KR20230057954A - Thermosetting composition, cured product thereof, semiconductor encapsulation material, prepreg, circuit board and build-up film - Google Patents

Abstract

[Problem] 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.
[Solution] The present invention is a thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), wherein the modified resin (C) comprises a polyol (c1) and a polyisocyanate (c2) is a urethane resin having an isocyanate group content of 0 mol/kg, the glass transition temperature of the modified resin (C) is -100 ° C. or more and 50 ° C. or less, and the number average molecular weight of the modified resin (C) is, 4,000 or more and 100,000 or less, and the content of the modified resin (C) 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 (A).

Description

Thermosetting composition, its cured product, semiconductor encapsulation material, prepreg, circuit board and build-up film

The present invention relates to a thermosetting composition, a cured product thereof, a semiconductor sealing material, a prepreg, a circuit board, and a build-up film.

DESCRIPTION OF RELATED ART In recent years, the request|requirement of miniaturization, weight reduction, and high speed of an electronic device is increasing, and density increase of a printed wiring board is progressing. Therefore, it is required to further reduce the wiring width and the wiring interval, and in order to keep the wiring width small, it is necessary that the metal layer (metal film) used as the wiring and the resin substrate have sufficient adhesion.

However, in the conventional printed wiring board, the adhesion between the metal layer and the resin is mainly due to the unevenness of the roughened metal foil or the roughened surface of the resin surface obtained by physical roughening such as plasma treatment or chemical roughening such as permanganic acid etching. In printed wiring board applications for high frequency applications, such as large servers and antennas, it causes signal attenuation (transmission loss) due to handling of high frequency signals, so adhesion is not dependent on the anchor effect. There is a need to improve the quality.

In order to improve adhesiveness, thermosetting compositions containing polyester additives have been proposed (for example, see Patent Documents 1 and 2).

International Publication No. 19/131413 Japanese Patent Laid-Open No. 2021-107493

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 is a thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), wherein the modified resin (C) uses a polyol (c1) and a polyisocyanate (c2) as raw materials. , A urethane resin having an isocyanate group content of 0 mol/kg, a glass transition temperature of the modified resin (C) being -100°C or more and 50°C or less, and a number average molecular weight of the modified resin (C) being 4,000 or more and 100,000 or less. and the content of the modified resin (C) 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 (A).

In addition, the present invention provides a cured product, a semiconductor encapsulating material, a prepreg, a circuit board, and a build-up film characterized in that they are formed by the thermosetting composition.

According to the thermosetting composition of the present invention, it is possible to achieve both excellent copper foil adhesion and heat resistance in the resulting 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 (midpoint 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 glass transition temperature is described in the Example mentioned later.

In addition, as in the present invention, when a urethane resin is added as the modified resin (C), it is generally concerned that the heat resistance significantly decreases, but in the present invention, by adding a specific urethane resin, excellent copper foil adhesion and heat resistance are compatible can do.

The glass transition temperature (midpoint glass transition temperature (Tmg)) of the thermosetting composition in a state in which the modifying resin (C) is not added is preferably 180°C or higher, more preferably 190°C or higher, and further It is preferably 200°C or higher, and the upper limit is 400°C.

Difference between the glass transition temperature of the thermosetting composition and the glass transition temperature of the thermosetting composition in a state in which the modifying resin (C) is not added (glass transition temperature of the thermosetting composition - addition of the modifying resin (C)) The glass transition temperature of the thermosetting composition in the non-curing state) is preferably -30°C or higher, more preferably -20°C or higher, still more preferably -10°C or higher, and the upper limit is 30°C.

Examples of the thermosetting resin (A) include epoxy resins, benzoxazine structure-containing resins, maleimide resins, polyphenylene ether resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, and the like, at least It is preferable to include an epoxy resin.

As said epoxy resin, 1 type, or 2 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 tetramethyl biphenyl type epoxy resin, di Glycidyloxynaphthalene compounds (1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc.), phenol novolak type epoxy resins, cresol novolak type epoxy resins, 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- Polys such as phenol coaxial novolac type epoxy resin, naphthol-cresol coaxial novolac type epoxy resin, naphthylene ether type epoxy resin, 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane Hydroxy naphthalene type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resins, biphenyl novolac type epoxy resins, phosphorus modified epoxy resins obtained by introducing phosphorus atoms into these various types of epoxy resins, and the like.

Especially, as said epoxy resin, a cresol novolak type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene- phenol addition reaction type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl novolak type epoxy resin, and naphthalene Naphthol novolac type epoxy resins containing skeletons, naphthol aralkyl type epoxy resins, naphthol-phenol coaxial novolak type epoxy resins, naphthol-cresol coaxial novolak type epoxy resins, naphthylene ether type epoxy resins, polyhydroxynaphthalene type epoxy resins Resins, crystalline biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, xanthene-type epoxy resins, and aromatic ring-modified novolak-type epoxy resins containing an alkoxy group (containing an aromatic ring and an alkoxy group containing a glycidyl group in formaldehyde) A compound having an aromatic ring linked thereto) is particularly preferable in view of obtaining a cured product having excellent heat resistance.

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, still more preferably 95% by mass or more, and the upper limit is 100% by mass.

As said maleimide resin, 1 type, or 2 or more types can be used, For example, resin represented by any of the following structural formulas is mentioned.

[In formula (1), R ¹ represents an a1-valent organic group, and R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. represents a group, and a1 represents an integer greater than or equal to 1]

[In Formula (2), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom having 7 to 20 carbon atoms. 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 each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms group or a group having 6 to 15 carbon atoms in which a saturated hydrocarbon group and an aromatic hydrocarbon group are combined. 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, even more preferably 90% by mass or more, and preferably 99% by mass, among the non-volatile matter of the thermosetting composition. % or less, more preferably 98% by mass or less.

The thermosetting agent (B) may be a compound capable of curing the thermosetting composition by reacting with the thermosetting resin (A) by heating, and one type or two or more types may be used. An amine compound, an amide compound, an active Ester resin, acid anhydride, phenol resin, cyanate ester resin, etc. are mentioned. Especially, as a heat curing agent (B), it is preferable to contain at least 1 sort(s) chosen from an active ester resin and a phenol resin.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives.

As said amide compound, dicyandiamide, the polyamide resin synthesize|combined from the dimer of linolenic acid, and ethylenediamine, etc. are mentioned.

The active ester resin is not particularly limited, but in general, ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are used in one molecule. A compound having two or more is preferably used. It is preferable that the said active ester resin is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and 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, a phenol compound and/or a naphthol compound is more preferable. 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, etc. or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-phenol addition type resin, etc. are mentioned.

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

Examples of the phenolic resin include phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (xylock resin), naphthol aralkyl resin, and triphenylol. Methane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (a compound containing polyhydric phenolic hydroxyl group in which a phenol nucleus is linked from a bismethylene group) ), naphthalene skeleton-containing phenolic resin, biphenyl-modified naphthol resin (polyhydric naphthol compound having a phenolic nucleus connected to a bismethylene group), aminotriazine-modified phenolic resin (polyhydric phenolic hydroxyl group-containing compound having a phenolic nucleus connected to melamine, benzoguanamine, etc.) ) or polyhydric phenolic hydroxyl group-containing resins such as alkoxy group-containing aromatic ring-modified novolak resins (compounds containing polyhydric phenolic hydroxyl groups in which formaldehyde phenol nuclei and alkoxy group-containing aromatic rings are linked), bisphenol A, bisphenol F, and the like, biphenyl compounds such as biphenyl and tetramethylbiphenyl; triphenylolmethane, tetraphenylolethane; dicyclopentadiene-phenol addition reaction type resins, phosphorus-modified phenolic compounds obtained by introducing phosphorus atoms into these various phenolic hydroxyl group-containing compounds, and the like.

As said cyanate ester resin, 1 type, or 2 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 Nate 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, poly Hydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak 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 novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol coaxial novolak cyanate ester resin, naphthol-cresol coaxial 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, etc. are 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 in terms of obtaining a cured product having particularly excellent heat resistance It is preferable to use an ester resin, a naphthylene ether type cyanate ester resin, or a novolac type cyanate ester resin. In view of obtaining a cured product having excellent dielectric properties, dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable

The thermosetting composition of the present invention may further contain a curing accelerator (B1). As said hardening accelerator (B1), 1 type, or 2 or more types can be used, For example, a phosphorus compound, a tertiary amine, an imidazole compound, an organic acid metal salt, a Lewis acid, an amine complex salt etc. are mentioned. In particular, when used as a semiconductor encapsulating material, triphenylphosphine is used as a phosphorus compound and 1,8-diazabicyclo-[ 5.4.0]-undecene (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 said maleimide compound (B2), 1 type, or 2 or more types can be used, For example, N-cyclohexyl maleimide, N-methyl maleimide, N-n-butyl maleimide, N-hexyl maleimide, N N-aliphatic maleimides such as -tert-butylmaleimide; N-aromatic maleimides such as N-phenylmaleimide, N-(P-methylphenyl)maleimide, and N-benzylmaleimide; 4,4'-diphenylmethanebismaleimide, 4,4'-diphenylsulfonebismaleimide, m-phenylenebismaleimide, bis(3-methyl-4-maleimidephenyl)methane, bis(3- Ethyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5- and bismaleimides such as diethyl-4-maleimide phenyl)methane.

Among them, as the maleimide compound (B2), bismaleimides are preferable in that the cured product has good heat resistance, and in particular, 4,4'-diphenylmethane bismaleimide and bis(3,5-dimethyl- 4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, and bis(3,5-diethyl-4-maleimidephenyl)methane are preferable.

When using the said maleimide compound (B2), you may contain the said amine compound, the said phenol compound, the said acid anhydride type compound, an imidazole compound, an organometallic salt, etc. as needed.

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

As polyol (c1) used for manufacture of the said urethane resin, polyester polyol, polyether polyol, polycarbonate polyol, etc. are mentioned. Among these, it is preferable to include a polyester polyol and/or a polycarbonate polyol from the viewpoint of obtaining further excellent copper foil adhesion and heat resistance.

As said polyester polyol, 1 type, or 2 or more types can be used, For example, polyester polyol obtained by making a polyol and polycarboxylic acid react; Polyester polyol obtained by ring-opening polymerization of a cyclic ester compound; Polyester polyol obtained by copolymerizing these, etc. are mentioned.

As said polyol used for manufacture of the said polyester polyol, 1 type(s) or 2 or more types 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-dodecanediol, diethylene glycol, triethylene glycol , triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 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 , aliphatic polyols such as trimethylolethane, trimethylolpropane, and pentaerythritol; polyols having alicyclic structures such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts thereof; polyols having aromatic structures such as bisphenol A and bisphenol F; and polyols obtained by modifying the polyols having the aromatic structure with alkylene oxide. Especially, it is preferable to contain the said aliphatic polyol from the point which further excellent copper foil adhesiveness and heat resistance are obtained.

The molecular weight of the polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, and still more preferably 700 or less. In addition, in this specification, a number average molecular weight represents the value computed based on the hydroxyl value based on the potentiometric titration method of JISK0070:1992.

Examples of the alkylene oxide used for modification of the polyol having an aromatic structure include an alkylene oxide having 2 or more and 4 or less (preferably 2 or more and 3 or less) carbon atoms, such as ethylene oxide and propylene oxide. 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, more preferably 16 moles or less, relative to 1 mole of the polyol having the aromatic structure. am.

As said polycarboxylic acid, 1 type, or 2 or more types can be used, For example, Aliphatic polycarboxylic acid, such as succinic acid, adipic acid, sebacic acid, dodecane dicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid; Anhydrides or esters thereof are exemplified.

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

As said cyclic ester compound, 1 type, or 2 or more types can be used, For example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, 3-penten-4-olide, 12-dodecanolide, and γ-dodecanolactone are exemplified.

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

At the time of the said reaction, you may make a catalyst coexist. As said catalyst, 1 type, or 2 or more types can be used, For example, Titanium type catalysts, such as tetraisopropyl titanate and tetrabutyl titanate; tin catalysts such as dibutyltin oxide; Organic sulfonic acid type catalysts, such as p-toluenesulfonic acid, etc. are mentioned. The amount of the catalyst is preferably 0.0001 part by mass or more, more preferably 0.0005 part by mass or more, preferably 0.01 part by mass or less, and more preferably 0.005 part by mass, based on 100 parts by mass in total of the polyol and the polycarboxylic acid. below the mass part.

Examples of the polyether polyol include one obtained by addition polymerization (ring-opening polymerization) of an alkylene oxide using one or two 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, 1,6-hexanediol, and the like. straight-chain diols of; branched chain diols such as neopentyl glycol, 1,2-propanediol, and 1,3-butanediol; triols such as glycerin, trimethylolethane, trimethylolpropane, and pyrogallol; polyols such as sorbitol, sucrose, and aconite sugar; tricarboxylic acids such as aconitic acid, trimellitic acid, and hemimellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propane trithiol etc. are mentioned.

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

Examples of the polycarbonate polyol include a reaction product of a carbonate ester and a polyol; Reactants, such as phosgene and bisphenol A, etc. are mentioned.

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

As a polyol which can react with the said carbonate ester, the polyol illustrated as the polyol used for manufacture of the said polyester polyol, for example; and high molecular weight polyols (number average molecular weight of 500 or more and 5,000 or less) such as polyether polyols (polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.).

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

As the polyisocyanate (c2), one type or two or more types can be used, and examples thereof include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide-modified diisocyanate. aromatic polyisocyanates such as phenylmethane diisocyanate, Kurdish diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; Alicyclic structure containing polyisocyanate, such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, etc. are mentioned.

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) per molecule is preferably 1 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 It is one or less, and it is two especially preferably.

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

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

Examples of the other additives include curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, optical whitening agents, silane coupling agents, waxes, and thermoplastic resins. These additives may be used independently or may use 2 or more types together.

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 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 - the 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 or less. When the difference in solubility parameter between the cured product and the modified resin (C) is in an appropriate range, it is possible to be compatible before thermal curing, and thermal curing (that is, the thermosetting resin (A) and the thermal curing agent ( With the reaction of B), the compatibility between the mixture (including the reaction process) and the modified resin (C) decreases, and after thermal curing, the reaction product of the thermosetting resin (A) and the thermal curing agent (B) It is thought that it becomes possible to phase-separate the modified resin (C).

The solubility parameter of the cured product is based on Fedors' method (Polymer Engineering and Science, 1974, vol. 14, No. 2), and each compound included in the cured product of the mixture of the curable resin (A) and the thermosetting agent (B) The solubility parameter of is calculated, and based on the mass-based ratio of each compound, it can be obtained as a weighted average value. In addition, for the solubility parameter of the modified resin (C), the solubility parameter of each compound-derived unit used as a raw material of the modified resin (C) is calculated based on Fedors' method, and the mass-based ratio of each compound-derived unit Based on this, it can be obtained as a weighted average value.

The glass transition temperature (midpoint 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 degrees C or less, More preferably, it is 30 degrees C or less.

The number average molecular weight of the modified resin (C) is 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, still more preferably less than 50,000. The number average molecular weight of the modified resin (C) shows a value calculated based on the hydroxyl value based on the potentiometric titration method of JIS K0070:1992.

The thermosetting composition is in a compatible state before the thermosetting reaction, but it is preferable that the thermosetting resin (A) and the modified resin (C) phase-separate after the thermosetting reaction. In the phase separation state after the thermal curing reaction, the reaction product of the thermosetting resin (A) and the thermosetting agent (B) forms an anatomy, and the modified resin (C) forms an island, and the sea-island type ( It is preferable to form a sea island type 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. While it is possible to uniformly disperse the modified resin (C) in a mixture of the thermosetting resin (A) and the heat curing agent (B) by being in a commercial state before the thermal curing reaction, the thermosetting resin (A) and the thermal curing agent after the thermal curing reaction Since it is possible to maintain the chemical and mechanical properties of the modified resin (C) itself by phase separation of the reactant of (B) and the modified resin (C), in the obtained cured product, the thermosetting resin (A) and the thermosetting agent (B) ) It is possible to uniformly disperse the domain of the modified resin (C) in the reactant, and it is thought that it becomes possible to provide a cured product having both better heat resistance and copper foil adhesion.

The presence or absence of phase separation in the cured product can be confirmed by the presence or absence of cloudiness in the cured product and the existence of dissections and drawings when the fracture surface of the cured product is observed with an atomic force microscope (AFM).

The content of the modified resin (C) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, based on 100 parts by mass of the thermosetting resin (A). It is preferably 60 parts by mass or less, more preferably 45 parts by mass or less. Moreover, it may be 35 parts by mass or less, more preferably 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 thermal expansion coefficient of the insulating layer can be further reduced. As the above inorganic filler, one type or two or more types can be used, and examples thereof include silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, aluminum hydroxide, hydroxide Magnesium, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc. are mentioned, Silica is preferable, and fused silica is more preferable. In addition, the shape of the said silica may be either crushed or spherical, and it is preferable that it is spherical from a viewpoint of suppressing the melt viscosity of a thermosetting composition, raising a compounding quantity.

In particular, when the thermosetting composition of the present invention is used for a semiconductor encapsulant (preferably a high thermal conductivity semiconductor encapsulant for power transistors and power ICs), silica (including fused silica and crystalline silica, preferably crystalline silica), Alumina and silicon nitride are preferred.

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, Especially preferably, it is 80 mass % or more, Preferably it is 95 mass % or less, More preferably, it is 90 mass % or less. When the content rate of the inorganic filler is increased, it is easy to improve the flame retardancy, heat-and-moisture resistance, and solder crack resistance, and lower the thermal expansion coefficient.

The thermosetting composition of the present invention may further contain a flame retardant (E). It is preferable that the said flame retardant (E) is non-halogen type which does not contain a halogen atom substantially. As said flame retardant (E), 1 type, or 2 or more types can be used, For example, phosphorus flame retardant, nitrogen type flame retardant, silicone type flame retardant, inorganic type flame retardant, organic metal salt type flame retardant etc. are mentioned.

As the phosphorus-based flame retardant, one type or two or more types can be used, and examples thereof include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing compounds such as phosphate amide. inorganic nitrogen-containing phosphorus compounds such as phosphorus compounds; Phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, general-purpose organic phosphorus compounds such as organic nitrogen-containing compounds, and 9,10-dihydro-9-oxa-10-phosphaphenane Trene = 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 organic phosphorus compounds such as cyclic organic phosphorus compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins. .

When using the phosphorus-based flame retardant, hydrotalcite, magnesium hydroxide, a boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, or the like may be used in combination with the phosphorus-based flame retardant.

The red phosphorus is preferably surface treated, and the surface treatment method includes, for example, (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. (ii) method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin such as phenol resin, (iii) magnesium hydroxide, A method of double-coating with a thermosetting resin such as a phenol resin on a film of an inorganic compound such as aluminum hydroxide, zinc hydroxide, or titanium hydroxide, and the like are exemplified.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine compounds, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds desirable. When using the said nitrogen-type flame retardant, you may use a metal hydroxide, a molybdenum compound, etc. together.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc., for example, (i) Sulfate aminotriazine compounds such as guanyl sulfate melamine, melem sulfate, and melam sulfate, (ii) phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol, and melamine, benzoguanamine, acetoguanamine, and form A cocondensate of melamine such as guanamine and formaldehyde, (iii) a mixture of a cocondensate of (ii) and a phenolic resin such as a condensate of phenolformaldehyde, (iv) the above (ii) and (iii) and those further modified with tung oil, isomerized linseed oil, and the like.

As a specific example of the said cyanuric acid compound, cyanuric acid, melamine cyanuric acid, etc. are mentioned, for example.

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of nitrogen-based flame retardant, other components of the thermosetting composition, and the degree of desired flame retardancy. It is preferably blended in the range of 0.05 to 10 parts by mass, particularly preferably in the range of 0.1 to 5 parts by mass, in 100 parts by mass of the thermosetting composition in which all are blended.

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 type or two or more types can be used, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide; Zinc molybdate, molybdenum trioxide, zinc tartrate, 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 metal oxides such as; metal carbonate compounds such as zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate; metal powders such as aluminum, 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 borax; Shipri (Bokusui Brown Co.), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O ₅ -MgO system, P ₂ O ₅ -B ₂ O ₃ -PbO- Low melting glass, such as MgO type, P-Sn-OF type, PbO-V ₂ O ₅ -TeO ₂ type, Al ₂ O ₃ -H ₂ O type, and lead borosilicate type, etc. are mentioned.

Examples of the organometallic salt-based flame retardant include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, metal atoms and aromatic compounds or heterocyclic compounds ionically bonded or coordinated. A compound etc. are mentioned.

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, and it becomes particularly suitable for the manufacture of printed circuit boards.

As the organic solvent (F), one type or two or more types can be used, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propylene glycol monomethyl ether; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ethyldiglycol acetate, and carbitol acetate; carbitol solvents such as cellosolve, methyl cellosolve, and butyl carbitol; Aromatic hydrocarbon solvents, such as toluene and xylene; Amide solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. are mentioned.

In particular, when the thermosetting composition of the present invention is used for printed wiring boards, examples of the organic solvent (F) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propylene glycol monomethyl ether; Acetate ester solvents, such as propylene glycol monomethyl ether acetate and ethyl diglycol acetate; carbitol solvents such as methyl cellosolve; Amide solvents, such as dimethylformamide, etc. are preferable.

Moreover, when using the thermosetting composition of this invention for a build-up film, as said organic solvent (F), Ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone; Acetate ester solvents, such as ethyl acetate, butyl acetate, cellosolve acetate, a propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents, such as toluene and xylene; Amide solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. are preferable.

When the organic solvent (F) is included, the content of the thermosetting composition is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, and 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 including conductive particles, it can be used as an electrically conductive paste and is suitable for an anisotropic electrically conductive material.

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

The thermosetting composition of this 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 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 molded product, an adhesive layer, a coating film, and a film.

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

As a method for producing 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 are mixed with an extruder, kneader, and roll as necessary. It can be obtained by sufficiently melting and mixing until it becomes uniform using the like.

When the thermosetting composition of the present invention is used for a semiconductor encapsulating material, it can be molded into a semiconductor package. Specifically, the composition is molded using a mold, a transfer molding machine, an injection molding machine, etc., and further, at 50 to 200 ° C. By heating for about 10 hours, a molded semiconductor device can be obtained.

Moreover, in order to manufacture a printed circuit board using the thermosetting composition of this invention, the method of impregnating a reinforcing base material with a curable composition, and overlapping copper foil and heat-pressing it is mentioned. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, a prepreg, which is a cured product, can be obtained by first heating the thermosetting composition (preferably at 50 to 170° C. depending on the type of organic solvent (F)). The resin content in the prepreg is preferably 20% by mass or more and 60% by mass or less. Then, the prepreg is laminated, the copper foil is overlapped, and the desired printed circuit board is obtained by heat-pressing at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

In the case of using the thermosetting composition of the present invention as a conductive paste, for example, a method for dispersing conductive particles (fine conductive particles) in the thermosetting composition to obtain a composition for an anisotropic conductive film, and a paste resin composition for circuit connection that is liquid at room temperature. or an anisotropic conductive adhesive.

As a method of obtaining an interlayer insulating material for a build-up substrate from the thermosetting composition of the present invention, for example, the thermosetting composition is applied to a wiring board on which a circuit is formed by using a spray coating method or a curtain coating method, and then cured. . Thereafter, after drilling a predetermined through-hole portion or the like as necessary, processing with a roughening agent and washing the surface with hot water to form irregularities to remove metals such as copper. plating treatment. As the plating method, electroless plating and electrolytic plating are preferable, and examples of the roughening agent include oxidizing agents, alkalis, organic solvents, and the like. A build-up substrate can be obtained by repeating such an operation in sequence as desired, and alternately building up and forming a resin insulating layer and a conductor layer of a predetermined circuit pattern. However, drilling of the through-hole portion is performed after formation of the outermost resin insulating layer. Further, the copper foil with a resin obtained by semi-curing the thermosetting composition on the copper foil is heated and pressed at 170 to 300 ° C. on a wiring board on which a circuit is formed, thereby forming a roughened surface, omitting the plating process step, and building a substrate. It is also possible to make

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

When the thermosetting composition of the present invention is used for a build-up film, the film is softened by the temperature conditions of the laminate in the vacuum lamination method (usually 70°C to 140°C), and applied to the circuit board simultaneously with the lamination of the circuit board. It is important to show fluidity (resin flow) capable of resin filling in existing via-holes or through-holes, and it is preferable to blend each of the above components so as to express 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 preferable that resin filling is usually made possible within this range. In the case of laminating both sides of the circuit board, it is preferable to fill about 1/2 of the through hole.

Specifically, the method for producing the adhesive film described above is to prepare the varnish-like thermosetting composition of the present invention, then apply the varnish-like composition to the surface of the support film (Y), and further heat or hot-air blasting. It can be manufactured by drying an organic solvent by etc., and forming the 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 preferably has a thickness of 10 to 100 μm.

Moreover, layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent adhesion of foreign substances or the like to the surface of the resin composition layer and scratches.

The above support film and protective film are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester such as polyethylene naphthalate, polycarbonate, and polycarbonate. Mead, release paper, metal foil, such as copper foil and aluminum foil, etc. are mentioned. In addition, the support film and the protective film may be subjected to release treatment other than mat treatment and corona treatment.

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

The support film Y described above is peeled off after laminating to a circuit board or after forming an insulating layer by curing by heating. If the support film Y is peeled off after the adhesive film is heat-cured, adhesion of foreign substances or the like in the curing step can be prevented. In the case of peeling after curing, release treatment is usually given to the supporting film beforehand.

Next, in the method of manufacturing a multilayer printed wiring board using the adhesive film obtained as described above, for example, when the layer (X) is protected with a protective film, after peeling them, the layer (X), It laminates on one side or both sides of a circuit board by, for example, a vacuum lamination method so as to directly contact the circuit board. The method of lamination may be a batch type or a continuous type using a roll. Also, before laminating, the adhesive film and the circuit board may be heated (preheated) as needed.

Laminate conditions include a compression temperature (lamination temperature) of preferably 70 to 140° C., a compression pressure of preferably 1 to 11 kgf/cm2 (9.8×10 ⁴ to 107.9×10 ⁴ N/m 2 ), and an air pressure of 20 mmHg. It is preferable to laminate under reduced pressure of (26.7 hPa) or less.

A method for obtaining the cured product of the present invention may be based on a general curing method for a thermosetting composition. For example, the heating temperature conditions may be appropriately selected according to the type or use of the curing agent to be combined, but the obtained obtained by the above method What is necessary is just to heat a composition in the temperature range of about 20-300 degreeC.

[Example]

Hereinafter, the present invention will be described in more detail by way of 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after the internal temperature was raised to 220°C, 0.03 part by mass of TiPT was added, and a condensation reaction was carried out at 220°C for 30 hours to synthesize polyester polyol 1 (abbreviated as PEs1).

The obtained PEs1 had a hydroxyl value of 16.0 and a number average molecular weight of 7,000.

[Synthesis Example 2] Synthesis of polyester polyol 2

169.5 parts by mass of ethylene 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after the internal temperature was raised to 220°C, 0.03 part by mass of TiPT was added, and a condensation reaction was carried out 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after the internal temperature was raised to 220°C, 0.03 part by mass of TiPT was added, and a condensation reaction was carried out at 220°C for 20 hours to synthesize polyester polyol 3 (abbreviated as PEs3).

The obtained PEs3 had a hydroxyl value of 56.1 and a number average molecular weight of 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after raising the internal temperature to 220°C, 0.1 part by mass of TiPT was added and condensation was carried out at 220°C for 20 hours to synthesize polyester polyol 4 (abbreviated as PEs4).

The obtained PEs4 had a hydroxyl value of 56.1 and a number average molecular weight of 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after the internal temperature was raised to 220°C, 0.03 parts by mass of TiPT was added, and a condensation reaction was carried out at 220°C for 15 hours to synthesize polyester polyol 5 (abbreviated as PEs5).

The obtained PEs5 had a hydroxyl value of 112.2 and a number average molecular weight of 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 introduced into the reaction apparatus, and heating and stirring were started.

Next, after the internal temperature was raised to 220°C, 0.03 part by mass of TiPT was added, and a condensation reaction was carried out 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

To a reaction apparatus, 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added, and 4,4'-diphenylmethane diisocyanate (trademark; manufactured by Toso Co., Ltd., "Mirionate MT", hereinafter abbreviated as MDI) 28.6 The mass part was put in. Next, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 1 (C1).

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°C.

[Synthesis Example 8] Synthesis of Urethane Resin 2

1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction apparatus, and 10.7 parts by mass of MDI was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 2 (C2).

The obtained urethane resin had a hydroxyl value of 11.2, a number average molecular weight of 10,000, and a glass transition temperature of -54°C.

[Synthesis Example 9] Synthesis of Urethane Resin 3

1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction apparatus, and 32.1 parts by mass of MDI was introduced. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 3 (C3).

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°C.

[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 apparatus, and 21.5 parts by mass of 1,3-xylylene diisocyanate (trademark; manufactured by Mitsubishi Chemical Corporation, “Takenate 500”) was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 10 hours to synthesize Urethane Resin 4 (C4).

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°C.

[Synthesis Example 11] Synthesis of Urethane Resin 5

1,000 parts by mass of PEs1 obtained in Synthesis Example 1 was added to the reaction apparatus, and 19.2 parts by mass of hexamethylene diisocyanate (trademark; manufactured by Tosoh Corporation, “HDI”) was charged. Next, after raising the internal temperature to 120°C, the reaction was continued for 10 hours to synthesize Urethane Resin 5 (C5).

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 -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 tolylene diisocyanate (trademark; manufactured by Mitsubishi Chemical Corporation, “Cosmonate T-80”) was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize urethane resin 6 (C6).

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 -51°C.

[Synthesis Example 13] Synthesis of Urethane Resin 7

1,000 parts by mass of PEs2 obtained in Synthesis Example 2 was added to the reaction apparatus, and 36.4 parts by mass of MDI was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 7 (C7).

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 added to the reaction apparatus, and 106.3 parts by mass of MDI was introduced. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 8 (C8).

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°C.

[Synthesis Example 15] Synthesis of Urethane Resin 9

1,000 parts by mass of PEs4 obtained in Synthesis Example 4 was added to the reaction apparatus, and 106.3 parts by mass of MDI was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize urethane resin 9 (C9).

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°C.

[Synthesis Example 16] Synthesis of Urethane Resin 10

1,000 parts by mass of PEs5 obtained in Synthesis Example 5 was added to the reaction apparatus, and 151.4 parts by mass of MDI was introduced. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 10 (C10).

The obtained urethane resin had a hydroxyl value of 37.4, a number average molecular weight of 3,000, and a glass transition temperature of -40°C.

[Synthesis Example 17] Synthesis of Urethane Resin 11

1,000 parts by mass of PEs5 obtained in Synthesis Example 5 was added to the reaction apparatus, and 222.6 parts by mass of MDI was introduced. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 11 (C11).

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°C.

[Synthesis Example 18] Synthesis of Urethane Resin 12

1,000 parts by mass of PEs6 obtained in Synthesis Example 6 was added to the reaction apparatus, and 59.5 parts by mass of MDI was introduced. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 12 (C12).

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°C.

[Synthesis Example 19] Synthesis of Urethane Resin 13

1,000 parts by mass of PEs6 obtained in Synthesis Example 6 was added to the reaction apparatus, and 106.3 parts by mass of MDI was introduced. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 13 (C13).

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°C.

[Synthesis Example 20] Synthesis of Urethane Resin 14

In a reaction apparatus, 1,000 parts by mass of polycarbonate polyol (trademark: manufactured by Asahi Kasei Co., Ltd., "Duranol T5652", number average molecular weight: 2000) produced from 1,5-pentanediol and 1,6-hexanediol was added. In addition, 93.8 parts by mass of MDI was charged. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 14 (C14).

The hydroxyl value of the obtained urethane resin was 13.2, the number average molecular weight was 8,500, and the glass transition temperature was -44°C.

[Synthesis Example 21] Synthesis of Urethane Resin 15

In a reaction apparatus, 1,000 parts by mass of polycarbonate polyol (trademark; manufactured by Asahi Kasei Co., Ltd., "Duranol T5651", number average molecular weight: 1000) produced from 1,5-pentanediol and 1,6-hexanediol was added. In addition, 200 parts by mass of MDI was charged. Subsequently, after raising the internal temperature to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 15 (C15).

The obtained urethane resin had a hydroxyl value of 18.7, a number average molecular weight of 6,000, and a glass transition temperature of -38°C.

[Synthesis Example 22] Synthesis of Urethane Resin 16

1,000 parts by mass of polycarbonate polyol (trademark; manufactured by Asahi Kasei Co., Ltd., "Duranol G3450J", number average molecular weight: 800) produced from 1,3-propanediol and 1,4-butanediol was added to the reaction apparatus, , 250 parts by mass of MDI was charged. Subsequently, after the internal temperature was raised to 120°C, the reaction was continued for 5 hours to synthesize Urethane Resin 16 (C16).

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°C.

[Example 1]

In a mixing container, 61.5 parts by mass of a polyhydroxynaphthalene type epoxy resin (trademark; manufactured by DIC Co., Ltd., "EPICLON HP-4700", abbreviated as "A1" in the table) as an epoxy resin, and a novolak type as a curing agent. 38.5 parts by mass of a phenol resin (trademark; manufactured by DIC Co., Ltd., "PHENOLITE TD-2131", abbreviated as "B1" in the table) and 10 parts by mass of the urethane resin 1 (C1) obtained in Synthesis Example 7 and stirred at an internal temperature of 130°C until they were commercially available. After adding 0.3 mass part of 2-ethyl-4-methylimidazole as a hardening accelerator and stirring for 20 seconds, the thermosetting composition which is the thermosetting composition of this invention was obtained by vacuum defoaming.

[Examples 2 and 3]

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

[Examples 4 to 15]

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

[Examples 16 to 18]

Instead of blending 10 parts by mass of Urethane Resin 1 (C1), a thermosetting composition was obtained in the same manner as in Example 1 except blending 5 parts by mass of each of the urethane resins (C14 to C16) listed in the table.

[Example 19]

85.4 parts by mass (42.7 parts by mass of solid content) of 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin in a mixing container, and an active ester resin (trademark; manufactured by DIC Corporation, “EPICLON HPC” as a curing agent) -8000-65T”, abbreviated as “B2” in the table) was mixed with 88.2 parts by mass (65% toluene solution, 57.3 parts by mass solid content) and 5 parts by mass of urethane resin 1 (C1) obtained in Synthesis Example 7, The mixture was stirred at an internal temperature of 130° C. while performing desolvation under reduced pressure until the mixture was dissolved. After adding 0.5 mass part of 4-dimethylaminopyridine as a hardening accelerator and stirring for 20 seconds, the thermosetting composition which is the thermosetting composition of this invention was obtained by vacuum defoaming.

[Comparative Example 1]

In a mixing container, 61.5 parts by mass of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin and 38.5 parts by mass of novolak type phenolic resin B1 as a curing agent were blended, and the mixture was stirred at an internal temperature of 130°C until mutually compatible. After adding 0.3 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator and stirring for 20 seconds, the thermosetting composition of the present invention was obtained by vacuum defoaming.

[Comparative Example 2]

In a mixing container, 85.4 parts by mass (42.7 parts by mass of solid content) of 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin and 88.2 parts by mass of active ester resin B2 (65% toluene solution, 57.3 parts by mass solid content) as a curing agent Parts by mass) were blended and stirred until mutually compatible at an internal temperature of 130°C while performing solvent removal under reduced pressure. After adding 0.5 mass part of 4-dimethylaminopyridine as a hardening accelerator and stirring for 20 seconds, the thermosetting composition which is the thermosetting composition of this invention was obtained by vacuum defoaming.

About the obtained thermosetting composition, the following evaluation was performed. The results are shown in a table together with the solubility parameter of the modified resin (C) used in each thermosetting composition.

[Evaluation method of copper foil adhesion]

The thermosetting compositions obtained in Examples and Comparative Examples were poured at 130°C into a mold plate sandwiched with a glass plate having a copper foil attached to one side of a rubber spacer having a thickness of 1 mm, and thermally cured at 175°C for 5 hours. The obtained cured product was cut into a size of 10 mm in width x 60 mm in length, and the 90° peel strength (N/cm) was measured using a peel tester.

Measuring instrument: Shimadzu Autograph (manufactured by Shimadzu Seisakujo Co., Ltd.)

Format: AG-1

Test speed: 50mm/m

[Evaluation method of heat resistance]

Heat resistance was evaluated by glass transition temperature. Specifically, the thermosetting compositions obtained in Examples and Comparative Examples were poured at 130°C into a mold plate sandwiched with a 1 mm-thick rubber spacer with a glass plate, and cured by heat at 175°C for 5 hours. The resulting cured product was cut into a size of 10 mm in width x 55 mm in length, and the storage modulus (E') and loss modulus (E") were measured under the following conditions.

When E'/E" is defined as tanδ, the temperature at which tanδ becomes the maximum is measured as the glass transition temperature (unit: ° C). The Tg of the thermosetting compositions obtained in Examples and Comparative Examples is The difference between the Tg of the epoxy resin composition obtained in Examples and Comparative Examples and the Tg of the epoxy resin composition in the absence of a modified resin was taken as evaluation 2 of the glass transition temperature.

Measuring instrument: dynamic viscoelasticity meter (manufactured by SI Nanotechnology Co., Ltd.)

Format: DMA6100

Measurement temperature range: 0℃~300℃

Heating rate: 5°C/min

Frequency: 1Hz

Measurement Mode: Tensile

[Table 1]

[Table 2]

[Table 3]

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

Claims (10)

A thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C),
The modified resin (C) is a urethane resin containing a polyol (c1) and a polyisocyanate (c2) as raw materials and having an isocyanate group content of 0 mol/kg,
The glass transition temperature of the modified resin (C) is -100°C or more and 50°C or less,
The number average molecular weight of the modified resin (C) is 4,000 or more and 100,000 or less,
A thermosetting composition characterized in that the content of the modified resin (C) is 0.1 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the thermosetting resin (A). According to claim 1,
The thermosetting composition in which the said polyol (c1) contains a polyester polyol and/or a polycarbonate polyol. According to claim 2,
The thermosetting composition in which the said polyester polyol contains an aliphatic glycol as a raw material. According to claim 1,
A thermosetting composition wherein the solubility parameter of the modified resin (C) is 9.7 (cal/cm 3 ) ^0.5 or more and 12.0 (cal/cm 3 ) ^{0.5 or} less. According to claim 1,
A thermosetting composition having a glass transition temperature of 180°C or higher. A cured product characterized by being formed by the thermosetting composition according to claim 1. A semiconductor encapsulating material formed of the thermosetting composition according to claim 1. A prepreg characterized in that it is a semi-hardened material of an impregnated base material having the thermosetting composition according to claim 1 and a reinforcing base material. A circuit board characterized by comprising a plate-like shaped material of the thermosetting composition according to claim 1 and copper foil. A build-up film comprising a cured product of the thermosetting composition according to claim 1 and a base film.