Thermosetting compositions, their cured products, semiconductor encapsulation materials, prepregs, circuit boards, and build-up films

Abstract

To provide a thermosetting composition capable of achieving both excellent copper foil adhesion and heat resistance.SOLUTION: The present invention provides the thermosetting composition containing a thermosetting resin (A), a thermosetting agent (B), and a modified resin (C). The modified resin (C) is a urethane resin using 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 higher and 50°C or lower. The number average molecular weight of the modified resin (C) is 4,000 or more and 100,000 or less. The content of the modified resin (C) is 0.1 pt.mass or more and 60 pts.mass or less based on 100 pts.mass of the thermosetting resin (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to thermosetting compositions, cured products thereof, semiconductor encapsulating materials, prepregs, circuit boards, and build-up films. [Background technology]

[0002] In recent years, the demand for smaller, lighter, and faster electronic devices has increased, leading to higher density printed circuit boards. Therefore, there is a need to further reduce wiring width and spacing. To maintain this small wiring width, the metal layer (metal film) that forms the wiring and the resin substrate must have sufficient adhesion.

[0003] However, in conventional printed circuit boards, the adhesion between the metal layer and the resin largely relies on the anchoring effect caused by the roughening of the metal foil's surface and the surface roughening obtained by physical roughening such as plasma treatment or chemical roughening such as permanganate etching. In high-frequency applications such as large servers and antennas, this can cause signal attenuation (transmission loss) due to the handling of high-frequency signals, so there is a need to improve adhesion without relying on the anchoring effect.

[0004] Thermosetting compositions containing polyester-based additives have been proposed to improve adhesion (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 19 / 131413 [Patent Document 2] Japanese Patent Publication No. 2021-107493 [Overview of the project] [Problems that the invention aims to solve]

[0006] 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 for Solving the Problem

[0007] The present invention is a thermosetting composition containing a thermosetting resin (A), a curing agent (B), and a modified resin (C), wherein the modified resin (C) is a urethane resin having an isocyanate group content of 0 mol / kg and using a polyol (c1) and a polyisocyanate (c2) as raw materials, the glass transition temperature of the modified resin (C) is -100°C or higher and 50°C or lower, the number average molecular weight of the modified resin (C) is 4,000 or higher and 100,000 or lower, 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). The present invention provides a thermosetting composition characterized by the above.

[0008] The present invention also provides a cured product, a semiconductor encapsulation material, a prepreg, a circuit board, and a build-up film, which are characterized by being formed from the above thermosetting composition.

Effects of the Invention

[0009] According to the thermosetting composition of the present invention, it is possible to achieve both excellent copper foil adhesion and heat resistance in the obtained cured product.

Modes for Carrying Out the Invention

[0010] The thermosetting composition of the present invention contains a thermosetting resin (A), a curing agent (B), and a modified resin (C) as essential components.

[0011] 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. The method for measuring the glass transition temperature in this specification is described in the examples below.

[0012] Incidentally, when a urethane resin is added as the modified resin (C) as in the present invention, there is generally a concern that the heat resistance will be significantly reduced. However, in the present invention, by adding a specific urethane resin, excellent copper foil adhesion and heat resistance can be achieved simultaneously.

[0013] The glass transition temperature (midpoint glass transition temperature (Tmg)) of the thermosetting composition in a state where the modified resin (C) is not added 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.

[0014] The difference between the glass transition temperature of the thermosetting composition and the glass transition temperature of the thermosetting composition in a state where the modified resin (C) is not added (glass transition temperature of the thermosetting composition - glass transition temperature of the thermosetting composition in a state where the modified resin (C) is not added) 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.

[0015] Examples of the thermosetting resin (A) include epoxy resins, resins containing a benzoxazine structure, maleimide resins, polyphenylene ether resins, vinyl benzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc., and it is preferably contains at least an epoxy resin.

[0016] The epoxy resin can be one or more types, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, diglycidyloxynaphthalene compounds (1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin Examples include epoxy resins, phenol aralkyl epoxy resins, naphthol novolac epoxy resins, naphthol aralkyl epoxy resins, naphthol-phenol copolymer novolac epoxy resins, naphthol-cresol copolymer novolac epoxy resins, naphthylene ether epoxy resins, polyhydroxynaphthalene epoxy resins such as 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkanes, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resins, biphenyl novolac epoxy resins, and phosphorus-modified epoxy resins obtained by introducing phosphorus atoms into these various epoxy resins.

[0017] Among these, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolac type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol copolymer novolac type epoxy resins, naphthol-cresol copolymer novolac type epoxy resins, naphthylene ether type epoxy resins, polyhydroxynaphthalene type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthene type epoxy resins, and alkoxy group-containing aromatic ring-modified novolac type epoxy resins (compounds in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked with formaldehyde) are particularly preferred because they yield cured products with excellent heat resistance.

[0018] The epoxy resin content in the thermosetting resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, with an upper limit of 100% by mass.

[0019] The maleimide resin can be one or more types, and examples include resins represented by any of the following structural formulas.

[0020] [ka]

[0021] [In formula (1), R 1 represents an α1-valent organic group, R 2 and R 3 Each of these independently represents 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, and a1 represents an integer of 1 or more.

[0022] [ka]

[0023] [In formula (2), R 4 , R 5 and R 6 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, L 1 and L 2 Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms, an aromatic hydrocarbon group with 6 to 10 carbon atoms, or a group with 6 to 15 carbon atoms that is a combination of a saturated hydrocarbon group and an aromatic hydrocarbon group. Each of a3, a4, and a5 independently represents an integer from 1 to 3, and n represents an integer from 0 to 10.

[0024] 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, preferably 99% by mass or less, and more preferably 98% by mass or less, in the nonvolatile content of the thermosetting composition.

[0025] The thermosetting agent (B) can be any compound that reacts with the thermosetting resin (A) upon heating to cure the thermosetting composition, and one or more types can be used. Examples include amine compounds, amide compounds, activated ester resins, acid anhydrides, phenol resins, cyanate ester resins, etc. In particular, it is preferable that the thermosetting agent (B) includes at least one selected from activated ester resins and phenol resins.

[0026] Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives.

[0027] Examples of the aforementioned amide compounds include dicyandiamide and polyamide resins synthesized from a linolenic acid dimer and ethylenediamine.

[0028] There are no particular restrictions on the activated ester resin, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred. The activated ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, activated ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and activated ester resins obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound are more preferred. 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 phenol compounds or naphthol compounds include hydroquinone, resorcinol, 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, phloroglucin, benzenetriol, and dicyclopentadiene-phenol addition resins.

[0029] Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0030] The phenol resins include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol addition resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenylol methane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyvalent phenolic hydroxyl group-containing compound in which the phenol nucleus is linked by a bismethylene group), naphthalene skeleton-containing phenol resin, and biphenyl-modified naphthol resin (a polyvalent naphthol in which the phenol nucleus is linked by a bismethylene group). Examples include polyvalent phenolic hydroxyl group-containing resins such as phenol compounds, aminotriazine-modified phenol resins (polyvalent phenolic hydroxyl group-containing compounds in which the phenol nucleus is linked with melamine, benzoguanamine, etc.), and alkoxy-group-containing aromatic ring-modified novolac resins (polyvalent phenolic hydroxyl group-containing compounds in which the phenol nucleus and alkoxy-group-containing aromatic ring are linked with formaldehyde), bisphenol compounds such as bisphenol A and bisphenol F, biphenyl compounds such as biphenyl and tetramethylbiphenyl; triphenylolle methane and tetraphenylolethane; dicyclopentadiene-phenol addition reaction type resins, and phosphorus-modified phenol compounds obtained by introducing phosphorus atoms into these various phenolic hydroxyl group-containing compounds.

[0031] The cyanate ester resin can be one or more types, for example, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin Examples include 180-type cyanate resins, triphenylmethane-type cyanate ester resins, tetraphenylethane-type cyanate ester resins, dicyclopentadiene-phenol addition reaction type cyanate ester resins, phenol aralkyl type cyanate ester resins, naphthol novolac type cyanate ester resins, naphthol aralkyl type cyanate ester resins, naphthol-phenol co-condensed novolac type cyanate ester resins, naphthol-cresol co-condensed novolac type cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac type cyanate ester resins, anthracene-type cyanate ester resins, and the like.

[0032] Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolac type cyanate ester resin are preferred for obtaining cured products with excellent heat resistance, while dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferred for obtaining cured products with excellent dielectric properties.

[0033] The thermosetting composition of the present invention may further contain a curing accelerator (B1). One or more curing accelerators (B1) can be used, and examples include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts, etc. Particularly when used as a semiconductor encapsulating material, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferred among tertiary amines, due to their excellent curability, heat resistance, electrical properties, and moisture resistance reliability.

[0034] The thermosetting composition of the present invention may further contain a maleimide compound (B2), provided that the maleimide compound (B2) is different from the maleimide resin. The maleimide compound (B2) can be one or more types, and examples include N-aliphatic maleimides such as N-cyclohexylmaleimide, N-methylmaleimide, Nn-butylmaleimide, N-hexylmaleimide, and N-tert-butylmaleimide; N-aromatic maleimides such as N-phenylmaleimide, N-(P-methylphenyl)maleimide, and N-benzylmaleimide; and bismaleimides such as 4,4'-diphenylmethanebismaleimide, 4,4'-diphenylsulfonebismaleimide, m-phenylenebismaleimide, bis(3-methyl-4-maleimoidphenyl)methane, bis(3-ethyl-4-maleimoidphenyl)methane, bis(3,5-dimethyl-4-maleimoidphenyl)methane, bis(3-ethyl-5-methyl-4-maleimoidphenyl)methane, and bis(3,5-diethyl-4-maleimoidphenyl)methane.

[0035] Among these, bismaleimides are preferred as the maleimide compound (B2) because they provide good heat resistance to the cured product, and 4,4'-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, and bis(3,5-diethyl-4-maleimidophenyl)methane are particularly preferred.

[0036] When using the maleimide compound (B2), it may optionally contain the amine compound, the phenol compound, the acid anhydride compound, the imidazole compound, the organometallic salt, etc.

[0037] The modified resin (C) is a urethane resin made from polyol (c1) and polyisocyanate (c2) as raw materials, with an isocyanate group content of 0 mol / kg.

[0038] Examples of polyols (c1) used in the production of the urethane resin include polyester polyols, polyether polyols, and polycarbonate polyols. Among these, it is preferable to include polyester polyols and / or polycarbonate polyols because they provide even better copper foil adhesion and heat resistance.

[0039] The aforementioned polyester polyol can be one or more types, and examples include polyester polyols obtained by reacting a polyol with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; and polyester polyols obtained by copolymerizing these.

[0040] One or more types of polyols can be used in the production of the polyester polyol, 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 Examples include aliphatic polyols such as pandiol, 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, and pentaerythritol; polyols having an alicyclic structure such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and their alkylene oxide adducts; polyols having an aromatic structure such as bisphenol A and bisphenol F; and polyols obtained by modifying the aforementioned aromatic polyols with alkylene oxides. Among these, it is preferable to include the aliphatic polyols in order to obtain even better copper foil adhesion and heat resistance.

[0041] The molecular weight of the polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, and even more preferably 700 or less. In this specification, the number-average molecular weight is the value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0042] Examples of alkylene oxides used to modify the polyol having the aromatic structure include alkylene oxides having 2 to 4 carbon atoms (preferably 2 to 3), such as ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is preferably 2 moles or more, more preferably 4 moles or more, preferably 20 moles or less, and more preferably 16 moles or less, per mole of the polyol having the aromatic structure.

[0043] The polycarboxylic acid can be one or more types, and examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; and their anhydrides or esterified products.

[0044] The content ratio (polyol / polycarboxylic acid) of the polyol used in the production of the polyester polyol is preferably 20 / 80 or more, more preferably 30 / 70 or more, even more preferably 40 / 60 or more, preferably 99 / 1 or less, more preferably 90 / 10 or less, and even more preferably 85 / 15 or less, on a mass basis.

[0045] The cyclic ester compound can be one or more types, such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, 3-penten-4-olide, 12-dodecanolide, and γ-dodecanolactone.

[0046] 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, preferably 250°C or lower, and more preferably 240°C or lower. The reaction time is preferably 1 hour or more and 100 hours or less.

[0047] A catalyst may be present during the above reaction. One or more catalysts can be used, and examples include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid. The amount of the catalyst is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, preferably 0.01 parts by mass or less, and more preferably 0.005 parts by mass or less, based on 100 parts by mass of the total of the polyol and the polycarboxylic acid.

[0048] Examples of the aforementioned polyether polyol include those obtained by addition polymerization (ring-opening polymerization) of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as initiators.

[0049] Examples of the initiators include linear diols such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; branched 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 hemimeric acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; and 1,2,3-propanetrithiol.

[0050] Examples of the alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

[0051] Examples of the polycarbonate polyol include reaction products of carbonate esters and polyols, and reaction products of phosgene and bisphenol A, etc.

[0052] Examples of the aforementioned carbonate esters include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate.

[0053] Examples of polyols that can react with the carbonate ester include the polyols exemplified in the production of the polyester polyol mentioned above; high molecular weight polyols (number average molecular weight of 500 to 5,000) such as polyether polyols (polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.).

[0054] 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, preferably 20,000 or less, and more preferably 15,000 or less.

[0055] The polyisocyanate (c2) can be one or more types, and examples include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and polyisocyanates containing alicyclic structures such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.

[0056] The hydroxyl value of the urethane resin in 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.

[0057] The number of hydroxyl groups contained in the urethane resin of the modified resin (C) is preferably 1 or more per molecule, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and particularly preferably 2.

[0058] The equivalent ratio of the hydroxyl group of the polyol (c1) used in the production of the urethane resin to the isocyanate group of the polyisocyanate (c2) [isocyanate group / hydroxyl group] is preferably 0.1 or more, more preferably 0.2 or more, and preferably 0.95 or less, more preferably 0.9 or less on a molar basis.

[0059] The modified resin (C) may contain other additives as required.

[0060] Examples of the other additives include curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, thermoplastic resins, etc. These additives may be used alone or in combination of two or more.

[0061] 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 11.7 (cal / cm 3 ) 0.5 or less.

[0062] The difference in solubility parameters 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 / cm³). 3 ) 0.5 The above is more than -1.5 (cal / cm 3 ) 0.5 More preferably -1 (cal / cm²) 3 ) 0.5 More preferably, 0 (cal / cm²) 3 ) 0.5 The above is particularly preferably 0.2 (cal / cm³). 3 ) 0.5 The above is preferable, preferably 2 (cal / cm²). 3 ) 0.5 More preferably 1.5 (cal / cm 3 ) 0.5 More preferably, 0.8 (cal / cm³) 3 ) 0.5 The following is the case: If the difference in solubility parameters between the cured product and the modified resin (C) is within an appropriate range, they can be miscible before thermal curing. However, as thermal curing occurs (i.e., the reaction between the thermosetting resin (A) and the thermosetting agent (B)), the miscibility between the mixture (including the reaction process) and the modified resin (C) decreases, and after thermal curing, it is possible to separate the reaction products of the thermosetting resin (A) and the thermosetting agent (B) from the modified resin (C).

[0063] The solubility parameter of the cured product can be determined by calculating the solubility parameter of each compound contained in the cured product of the mixture of curable resin (A) and thermosetting agent (B) based on Fedors' method (Polymer Engineering and Science, 1974, vol. 14, No. 2), and then calculating the weighted average value based on the mass-based ratio of each compound. Furthermore, the solubility parameter of the modified resin (C) can be determined by calculating the solubility parameter of the units derived from each compound used as a raw material for the modified resin (C), based on Fedors' method, and then calculating the weighted average value based on the mass-based ratio of the units derived from each compound.

[0064] 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 40°C or lower, and more preferably 30°C or lower.

[0065] 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, and even more preferably 50,000 or less. The number-average molecular weight of the modified resin (C) is the value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0066] Preferably, the thermosetting composition is in a miscible state before the thermosetting reaction, but after the thermosetting reaction, the thermosetting resin (A) and the modified resin (C) undergo phase separation. 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 separation 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. Because the modified resin (C) is in a miscible state before the thermosetting reaction, it is possible to uniformly disperse the modified resin (C) in the mixture of thermosetting resin (A) and thermosetting agent (B). On the other hand, because the reaction products of thermosetting resin (A) and thermosetting agent (B) and the modified resin (C) undergo phase separation after the thermosetting reaction, it is possible to maintain the chemical and mechanical properties of the modified resin (C) itself. Therefore, in the resulting cured product, it is possible to uniformly disperse the domains of the modified resin (C) in the reaction products of thermosetting resin (A) and thermosetting agent (B), and it is thought that this will provide a cured product that has both superior heat resistance and copper foil adhesion.

[0067] The presence or absence of phase separation in the cured material can be confirmed by the presence or absence of cloudiness in the cured material, or by the presence of a sea area and an island area when observing the fracture surface of the cured material using an atomic force microscope (AFM).

[0068] 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, even more preferably 1 part by mass or more, preferably 60 parts by mass or less, and more preferably 45 parts by mass or less, per 100 parts by mass of the thermosetting resin (A). It may also be 35 parts by mass or less, even more preferably 15 parts by mass or less, and particularly 10 parts by mass or less.

[0069] The thermosetting composition of the present invention may further contain an inorganic filler (D). Including the inorganic filler (D) can further reduce the thermal expansion coefficient of the insulating layer. One or more types of inorganic fillers can be used, and examples include 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. Silica is preferred, and fused silica is more preferred. The shape of the silica may be either crushed or spherical, but from the viewpoint of suppressing the melt viscosity of the thermosetting composition while increasing the amount of silica added, it is preferable to be spherical. In particular, when the thermosetting composition of the present invention is used as 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.

[0070] 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, even more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less. Increasing the content of the inorganic filler makes it easy to improve flame retardancy, moisture and heat resistance, solder crack resistance, and thermal expansion coefficient.

[0071] The thermosetting composition of the present invention may further contain a flame retardant (E). Preferably, the flame retardant (E) is a non-halogen type that is substantially free of halogen atoms. One or more types of flame retardants (E) can be used, and examples include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, and the like.

[0072] The phosphorus-based flame retardant can be one or more types, and examples include inorganic nitrogen-containing phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, polyammonium phosphate, and other ammonium phosphates, and inorganic nitrogen-containing phosphorus compounds such as phosphate amides; general-purpose organophosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and organic nitrogen-containing phosphorus compounds; as well as cyclic organophosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene=10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene=10-oxide, and 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene=10-oxide, and derivatives obtained by reacting these with compounds such as epoxy resins and phenolic resins.

[0073] When using the aforementioned phosphorus-based flame retardant, hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc., may be used in combination with the phosphorus-based flame retardant.

[0074] The red phosphorus is preferably surface-treated. Examples of surface treatment methods include (i) coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin such as phenolic resin; and (iii) double coating with a thermosetting resin such as phenolic resin on top of a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide.

[0075] Examples of nitrogen-based flame retardants include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine compounds, with triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds being preferred. When using the nitrogen-based flame retardant, metal hydroxides, molybdenum compounds, etc., may be used in combination.

[0076] Examples of the aforementioned triazine compounds include melamine, acetoganamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine, etc., as well as (i) sulfate aminotriazine compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate; (ii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoganamine, and formuanamine and formaldehyde; (iii) mixtures of the co-condensate of (ii) with phenol resins such as phenolformaldehyde condensates; and (iv) the above (ii) and (iii) further modified with tung oil, isomerized linseed oil, etc.

[0077] Specific examples of the cyanuric acid compounds mentioned above include, for example, cyanuric acid and melamine cyanurate.

[0078] The amount of nitrogen-based flame retardant to be blended is appropriately selected depending on the type of nitrogen-based flame retardant, the other components of the thermosetting composition, and the desired degree of flame retardancy. For example, it is preferable to blend it in the range of 0.05 to 10 parts by mass, and particularly preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of the thermosetting composition containing the epoxy resin, curing agent, non-halogen-based flame retardant, and other fillers and additives.

[0079] The aforementioned silicone-based flame retardant can be any organic compound containing silicon atoms, and examples include silicone oil, silicone rubber, and silicone resin.

[0080] The inorganic flame retardant can be one or more types, for example: metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide; metal oxides such as 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, and tungsten oxide; zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, and carbonic acid. Examples include metal carbonate compounds such as aluminum, 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; and low-melting-point glasses such as Sheeplee (Voxui-Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3 system, ZnO-P2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-OF system, PbO-V2O5-TeO2 system, Al2O3-H2O system, and lead borosilicate system.

[0081] Examples of the organometallic salt-based flame retardants include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, and compounds in which a metal atom is ionically bonded or coordinately bonded to an aromatic compound or heterocyclic compound.

[0082] The thermosetting composition of the present invention may further contain an organic solvent (F). The inclusion of the organic solvent (F) in the thermosetting composition can reduce its viscosity, making it particularly suitable for the manufacture of printed circuit boards.

[0083] As the organic solvent (F), one or more types can be used, and examples 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, ethyl diglycol acetate, and carbitol acetate; carbitol solvents such as cellosolve, methyl cellosolve, and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0084] In particular, when the thermosetting composition of the present invention is used for printed circuit boards, the organic solvent (F) is preferably a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; an ether solvent such as propylene glycol monomethyl ether; an acetate ester solvent such as propylene glycol monomethyl ether acetate or ethyl diglycol acetate; a carbitol solvent such as methyl cellosolve; or an amide solvent such as dimethylformamide.

[0085] Furthermore, when the thermosetting composition of the present invention is used in a build-up film, the organic solvent (F) is preferably a ketone solvent such as acetone, methyl ethyl ketone, or cyclohexanone; an acetate ester solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, or carbitol acetate; a carbitol solvent such as cellosolve or butyl carbitol; an aromatic hydrocarbon solvent such as toluene or xylene; or an amide solvent such as dimethylformamide, dimethylacetamide, or N-methylpyrrolidone.

[0086] If an organic solvent (F) is included, its content is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less in the thermosetting composition.

[0087] The thermosetting composition of the present invention may further contain conductive particles. The inclusion of conductive particles allows it to be used as a conductive paste, making it suitable for anisotropic conductive materials.

[0088] The thermosetting composition of the present invention may further contain rubber, fillers, etc. The inclusion of rubber, fillers, etc. makes it suitable for build-up films.

[0089] The thermosetting composition of the present invention may further contain various additives such as silane coupling agents, release agents, pigments, and emulsifiers.

[0090] The thermosetting composition of the present invention can be obtained by mixing the above components and can be cured by thermosetting. Examples of the shape of the cured product include laminates, cast products, adhesive layers, coatings, films, etc.

[0091] Applications of the thermosetting composition of the present invention include semiconductor encapsulating materials, printed circuit board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, and build-up adhesive films. Among these applications, in the case of insulating materials for printed circuit boards and electronic circuit boards, and build-up adhesive films, it can be used as an insulating material for so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Among these, its use in printed circuit board materials and build-up adhesive films is preferable due to its high heat resistance and solvent solubility.

[0092] A method for preparing a semiconductor encapsulating material from the thermosetting composition of the present invention involves thoroughly melting and mixing the thermosetting resin (A), thermosetting agent (B), and modified resin (C), along with any other components used as needed, until uniform, using an extruder, needle, roll, or the like as necessary.

[0093] When the thermosetting composition of the present invention is used as a semiconductor encapsulation material, a semiconductor package can be formed. Specifically, the composition can be molded using a casting, transfer molding machine, injection molding machine, etc., and then heated at 50 to 200°C for 2 to 10 hours to obtain a molded semiconductor device.

[0094] Furthermore, a method for manufacturing a printed circuit board using the thermosetting composition of the present invention involves impregnating a reinforcing substrate with the curable composition, layering copper foil on top, and then heating and pressing the substrate together. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, first, the thermosetting composition can be heated (preferably to 50-170°C depending on the type of organic solvent (F)) to obtain a cured prepreg. The resin content in the prepreg is preferably 20% by mass or more and 60% by mass or less. Next, the prepregs are laminated, copper foil is layered on top, and then heated and pressed together at 170-300°C under a pressure of 1-10 MPa for 10 minutes to 3 hours to obtain the desired printed circuit board.

[0095] When the thermosetting composition of the present invention is used as a conductive paste, examples include dispersing conductive particles (fine conductive particles) in the thermosetting composition to create a composition for an anisotropic conductive film, or creating a paste resin composition for circuit connection or an anisotropic conductive adhesive that is liquid at room temperature.

[0096] As a method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting product of the present invention, for example, the thermosetting composition is applied to a wiring board with a circuit formed on it using a spray coating method, a curtain coating method, etc., and then cured. After that, holes such as predetermined through-holes are drilled as needed, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and then plated with a metal such as copper. Electroless plating and electrolytic plating are preferred as the plating method, and examples of roughening agents include oxidizing agents, alkalis, and organic solvents. By sequentially repeating these operations as desired, a build-up substrate can be obtained by alternately building up a resin insulating layer and a conductor layer of a predetermined circuit pattern. However, the drilling of through-holes is performed after the formation of the outermost resin insulating layer. Alternatively, a resin-coated copper foil, on which the thermosetting composition has been partially cured, can be heated and pressed onto a wiring board with a circuit formed on it at 170-300°C to form a roughened surface, thus eliminating the plating process and allowing for the production of a build-up substrate.

[0097] A method for producing a build-up film from the thermosetting composition of the present invention includes, for example, a method of applying the thermosetting composition of the present invention onto a support film to form a resin composition layer and thereby producing a build-up film for a multilayer printed circuit board.

[0098] When the thermosetting composition of the present invention is used in a build-up film, it is essential that the film softens under the lamination temperature conditions in the vacuum lamination method (usually 70°C to 140°C) and exhibits fluidity (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to formulate the above components in such a way as to exhibit these characteristics.

[0099] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0100] The adhesive film described above can be manufactured by first preparing a varnish-like thermosetting composition of the present invention, then applying this varnish-like composition to the surface of a support film (Y), and finally drying the organic solvent by heating or blowing hot air to form a layer (X) of the thermosetting composition.

[0101] The thickness of the formed layer (X) is usually greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, it is preferable that the thickness of the resin composition layer be 10 to 100 μm.

[0102] Furthermore, layer (X) in the present invention may be protected by a protective film, as described later. By protecting it with a protective film, it is possible to prevent dirt and other debris from adhering to the surface of the resin composition layer and to prevent scratches.

[0103] The aforementioned support film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0104] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0105] The support film (Y) described above is peeled off after lamination to the circuit board or after an insulating layer is formed by heat curing. Peeling off the support film (Y) after heat curing the adhesive film prevents the adhesion of dust and other debris during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0106] Next, a method for manufacturing a multilayer printed circuit board using the adhesive film obtained as described above involves, for example, if layer (X) is protected by a protective film, peeling it off, and then laminating layer (X) to one or both sides of the circuit board, for example, by vacuum lamination, so that it is in direct contact with the circuit board. The lamination method may be batch or continuous on a roll. The adhesive film and the circuit board may also be heated (preheated) before lamination as necessary.

[0107] The lamination conditions are preferably a bonding temperature (lamination temperature) of 70 to 140°C and a bonding pressure of preferably 1 to 11 kgf / cm². 2 (9.8 × 10⁴ ~ 10⁷.9 × 10⁴ N / m 2 It is preferable to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0108] The method for obtaining the cured product of the present invention can be based on general curing methods for thermosetting compositions. For example, the heating temperature conditions can be appropriately selected depending on the type and application of the curing agent used. The composition obtained by the above method should be heated in a temperature range of approximately 20 to 300°C. [Examples]

[0109] The present invention will be described in more detail below with reference to examples.

[0110] [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 apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.03 parts by mass of TiPT were 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.

[0111] [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 charged into the reaction apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.03 parts by mass of TiPT were 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.

[0112] [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 apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.03 parts by mass of TiPT were 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.

[0113] [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 apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.1 parts by mass of TiPT were added, and a condensation reaction 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.

[0114] [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 apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.03 parts by mass of TiPT were 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.

[0115] [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 apparatus, and heating and stirring were started. Next, after raising the internal temperature to 220°C, 0.03 parts by mass of TiPT were 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.

[0116] [Synthesis Example 7] Synthesis of Urethane Resin 1 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 28.6 parts by mass of 4,4'-diphenylmethane diisocyanate (trademark; manufactured by Tosoh Corporation, "Millionate MT", hereinafter abbreviated as MDI) were charged in. Then, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 1(C1). 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 -50°C.

[0117] [Synthesis Example 8] Synthesis of Urethane Resin 2 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 10.7 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and 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.

[0118] [Synthesis Example 9] Synthesis of Urethane Resin 3 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 32.1 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 3(C3). The obtained urethane resin had a hydroxyl value of 11.2, a number-average molecular weight of 70,000, and a glass transition temperature of -49°C.

[0119] [Synthesis Example 10] Synthesis of Urethane Resin 4 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 21.5 parts by mass of 1,3-xylylene diisocyanate (trademark; manufactured by Mitsui Chemicals, Inc., "Takenate 500") were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 10 hours to synthesize urethane resin 4(C4). 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 -53°C.

[0120] [Synthesis Example 11] Synthesis of Urethane Resin 5 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 19.2 parts by mass of hexamethylene diisocyanate (trademark; manufactured by Tosoh Corporation, 'HDI') were charged in. Next, the internal temperature was raised to 120°C, and the reaction was continued for 10 hours to synthesize urethane resin 5(C5). 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.

[0121] [Synthesis Example 12] Synthesis of Urethane Resin 6 1,000 parts by mass of PEs1 obtained in Synthesis Example 1 were added to the reaction apparatus, and 19.9 parts by mass of tolylene diisocyanate (trademark; manufactured by Mitsui Chemicals, Inc., "Cosmonate T-80") were charged in. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 6(C6). 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.

[0122] [Synthesis Example 13] Synthesis of Urethane Resin 7 1,000 parts by mass of PEs2 obtained in Synthesis Example 2 were added to the reaction apparatus, and 36.4 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and 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.

[0123] [Synthesis Example 14] Synthesis of Urethane Resin 8 1,000 parts by mass of PEs3 obtained in Synthesis Example 3 were added to the reaction apparatus, and 106.3 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 8(C8). The obtained urethane resin had a hydroxyl value of 8.0, a number-average molecular weight of 14,000, and a glass transition temperature of -46°C.

[0124] [Synthesis Example 15] Synthesis of Urethane Resin 9 1,000 parts by mass of PEs4 obtained in Synthesis Example 4 were added to the reaction apparatus, and 106.3 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 9(C9). The obtained urethane resin had a hydroxyl value of 8.0, a number-average molecular weight of 14,000, and a glass transition temperature of -7°C.

[0125] [Synthesis Example 16] Synthesis of urethane resin 10 1,000 parts by mass of PEs5 obtained in Synthesis Example 5 were added to the reaction apparatus, and 151.4 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and 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.

[0126] [Synthesis Example 17] Synthesis of urethane resin 11 1,000 parts by mass of PEs5 obtained in Synthesis Example 5 were added to the reaction apparatus, and 222.6 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 11(C11). The obtained urethane resin had a hydroxyl value of 9.4, a number-average molecular weight of 12,000, and a glass transition temperature of -29°C.

[0127] [Synthesis Example 18] Synthesis of urethane resin 12 1,000 parts by mass of PEs6 obtained in Synthesis Example 6 were added to the reaction apparatus, and 59.5 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 12(C12). The obtained urethane resin had a hydroxyl value of 28.1, a number-average molecular weight of 4,000, and a glass transition temperature of -41°C.

[0128] [Synthesis Example 19] Synthesis of urethane resin 13 1,000 parts by mass of PEs6 obtained in Synthesis Example 6 were added to the reaction apparatus, and 106.3 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 13(C13). The obtained urethane resin had a hydroxyl value of 8.0, a number-average molecular weight of 14,000, and a glass transition temperature of -36°C.

[0129] [Synthesis Example 20] Synthesis of urethane resin 14 1,000 parts by mass of a polycarbonate polyol (trademark; manufactured by Asahi Kasei Corporation, "Duranol T5652", number average molecular weight 2000) produced from 1,5-pentanediol and 1,6-hexanediol was added to the reaction apparatus, and 93.8 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 14(C14). 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.

[0130] [Synthesis Example 21] Synthesis of urethane resin 15 1,000 parts by mass of a polycarbonate polyol (trademark; manufactured by Asahi Kasei Corporation, "Duranol T5651", number average molecular weight 1,000) produced from 1,5-pentanediol and 1,6-hexanediol was added to the reaction apparatus, and 200 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and 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.

[0131] [Synthesis Example 22] Synthesis of urethane resin 16 1,000 parts by mass of a polycarbonate polyol (trademark; manufactured by Asahi Kasei Corporation, "Duranol G3450J", number average molecular weight 800) produced from 1,3-propanediol and 1,4-butanediol was added to the reaction apparatus, and 250 parts by mass of MDI were charged. Next, the internal temperature was raised to 120°C, and the reaction was continued for 5 hours to synthesize urethane resin 16(C16). The obtained urethane resin had a hydroxyl value of 22.4, a number-average molecular weight of 5,000, and a glass transition temperature of -9°C.

[0132] [Example 1] In a mixing container, 61.5 parts by mass of polyhydroxynaphthalene type epoxy resin (trademark; manufactured by DIC Corporation, "EPICLON HP-4700," abbreviated as "A1" in the table) was added as the epoxy resin, 38.5 parts by mass of novolac type phenol resin (trademark; manufactured by DIC Corporation, "PHENOLITE TD-2131," abbreviated as "B1" in the table) was added as the curing agent, and 10 parts by mass of urethane resin 1 (C1) obtained in Synthesis Example 7 was added, and the mixture was stirred at an internal temperature of 130°C until it became miscible. 0.3 parts by mass of 2-ethyl-4-methylimidazole was added as a curing accelerator, and after stirring for 20 seconds, the mixture was degassed under vacuum to obtain the thermosetting composition of the present invention.

[0133] [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 urethane resin 1(C1) were used, respectively.

[0134] [Examples 4-15] 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 urethane resin 1 (C1).

[0135] [Examples 16-18] A thermosetting composition was obtained in the same manner as in Example 1, except that instead of incorporating 10 parts by mass of urethane resin 1 (C1), 5 parts by mass of each of the urethane resins (C14 to C16) listed in the table were incorporated.

[0136] [Example 19] In a mixing container, 85.4 parts by mass (42.7 parts by mass) of a 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as the epoxy resin, 88.2 parts by mass (65% toluene solution, 57.3 parts by mass) of active ester resin (trademark; manufactured by DIC Corporation, "EPICLON HPC-8000-65T", abbreviated as "B2" in the table) as the curing agent, and 5 parts by mass of urethane resin 1 (C1) obtained in Synthesis Example 7 were mixed and stirred at an internal temperature of 130°C while removing the solvent under reduced pressure until the mixture became miscible. 0.5 parts by mass of 4-dimethylaminopyridine was added as a curing accelerator, and after stirring for 20 seconds, the mixture was degassed under vacuum to obtain the thermosetting composition of the present invention.

[0137] [Comparative Example 1] In a mixing container, 61.5 parts by mass of polyhydroxynaphthalene type epoxy resin A1 was added as the epoxy resin, and 38.5 parts by mass of novolac type phenol resin B1 was added as the curing agent. The mixture was stirred at an internal temperature of 130°C until it became miscible. 0.3 parts by mass of 2-ethyl-4-methylimidazole was added as a curing accelerator, and after stirring for 20 seconds, the mixture was degassed under vacuum to obtain the thermosetting composition of the present invention.

[0138] [Comparative Example 2] In a mixing container, 85.4 parts by mass (42.7 parts by mass) of a 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as the epoxy resin and 88.2 parts by mass (65% toluene solution, 57.3 parts by mass) of active ester resin B2 as the curing agent were mixed and stirred at an internal temperature of 130°C while removing the solvent under reduced pressure until the mixture became miscible. 0.5 parts by mass of 4-dimethylaminopyridine was added as a curing accelerator, and after stirring for 20 seconds, the mixture was degassed under vacuum to obtain the thermosetting composition of the present invention.

[0139] The obtained thermosetting compositions were evaluated as follows. The results, along with the solubility parameters of the modified resin (C) used in each thermosetting composition, are shown in the table.

[0140] [Method for evaluating copper foil adhesion] The thermosetting compositions obtained in the examples and comparative examples were poured at 130°C into a casting plate in which a 1 mm thick rubber spacer was sandwiched between glass plates with copper foil on one side, and then heat-cured at 175°C for 5 hours. The resulting cured material was cut to a size of 10 mm wide x 60 mm long, and the 90° peel strength (N / cm) was measured using a peel tester. Measuring instrument: Shimadzu Autograph (manufactured by Shimadzu Corporation) Model:AG-1 Test speed: 50 mm / m

[0141] [Method for evaluating heat resistance] Heat resistance was evaluated by the glass transition temperature. Specifically, the thermosetting compositions obtained in the examples and comparative examples were poured at 130°C into a casting plate with a 1 mm thick rubber spacer sandwiched between glass plates, and then heat-cured at 175°C for 5 hours. The resulting cured material was cut to a size of 10 mm wide x 55 mm long, and the storage modulus (E') and loss modulus (E") were measured under the following conditions. When E' / E'' is taken as tanδ, the temperature at which tanδ is maximum was defined as the glass transition temperature (unit: °C) and measured. The Tg of the thermosetting compositions obtained in the examples and comparative examples was defined as glass transition temperature evaluation 1, and the difference between the Tg of the epoxy resin compositions obtained in the examples and comparative examples and the Tg of the epoxy resin composition without modified resin was defined as glass transition temperature evaluation 2. Measuring instrument: Dynamic viscoelasticity measuring instrument (manufactured by SII Nanotechnology Co., Ltd.) Model:DMA6100 Measurement temperature range: 0℃ to 300℃ Heating rate: 5°C / min Frequency: 1Hz Measurement mode: Tensile

[0142] [Table 1]

[0143] [Table 2]

[0144] [Table 3]

[0145] Examples 1 to 19, which are thermosetting compositions of the present invention, exhibited excellent heat resistance and copper foil adhesion in the resulting cured products. On the other hand, Comparative Examples 1 and 2, which did not contain modified resin (C), exhibited inferior copper foil adhesion.

Claims

1. 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 having an isocyanate group content of 0 mol / kg, made from a polyol (c1) which is a polyester polyol and / or a polycarbonate polyol and a polyisocyanate (c2) as raw materials. The glass transition temperature of the modified resin (C) is -100°C or higher and 50°C or lower. 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 per 100 parts by mass of the thermosetting resin (A).

2. The thermosetting resin (A) comprises at least an epoxy resin, The thermosetting composition according to claim 1, wherein the epoxy resin is a polyhydroxynaphthalene type epoxy resin and / or a naphthylene ether type epoxy resin.

3. The thermosetting composition according to claim 1, wherein the polyester polyol contains an aliphatic glycol as a raw material.

4. The solubility parameter of the modified resin (C) is 9.7 (cal / cm³). ３ ) ０．５ More than 12.0 (cal / cm ３ ) ０．５ The thermosetting composition according to claim 1, which is as follows:

5. The thermosetting composition according to claim 1, wherein the glass transition temperature of the cured product of the thermosetting composition is 180°C or higher.

6. A cured product characterized by being formed by the thermosetting composition described in claim 1.

7. A semiconductor encapsulation material characterized by being formed from the thermosetting composition described in claim 1.

8. A prepreg characterized by being a semi-cured product of an impregnated substrate having the thermosetting composition described in claim 1 and a reinforcing substrate.

9. A circuit board characterized by comprising a plate-shaped excipient of the thermosetting composition described in claim 1 and copper foil.

10. A build-up film characterized by comprising a cured product of the thermosetting composition described in claim 1 and a base film.

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