreover, when manufacturing a printed circuit board using the thermosetting composition of this invention, the method of impregnating a reinforcing base material with a curable composition, laminating|stacking copper foil, and performing thermocompression bonding is mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass felt, glass roving cloth, and the like. More specifically, first, a prepreg as a cured product can be obtained by heating the thermosetting composition (preferably at 50° C. to 170° C. depending on the type of organic solvent (F)). In the prepreg, the resin content is preferably not less than 20% by mass and not more than 60% by mass. Next, the prepreg is laminated and laminated with copper foil, and heated and pressed at 170° C. to 300° C. for 10 minutes to 3 hours under a pressure of 1 MPa to 10 MPa to obtain a target printed circuit board.

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 form an anisotropic conductive film A method of using the composition; a method of preparing a paste resin composition for circuit connection or an anisotropic conductive adhesive that is liquid at room temperature.

As a method of obtaining an interlayer insulating material for a buildup board from the thermosetting composition of the present invention, for example, the thermosetting composition is applied to a circuit-formed wiring board using a spray coating method, a curtain coating method, etc., and then cured. Thereafter, predetermined through-holes and the like are drilled as necessary, and then treated with a roughening agent, and the surface is washed with hot water to form irregularities, and then plated with metal such as copper. As the plating method, electroless plating and electrolytic plating treatment are preferable, and examples of the roughening agent include oxidizing agents, alkali, organic solvents, and the like. Such operations are repeated sequentially as necessary to alternately build up resin insulating layers and conductor layers of predetermined circuit patterns, whereby a buildup board can be obtained. However, the opening of the through-hole portion is performed after the outermost resin insulating layer is formed. In addition, the roughness can also be omitted by bonding the resin-coated copper foil obtained by semi-hardening the thermosetting composition on the copper foil to the wiring board on which the circuit is formed at 170°C to 300°C. Build-up substrates are produced through the steps of formation of chemical surface and plating treatment.

As for the method of producing a buildup film from the thermosetting composition of the present invention, for example, coating the thermosetting composition of the present invention on a support film to form a resin composition layer to form a buildup film for a multilayer printed wiring board Methods.

When using the thermosetting composition of the present invention for a build-up film, it is important that the film is softened under the lamination temperature conditions (usually 70°C to 140°C) in the vacuum lamination method, and At the same time as laminating the circuit board, it shows fluidity (resin flow) that can fill the resin in the via hole (via hole) or the through hole (through hole) existing in the circuit board. In order to show such characteristics, it is preferable To prepare the ingredients.

Here, the diameter of the through-hole of the multilayer printed wiring board is usually 0.1 mm to 0.5 mm, and the depth is usually 0.1 mm to 1.2 mm. Usually, it is preferable to allow resin filling within the above range. In addition, when laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

Regarding the method for producing the above-mentioned adhesive film, specifically, it can be produced in the following manner: after preparing the varnish-like thermosetting composition of the present invention, coating the varnish-like thermosetting composition on the surface of the support film (Y) composition, and further drying the organic solvent by heating or blowing hot air, etc., to form a layer (X) of a thermosetting composition.

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

Moreover, the layer (X) of this invention can be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dirt and the like from adhering to the surface of the resin composition layer or damage to the surface of the resin composition layer.

The support film and protective film can be listed: polyethylene, polypropylene, polyvinyl chloride and other polyolefins; polyethylene terephthalate (hereinafter sometimes referred to as "PET (polyethylene terephthalate)"); polyethylene naphthalate Polyester such as ethylene glycol; polycarbonate; polyimide; and release paper or metal foil such as copper foil and aluminum foil, etc. In addition, matting treatment and corona treatment can be applied to the support film and protective film, and release treatment can also be performed.

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

The support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heating and hardening. When the support film (Y) is peeled off after heating and curing the adhesive film, it is possible to prevent adhesion of dirt and the like in the curing step. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

Next, regarding the method of producing a multilayer printed wiring board using the adhesive film obtained in the above manner, for example, when the layer (X) is protected by a protective film, after peeling off the protective film, in a manner of directly contacting the circuit board, for example The layer (X) is laminated on one side or both sides of the circuit board by a vacuum lamination method. The method of lamination may be a batch method or a continuous method using a roll. Moreover, before lamination, you may heat (preheat) an adhesive film and a circuit board as needed.

As for lamination conditions, it is preferable to set the crimping temperature (lamination temperature) at 70°C to 140°C, and to set the crimping pressure at 1 kgf/cm ² to 11 kgf/cm ² (9.8×10 ⁴ N /m ² to 107.9×10 ⁴ N/m ² ), and the lamination is performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

As a method of obtaining the cured product of the present invention, it is sufficient to follow the general curing method of thermosetting compositions. For example, the heating temperature conditions can be appropriately selected according to the type or use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range of about °C. [Example]

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

[Synthesis Example 1] Synthesis of Polyester Polyol 1 101.5 parts by mass of diethylene glycol, 300.8 parts by mass of neopentyl glycol, 113.1 parts by mass of 1,6-hexanediol, and 675.2 parts by mass of adipic acid were charged into the reaction device, and heating and stirring were started. Then, after the internal temperature was raised to 220°C, 0.03 parts by mass of tetraisopropyl titanate (TiPT) was charged, and condensation reaction was carried out at 220°C for 30 hours to synthesize polyester polyol 1 (referred to as PEs1) . The hydroxyl value of the obtained PEs1 was 16.0, and the number average molecular weight was 7,000.

[Synthesis Example 2] Synthesis of Polyester Polyol 2 169.5 parts by mass of diethylene glycol, 82.1 parts by mass of neopentyl glycol, 217.3 parts by mass of 1,6-hexanediol, and 740.5 parts by mass of adipic acid were charged into the reaction device, and heating and stirring were started. Next, after raising the internal temperature to 220° C., 0.03 parts by mass of TiPT was charged, and a condensation reaction was performed at 220° C. for 30 hours to synthesize polyester polyol 2 (abbreviated as PEs2). The obtained PEs2 had a hydroxyl value of 20.4 and a number average molecular weight of 5,500.

[Synthesis Example 3] Synthesis of Polyester Polyol 3 161.3 parts by mass of diethylene glycol, 207.6 parts by mass of neopentyl glycol, 177.4 parts by mass of 1,6-hexanediol, and 635.4 parts by mass of adipic acid were charged into the reaction device, and heating and stirring were started. Then, after raising the internal temperature to 220° C., 0.03 parts by mass of TiPT was charged, and a condensation reaction was performed at 220° C. for 20 hours to synthesize polyester polyol 3 (abbreviated as PEs3). The hydroxyl value of the obtained PEs3 was 56.1, and the number average molecular weight was 2,000.

[Synthesis Example 4] Synthesis of Polyester Polyol 4 527.6 parts by mass of 1,6-hexanediol and 572.4 parts by mass of phthalic anhydride were charged into the reaction device, and heating and stirring were started. Then, after raising the internal temperature to 220° C., 0.1 part by mass of TiPT was charged, and a condensation reaction was performed at 220° C. for 20 hours to synthesize polyester polyol 4 (abbreviated as PEs4). The hydroxyl value of the obtained PEs4 was 56.1, and the number average molecular weight was 2,000.

[Synthesis Example 5] Synthesis of Polyester Polyol 5 577.9 parts by mass of neopentyl glycol and 623.2 parts by mass of adipic acid were charged into the reaction device, and heating and stirring were started. Next, after raising the internal temperature to 220° C., 0.03 parts by mass of TiPT was charged, and a condensation reaction was performed at 220° C. for 15 hours to synthesize polyester polyol 5 (abbreviated as PEs5). The hydroxyl value of the obtained PEs5 was 112.2, and the number average molecular weight was 1,000.

[Synthesis Example 6] Synthesis of Polyester Polyol 6 538.7 parts by mass of neopentyl glycol and 659.4 parts by mass of adipic acid were charged into the reaction device, and heating and stirring were started. Then, after raising the internal temperature to 220° C., 0.03 parts by mass of TiPT was charged, and a condensation reaction was performed at 220° C. for 20 hours to synthesize polyester polyol 6 (abbreviated as PEs6). The obtained PEs6 had a hydroxyl value of 56.1 and a number average molecular weight of 2,000.

[Synthesis Example 7] Synthesis of Urethane Resin 1 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction device, and 4,4'-diphenylmethane diisocyanate (trademark; manufactured by Tosoh Co., Ltd., "Milionide ( Millionate) MT", hereinafter referred to as MDI) 28.6 parts by mass. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 1 (C1) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was -50 degreeC.

[Synthesis Example 8] Synthesis of Urethane Resin 2 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was charged to the reaction apparatus, and 10.7 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 2 (C2) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 11.2, the number average molecular weight was 10,000, and the glass transition temperature was -54 degreeC.

[Synthesis Example 9] Synthesis of Urethane Resin 3 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was charged to the reaction apparatus, and 32.1 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 3 (C3) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 11.2, the number average molecular weight was 70,000, and the glass transition temperature was -49 degreeC.

[Synthesis Example 10] Synthesis of Urethane Resin 4 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction device, and 1,3-xylylene diisocyanate (trademark; manufactured by Mitsui Chemicals Co., Ltd., "Takenate 500" ) 21.5 parts by mass. Then, after raising internal temperature to 120 degreeC, reaction was continued for 10 hours, and the urethane resin 4 (C4) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was -53 degreeC.

[Synthesis Example 11] Synthesis of Urethane Resin 5 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was charged into the reaction apparatus, and 19.2 parts by mass of hexamethylene diisocyanate (trademark; manufactured by Tosoh Co., Ltd., "HDI") was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 10 hours, and the urethane resin 5 (C5) was synthesize|combined. The obtained urethane resin had a hydroxyl value of 3.2, a number average molecular weight of 35,000, and a glass transition temperature of -54°C.

[Synthesis Example 12] Synthesis of Urethane Resin 6 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction apparatus, and 19.9 parts by mass of toluene diisocyanate (trademark; manufactured by Mitsui Chemicals, Inc., "Cosmonate T-80") was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 6 (C6) was synthesize|combined. The obtained urethane resin had a hydroxyl value of 3.2, a number average molecular weight of 35,000, and a glass transition temperature of -51°C.

[Synthesis Example 13] Synthesis of Urethane Resin 7 1,000 parts by mass of PEs2 obtained in Synthesis Example 2 was charged to the reaction device, and 36.4 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 7 (C7) was synthesize|combined. The obtained urethane resin had a hydroxyl value of 4.0, a number average molecular weight of 28,000, and a glass transition temperature of -49°C.

[Synthesis Example 14] Synthesis of Urethane Resin 8 1,000 parts by mass of PEs3 obtained in Synthesis Example 3 was charged to the reaction apparatus, and 106.3 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 8 (C8) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was -46 degreeC.

[Synthesis Example 15] Synthesis of Urethane Resin 9 1,000 parts by mass of PEs4 obtained in Synthesis Example 4 was charged to the reaction apparatus, and 106.3 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 9 (C9) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was -7 degreeC.

[Synthesis Example 16] Synthesis of Urethane Resin 10 1,000 parts by mass of PEs5 obtained in Synthesis Example 5 was charged to the reaction device, and 151.4 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 10 (C10) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 37.4, the number average molecular weight was 3,000, and the glass transition temperature was -40 degreeC.

[Synthesis Example 17] Synthesis of Urethane Resin 11 1,000 parts by mass of PEs5 obtained in Synthesis Example 5 was charged to the reaction apparatus, and 222.6 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 11 (C11) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 9.4, the number average molecular weight was 12,000, and the glass transition temperature was -29 degreeC.

[Synthesis Example 18] Synthesis of Urethane Resin 12 1,000 parts by mass of PEs6 obtained in Synthesis Example 6 was charged to the reaction apparatus, and 59.5 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 12 (C12) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 28.1, the number average molecular weight was 4,000, and the glass transition temperature was -41 degreeC.

[Synthesis Example 19] Synthesis of Urethane Resin 13 1,000 parts by mass of PEs6 obtained in Synthesis Example 6 was charged to the reaction apparatus, and 106.3 parts by mass of MDI was charged. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 13 (C13) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was -36 degreeC.

[Synthesis Example 20] Synthesis of Urethane Resin 14 Add polycarbonate polyol (trademark; manufactured by Asahi Kasei Co., Ltd., "Duranol) T5652" made of 1,5-pentanediol and 1,6-hexanediol to the reaction device, the number average molecular weight 2000) 1,000 parts by mass, and packed with 93.8 parts by mass of MDI. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 14 (C14) was synthesize|combined. The obtained urethane resin had a hydroxyl value of 13.2, a number average molecular weight of 8,500, and a glass transition temperature of -44°C.

[Synthesis Example 21] Synthesis of Urethane Resin 15 Add polycarbonate polyol (trademark; manufactured by Asahi Kasei Co., Ltd., "Duranol) T5651" made of 1,5-pentanediol and 1,6-hexanediol to the reaction device, the number average molecular weight 2000) 1,000 parts by mass, and 200 parts by mass of MDI. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and the urethane resin 15 (C15) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 18.7, the number average molecular weight was 6,000, and the glass transition temperature was -38 degreeC.

[Synthesis Example 22] Synthesis of Urethane Resin 16 Add polycarbonate polyol (trademark; manufactured by Asahi Kasei Co., Ltd., "Duranol) G3450J" made of 1,3-propanediol and 1,4-butanediol to the reaction device, number average molecular weight 800) 1,000 parts by mass and 250 parts by mass of MDI. Then, after raising internal temperature to 120 degreeC, reaction was continued for 5 hours, and urethane resin 16 (C16) was synthesize|combined. The hydroxyl value of the obtained urethane resin was 22.4, the number average molecular weight was 5,000, and the glass transition temperature was -9 degreeC.

[Example 1] Mix polyhydroxynaphthalene-type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON) HP-4700" as an epoxy resin in a mixing container, abbreviated as "A1" in the table ) 61.5 parts by mass, novolak-type phenolic resin (trademark; manufactured by DIC Co., Ltd., "Phenolite (PHENOLITE) TD-2131", abbreviated as "B1" in the table) as a hardener 38.5 Parts by mass, 10 parts by mass of the urethane resin 1 (C1) obtained in Synthesis Example 7, were stirred at an internal temperature of 130° C. until compatibilized. After adding 0.3 parts by mass of 2-ethyl-4-methylimidazole as a hardening accelerator and stirring for 20 seconds, vacuum defoaming was performed to obtain a thermosetting composition as a thermosetting composition of the present invention.

[Example 2 and Example 3] A thermosetting composition was obtained in the same manner as in Example 1 except that 5 parts by mass and 20 parts by mass of the urethane resin 1 (C1) were used.

[Example 4 to Example 15] A thermosetting composition was obtained in the same manner as in Example 1 except that the urethane resins (C2 to C13) described in the table were used instead of the urethane resin 1 (C1).

[Example 16 to Example 18] Instead of preparing 10 parts by mass of urethane resin 1 (C1), 5 parts by mass of urethane resins (C14 to C16) described in the table were prepared separately, and the same manner as in Example 1 was prepared. A thermosetting composition is obtained.

[Example 19] 85.4 parts by mass (42.7 parts by mass of solid content) of 50% methyl ethyl ketone solution (42.7 parts by mass) of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin, and active ester resin (trademark; Di Aisheng) as a hardener were prepared in a mixing container. (DIC) Co., Ltd., "Epiclon (EPICLON) HPC-8000-65T", abbreviated as "B2" in the table) 88.2 parts by mass (65% toluene solution, solid content 57.3 parts by mass), Synthesis Example 7 5 parts by mass of the urethane resin 1 (C1) obtained in , was stirred at an internal temperature of 130° C. until compatibilized while desolvating under reduced pressure. After adding 0.5 parts by mass of 4-dimethylaminopyridine as a curing accelerator and stirring for 20 seconds, vacuum defoaming was performed to obtain a thermosetting composition which is a thermosetting composition of the present invention.

[Comparative Example 1] 61.5 parts by mass of polyhydroxynaphthalene-type epoxy resin A1 as an epoxy resin and 38.5 parts by mass of novolac-type phenol resin B1 as a hardener were prepared in a mixing container, and stirred at an internal temperature of 130° C. until they were compatible. After adding 0.3 parts by mass of 2-ethyl-4-methylimidazole as a hardening accelerator and stirring for 20 seconds, vacuum defoaming was performed to obtain the thermosetting composition of the present invention.

[Comparative Example 2] 85.4 parts by mass (solid content 42.7 parts by mass) of 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as epoxy resin, 88.2 parts by mass of active ester resin B2 as hardener ( 65% toluene solution, 57.3 parts by mass of solid content), stirring at an internal temperature of 130° C. until compatibility was achieved while desolvating under reduced pressure. After adding 0.5 parts by mass of 4-dimethylaminopyridine as a curing accelerator and stirring for 20 seconds, vacuum defoaming was performed to obtain a thermosetting composition which is a thermosetting composition of the present invention.

The following evaluations were performed on the obtained thermosetting composition. The solubility parameters of the modified resin (C) used in each thermosetting composition are shown in the table together with the results.

〔Evaluation method of copper foil adhesion〕 The thermosetting compositions obtained in Examples and Comparative Examples were poured at 130°C into a cast plate made of glass with copper foil attached on one side, and thermally cured at 175°C for 5 hours. The plate is formed by sandwiching a 1 mm thick rubber spacer. The obtained cured product was cut into a size of 10 mm wide x 60 mm long, and the 90° peel strength (N/cm) was measured using a peel tester. Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation) Model: AG-1 Test speed: 50 mm/min

[Evaluation method of heat resistance] Regarding the evaluation of heat resistance, evaluation was performed by glass transition temperature. Specifically, the thermosetting compositions obtained in Examples and Comparative Examples were poured at 130° C. into cast plates sandwiched by glass plates for 5 hours, and thermally cured at 175° C. for 5 hours. mm thick rubber spacer. The obtained cured product was cut into a size of 10 mm wide x 55 mm long, and the storage elastic modulus (E') and loss elastic modulus (E") were measured under the following conditions. When E'/E" is defined as tan δ, the temperature at which tan δ becomes the maximum is measured as the glass transition temperature (unit; ° C). The Tg of the thermosetting composition obtained in Examples and Comparative Examples is defined as glass In the evaluation 1 of the glass transition temperature, the difference between the Tg of the thermosetting composition obtained in Examples and Comparative Examples and the Tg of the thermosetting composition without adding the modified resin was used as the evaluation 2 of the glass transition temperature. Measuring equipment: Dynamic viscoelasticity tester (manufactured by Seiko Electronics Nanotechnology (SII Nanotechnology) Co., Ltd.) Model: DMA6100 Measuring temperature range: 0℃～300℃ Heating rate: 5°C/min Frequency: 1Hz Measurement Mode: Tensile

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Thermosetting resin (A) type A1 A1 A1 A1 A1 A1 A1 Blending amount (parts by mass, solid content) 61.5 61.5 61.5 61.5 61.5 61.5 61.5 Thermohardener (B) type B1 B1 B1 B1 B1 B1 B1 Blending amount (parts by mass, solid content) 38.5 38.5 38.5 38.5 38.5 38.5 38.5 Modified resin (C) type C1 C1 C1 C2 C3 C4 C5 Blending amount (parts by mass) 10 5 20 10 10 10 10 Solubility parameter (cal/cm ³ ) ^0.5 10.26 10.26 10.26 10.26 10.26 10.24 10.21 hardening accelerator type 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole Blending amount (parts by mass) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Evaluation of Copper Foil Adhesion 90°peel strength (N/cm) 6.6 6.8 6.7 6.5 6.8 6.9 6.7 Evaluation of heat resistance Evaluation of glass transition temperature 1 (°C) 241 240 242 239 242 238 239 Evaluation of glass transition temperature 2 (°C) Difference from when no modified resin (C) was added (°C) -7 -8 -6 -9 -6 -10 -9 Glass transition temperature (°C) without adding modified resin (C) 248 248 248 248 248 248 248

[Table 2] Table 2 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Thermosetting resin (A) type A1 A1 A1 A1 A1 A1 A1 Blending amount (parts by mass, solid content) 61.5 61.5 61.5 61.5 61.5 61.5 61.5 Thermohardener (B) type B1 B1 B1 B1 B1 B1 B1 Blending amount (parts by mass, solid content) 38.5 38.5 38.5 38.5 38.5 38.5 38.5 Modified resin (C) type C6 C7 C8 C9 C10 C11 C12 Blending amount (parts by mass) 10 10 10 10 10 10 10 Solubility parameter (cal/cm ³ ) ^0.5 10.25 10.54 10.58 11.32 10.53 10.51 10.32 hardening accelerator type 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole Blending amount (parts by mass) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Evaluation of Copper Foil Adhesion 90°peel strength (N/cm) 6.9 7 7 6.8 6.3 6.4 6.3 Evaluation of heat resistance Evaluation of glass transition temperature 1 (°C) 237 229 230 239 232 244 241 Evaluation of glass transition temperature 2 (°C) Difference from when no modified resin (C) was added (°C) -11 -19 -18 -9 -16 -4 -7 Glass transition temperature (°C) without adding modified resin (C) 248 248 248 248 248 248 248

[table 3] table 3 Example 15 Example 16 Example 17 Example 18 Example 19 Comparative example 1 Comparative example 2 Thermosetting resin (A) type A1 A1 A1 A1 A1 A1 A1 Blending amount (parts by mass, solid content) 61.5 61.5 61.5 61.5 42.7 61.5 42.7 Thermohardener (B) type B1 B1 B1 B1 B2 B1 B2 Blending amount (parts by mass, solid content) 38.5 38.5 38.5 38.5 57.3 38.5 57.3 Modified resin (C) type C13 C14 C15 C16 C1 - - Blending amount (parts by mass) 10 5 5 5 5 - - Solubility parameter (cal/cm ³ ) ^0.5 10.31 10.14 10.40 10.92 10.26 - - hardening accelerator type 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 2-Ethyl-4-methylimidazole 4-Dimethylaminopyridine 2-Ethyl-4-methylimidazole 4-Dimethylaminopyridine Blending amount (parts by mass) 0.3 0.3 0.3 0.3 0.5 0.3 0.5 Evaluation of Copper Foil Adhesion 90°peel strength (N/cm) 6.5 6.6 6.8 7.0 6.6 5.5 5.7 Evaluation of heat resistance Evaluation of glass transition temperature 1 (°C) 247 242 236 232 230 248 234 Evaluation of glass transition temperature 2 (°C) Difference from when no modified resin (C) was added (°C) -1 -6 -12 -16 -4 - - Glass transition temperature (°C) without adding modified resin (C) 248 248 248 248 234 248 234

Examples 1 to 19, which are the thermosetting compositions of the present invention, exhibited excellent heat resistance and copper foil adhesion in the obtained cured products. On the other hand, Comparative Example 1 - Comparative Example 2 are examples which do not contain modified resin (C), and copper foil adhesiveness is inferior.

Claims (10)

A thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), the thermosetting composition is characterized in that The modified resin (C) is a urethane resin made from polyol (c1) and polyisocyanate (c2) with an isocyanate group content of 0 mol/kg, The modified resin (C) has a glass transition temperature of not less than -100°C and not more than 50°C, The modified resin (C) has a number average molecular weight of not less than 4,000 and not more than 100,000, The content of the modified resin (C) is not less than 0.1 parts by mass and not more than 60 parts by mass relative to 100 parts by mass of the thermosetting resin (A). The thermosetting composition according to claim 1, wherein the polyol (c1) includes polyester polyol and/or polycarbonate polyol. The thermosetting composition according to claim 2, wherein the polyester polyol contains aliphatic diol as a raw material. The thermosetting composition according to Claim 1, wherein the solubility parameter of the modified resin (C) is not less than 9.7 (cal/cm ³ ) ^0.5 and not more than 12.0 (cal/cm ³ ) ^0.5 . The thermosetting composition according to claim 1, wherein the glass transition temperature of the thermosetting composition is 180° C. or higher. A cured product, characterized in that it is formed from the thermosetting composition according to claim 1. A semiconductor sealing material, characterized in that it is formed from the thermosetting composition as described in claim 1. A prepreg characterized in that it is a semi-cured material impregnated with a base material comprising the thermosetting composition according to claim 1 and a reinforcing base material. A circuit board, characterized by comprising a plate-shaped object of the thermosetting composition according to claim 1 and copper foil. A buildup film, characterized by comprising a cured product of the thermosetting composition according to claim 1 and a base film.