CN116003959A

CN116003959A - Thermosetting composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and build-up film

Info

Publication number: CN116003959A
Application number: CN202211258949.2A
Authority: CN
Inventors: 二宫淳; 三轮広治; 泷川优子
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2021-10-21
Filing date: 2022-10-14
Publication date: 2023-04-25
Also published as: JP2023062672A; TW202319459A; KR20230057954A

Abstract

The invention provides a thermosetting composition, a cured product thereof, a semiconductor sealing material, a prepreg, a circuit board and a build-up film, which can achieve both excellent copper foil adhesion and heat resistance. The present invention provides a thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), wherein the modified resin (C) is a urethane resin having an isocyanate group content of 0mol/kg and containing a polyol (C1) and a polyisocyanate (C2) as raw materials, the modified resin (C) has a glass transition temperature of-100 ℃ to 50 ℃, the modified resin (C) has a number average molecular weight of 4,000 to 100,000, and the modified resin (C) has a content of 0.1 parts by mass to 60 parts by mass based on 100 parts by mass of the thermosetting resin (A).

Description

Thermosetting composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and build-up film

Technical Field

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.

Background

In recent years, demands for miniaturization, weight saving, and high speed of electronic devices have been increasing, and the density of printed wiring boards has been increasing. Therefore, further reduction in wiring width and wiring interval is required, and in order to keep the wiring width small, the metal layer (metal film) forming the wiring and the resin base material are required to have sufficient adhesion.

However, in the conventional printed wiring boards, adhesion between the metal layer and the resin is mainly dependent on an anchor effect due to the roughness of the roughened metal foil, the surface roughness obtained by physical roughening such as plasma treatment or chemical roughening such as permanganic acid etching on the resin surface, and when the printed wiring boards are used for high-frequency applications such as large-scale servers and antennas, the adhesion is required to be improved without depending on the anchor effect because the high-frequency signals are processed to cause signal attenuation (transmission loss).

In order to improve adhesion, thermosetting compositions containing polyester additives have been proposed (for example, see patent document 1 and patent document 2).

[ Prior Art literature ]

[ patent literature ]

Patent document 1: international publication No. 19/131413

Patent document 2: japanese patent laid-open No. 2021-107493

Disclosure of Invention

[ problem to be solved by the invention ]

The invention provides a thermosetting composition which can achieve both excellent copper foil adhesion and heat resistance.

[ means of solving the problems ]

The present invention provides a thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), wherein the modified resin (C) is a urethane resin containing 0mol/kg of isocyanate groups and starting from a polyol (C1) and a polyisocyanate (C2), the modified resin (C) has a glass transition temperature of-100 ℃ to 50 ℃, the modified resin (C) has a number average molecular weight of 4,000 to 100,000, and the modified resin (C) has a content of 0.1 parts by mass to 60 parts by mass based on 100 parts by mass of the thermosetting resin (A).

The present invention also provides a cured product, a semiconductor sealing material, a prepreg, a circuit board, and a build-up film, each of which is characterized by being formed from the thermosetting composition.

[ Effect of the invention ]

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

Detailed Description

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

The glass transition temperature (intermediate point glass transition temperature (Tmg)) of the thermosetting composition is preferably 180 ℃ or higher, more preferably 190 ℃ or higher, still more preferably 200 ℃ or higher, and the upper limit is 400 ℃. In the present specification, a method for measuring the glass transition temperature is described in examples described below.

Further, as the modified resin (C) in the present invention, there is a general concern that the heat resistance will be greatly reduced when a urethane resin is added, but in the present invention, excellent copper foil adhesion and heat resistance can be simultaneously achieved by adding a specific urethane resin.

The glass transition temperature (intermediate point glass transition temperature (Tmg)) of the thermosetting composition in a state where the modified resin (C) is not added is preferably 180 ℃ or higher, more preferably 190 ℃ or higher, still more preferably 200 ℃ or higher, and the upper limit is 400 ℃.

The difference between the glass transition temperature of the thermosetting composition and the glass transition temperature of the thermosetting composition in the state where the modified resin (C) is not added (the glass transition temperature of the thermosetting composition—the glass transition temperature of the thermosetting composition in the state where the modified resin (C) is not added) is preferably-30 ℃ or higher, more preferably-20 ℃ or higher, still more preferably-10 ℃ or higher, and the upper limit is 30 ℃.

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

As the epoxy resin, one or two or more kinds may be used, and examples thereof include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, diglycidyl naphthalene compound (1, 6-diglycidyl naphthalene, 2, 7-diglycidyl naphthalene, etc.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, naphthylene ether type epoxy resin, polyhydroxy naphthalene type epoxy resin such as 1, 1-bis (2, 7-diglycidyl oxy-1-naphthyl) alkane, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl novolac type epoxy resin, phosphorus modified epoxy resin having phosphorus atoms introduced into the various epoxy resins, etc.

Among them, in terms of obtaining a cured product excellent in heat resistance, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl novolak type epoxy resin, or naphthol novolak type epoxy resin containing a naphthalene skeleton, naphthol aralkyl type epoxy resin, naphthol-phenol novolak type epoxy resin, naphthol-cresol novolak type epoxy resin are particularly preferable; a naphthylene ether type epoxy resin, a polyhydroxynaphthalene type epoxy resin, or a crystalline biphenyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, a xanthene type epoxy resin, or an alkoxy group-containing aromatic ring-modified novolak type epoxy resin (a compound obtained by linking a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring with formaldehyde), and the like.

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

One or two or more types of maleimide resins may be used, and examples thereof include resins represented by any of the following structural formulas.

[ chemical 1]

[ in formula (1), R ¹ An organic group having a1 valence, R ² R is R ³ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a1 represents an integer of 1 or more]

[ chemical 2]

[ in formula (2), R ⁴ 、R ⁵ R is R ⁶ Independently represent 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 L and L ² Each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination of a saturated hydrocarbon group and an aromatic hydrocarbon groupA group having 6 to 15 carbon atoms. 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) in the nonvolatile component of the thermosetting composition is preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and preferably 99 mass% or less, more preferably 98 mass% or less.

The thermosetting agent (B) may be any compound that can harden the thermosetting composition by reacting with the thermosetting resin (a) by heating, and one or two or more kinds of compounds can be used, and examples thereof include: amine compounds, amide compounds, active ester resins, acid anhydrides, phenol resins, cyanate resins, and the like. Among them, the thermosetting agent (B) preferably contains at least one selected from the group consisting of an active ester resin and a phenol resin.

The amine compounds include: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ Amine complexes, guanidine derivatives, etc.

The amide compounds include: dicyandiamide, polyamide resins synthesized from dimers of linolenic acid and ethylenediamine, and the like.

The active ester resin is not particularly limited, and compounds having two or more ester groups having high reactivity in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, can be generally preferably used. The active ester resin is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxyl compound is preferable, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and/or a naphthol compound is 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, and the like, or halides thereof. Examples of the phenol compound or the naphthol compound 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, phloroglucinol, dicyclopentadiene-phenol addition resins, and the like.

The acid anhydride may be exemplified by: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

The phenol resins include: phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins (zelock resins), naphthol aralkyl resins, triphenolmethane resins, tetraphenolethane resins, naphthol novolac resins, naphthol-phenol copoly novolac resins, naphthol-cresol copoly novolac resins, biphenyl modified phenol resins (polyhydric phenol hydroxyl group-containing compounds having a phenol nucleus linked by a dimethylene group), phenol resins having a naphthalene skeleton, biphenyl modified naphthol resins (polyhydric naphthol compounds having a phenol nucleus linked by a dimethylene group), aminotriazine modified phenol resins (polyhydric phenol hydroxyl group-containing compounds having a phenol nucleus linked by a melamine, benzoguanamine or the like), or alkoxy group-containing aromatic ring modified novolac resins (polyhydric phenol hydroxyl group-containing compounds having a phenol nucleus linked by an alkoxy group-containing aromatic ring) or the like, bisphenol compounds such as bisphenol a, bisphenol compounds such as bisphenol F, biphenyl, tetramethylbiphenyl or the like; trisphenol methane, tetraphenol ethane; dicyclopentadiene-phenol addition reaction type resins, phosphorus-modified phenol compounds in which a phosphorus atom is introduced into the various phenolic hydroxyl group-containing compounds, and the like.

As the cyanate resin, one or two or more kinds may be used, and examples thereof include: bisphenol a type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol thioether type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolak type cyanate resin, cresol novolak type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol novolak type cyanate resin, naphthol aralkyl type cyanate resin, naphthol-phenol novolak type cyanate resin, naphthol-cresol novolak type cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate resin, biphenyl modified novolak type cyanate resin, anthracene type cyanate resin, and the like.

Among the above-mentioned cyanate resins, bisphenol a type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, polyhydroxynaphthalene type cyanate resin, naphthylene ether type cyanate resin, and novolak type cyanate resin are preferable in particular from the viewpoint of obtaining a cured product excellent in heat resistance, and dicyclopentadiene-phenol addition reaction type cyanate resin is preferable from the viewpoint of obtaining a cured product excellent in dielectric characteristics.

The thermosetting composition of the present invention may further contain a hardening accelerator (B1). As the hardening accelerator (B1), one or two or more kinds may be used, and examples thereof include: phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, lewis acids, amine complex salts, and the like. Particularly when used for the use of semiconductor sealing materials, triphenylphosphine is preferable as the phosphorus compound, and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, in view of excellent curability, heat resistance, electrical characteristics, moisture resistance and reliability.

The thermosetting composition of the present invention may further contain a maleimide compound (B2). Wherein the maleimide compound (B2) is different from the maleimide resin. As the maleimide compound (B2), one or two or more kinds may be used, and examples thereof include: n-aliphatic maleimides such as N-cyclohexylmaleimide, N-methylmaleimide, N-N-butylmaleimide, N-hexylmaleimide and N-t-butylmaleimide; n-aromatic maleimides such as N-phenylmaleimide, N- (P-methylphenyl) maleimide and N-benzylmaleimide; bis-maleimides such as 4,4 '-diphenylmethane bismaleimide, 4' -diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, and the like.

Among them, the maleimide compound (B2) is preferably a bismaleimide type, particularly preferably 4,4' -diphenylmethane bismaleimide, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, or the like, in terms of improving the heat resistance of the cured product.

In the case of using the maleimide compound (B2), the amine compound, the phenol compound, the acid anhydride-based compound, the imidazole compound, the organic metal salt, and the like may be contained as necessary.

The modified resin (C) is a urethane resin having an isocyanate group content of 0mol/kg, which is produced from a polyol (C1) and a polyisocyanate (C2).

The polyol (c 1) used for the production of the urethane resin includes: polyester polyols, polyether polyols, polycarbonate polyols, and the like. Among these, polyester polyols and/or polycarbonate polyols are preferably contained in order to obtain more excellent copper foil adhesion and heat resistance.

As the polyester polyol, one or two or more kinds may be used, and examples thereof include: a polyester polyol obtained by reacting a polyol with a polycarboxylic acid; polyester polyol obtained by ring-opening polymerization of a cyclic ester compound; and polyester polyols obtained by copolymerizing them.

As the polyol used in the production of the polyester polyol, one or two or more kinds may be used, and examples thereof include: aliphatic polyols such as 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, tetraethylene glycol, neopentyl glycol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-methyl-1, 8-octanediol, 2, 4-diethyl-1, 5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and the like; polyhydric alcohols having an alicyclic structure such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol a, and alkylene oxide adducts thereof; polyhydric alcohols having an aromatic structure such as bisphenol A and bisphenol F; and a polyol obtained by modifying the polyol having an aromatic structure with an alkylene oxide. Among them, the aliphatic polyol is preferably contained in terms of obtaining more excellent copper foil adhesion and heat resistance.

The molecular weight of the polyol is preferably 50 or more, and is preferably 1,500 or less, more preferably 1,000 or less, and further preferably 700 or less. Further, in the present specification, the number average molecular weight means a molecular weight according to japanese industrial standard (Japanese Industrial Standards, JIS) K0070: 1992 and calculated based on hydroxyl value.

Examples of the alkylene oxide used for the modification of the polyol having an aromatic structure include alkylene oxides having 2 to 4 carbon atoms (preferably 2 to 3 carbon atoms), such as ethylene oxide and propylene oxide. The addition mole number 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 an aromatic structure.

As the polycarboxylic acid, one or two or more kinds may be used, and examples thereof 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 naphthalene dicarboxylic acid; anhydrides or esters thereof, and the like.

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

As the cyclic ester compound, one or two or more kinds may be used, and examples thereof include: gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, epsilon-caprolactone, epsilon-methyl caprolactone, epsilon-ethyl caprolactone, epsilon-propyl caprolactone, 3-pentene-4-lactone (3-pen-4-olide), 12-dodecalactone (12-dodecanol), gamma-dodecalactone.

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

The catalyst may also be allowed to coexist when the reaction is performed. As the catalyst, one or two or more kinds may be used, and examples thereof include: titanium 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, and preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, relative to 100 parts by mass of the total of the polyol and the polycarboxylic acid.

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

Examples of the initiator 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, pyrogallol, etc.; polyols such as sorbitol, sucrose, aconite sugar (aconite sugar); tricarboxylic acids such as aconitic acid, trimellitic acid, 1,2, 3-trimellitic acid, etc.; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2, 3-propane trithiol, and the like.

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

Examples of the polycarbonate polyol include: the reaction product of a carbonate with a polyol; phosgene (phosgene) and bisphenol a, and the like.

Examples of the carbonate include: methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonates, diphenyl carbonate, and the like.

Examples of the polyol that can be reacted with the carbonate include: a polyol exemplified as a polyol used in the production of the polyester polyol; and high molecular weight polyols (number average molecular weight 500 or more and 5,000 or less) such as polyether polyols (polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.), etc.

The number average molecular weight of the polyol (c 1) used in the production of the urethane resin is preferably 500 or more, more preferably 700 or more, and preferably 20,000 or less, more preferably 15,000 or less.

As the polyisocyanate (c 2), one or two or more kinds may be used, and examples thereof include: aromatic polyisocyanates such as 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tetramethyl xylylene diisocyanate, and the like; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic structure-containing polyisocyanates such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like.

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

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

The equivalent ratio [ isocyanate group/hydroxyl group ] of the hydroxyl group of the polyol (c 1) to the isocyanate group of the polyisocyanate (c 2) used in the production of the urethane resin 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.

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

As the other additives, for example, it is possible to use: hardening catalysts, antioxidants, adhesion imparting agents, plasticizers, stabilizers, fillers, dyes, pigments, optical brighteners, silane coupling agents, waxes, thermoplastic resins, and the like. These additives may be used alone or in combination of two or more.

The solubility parameter of the modified resin (C) is preferably 9.7 (cal/cm ³ ) ^0.5 The above is more preferably 10.0 (cal/cm ³ ) ^0.5 Above, and preferably 12.0 (cal/cm ³ ) ^0.5 Hereinafter, it is more preferably 11.7 (cal/cm ³ ) ^0.5 The following is given.

The thermosetting treeThe difference in solubility parameter between the cured product of the mixture of the fat (A) and the thermosetting agent (B) and the modified resin (C), the mixture-modified resin (C), is preferably-2 (cal/cm) ³ ) ^0.5 Above, more preferably-1.5 (cal/cm ³ ) ^0.5 Above, more preferably-1 (cal/cm ³ ) ^0.5 The above is more preferably 0 (cal/cm ³ ) ^0.5 The above is particularly preferably 0.2 (cal/cm ³ ) ^0.5 Above, and preferably 2 (cal/cm) ³ ) ^0.5 Hereinafter, it is more preferably 1.5 (cal/cm ³ ) ^0.5 Hereinafter, it is more preferably 0.8 (cal/cm ³ ) ^0.5 The following is given. It is considered that by making the difference in solubility parameter between the cured product and the modified resin (C) within a proper range, the cured product is compatible before thermosetting, and the compatibility between the mixture (including the substance during the reaction) and the modified resin (C) is reduced in association with thermosetting (i.e., reaction of the thermosetting resin (a) and the thermosetting agent (B)), the reaction product of the thermosetting resin (a) and the thermosetting agent (B) and the modified resin (C) can be phase-separated after thermosetting.

The solubility parameter of the cured product can be obtained by calculating the solubility parameter of each compound contained in the cured product of the mixture of the curable resin (a) and the thermosetting agent (B) based on the method of Fei Duosi (Fedors) (polymer engineering and science (Polymer Engineering and Science), 1974, vol.14, no. 2) and obtaining the ratio of the mass basis of each compound as a weighted average. The solubility parameter of the modified resin (C) can be calculated based on the method of Fei Duosi (Fedors) and the solubility parameter of the unit derived from each compound used as a raw material of the modified resin (C) can be obtained as a weighted average based on the ratio of the mass references of the unit derived from each compound.

The modified resin (C) has a glass transition temperature (intermediate point glass transition temperature (Tmg)) of-100 ℃ or higher, preferably-80 ℃ or higher, more preferably-70 ℃ or higher, and 50 ℃ or lower, preferably 40 ℃ or lower, more preferably 30 ℃ or lower.

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 further preferably 50,000 or less. The number average molecular weight of the modified resin (C) represents the value according to JIS K0070: 1992 and calculated based on hydroxyl value.

The thermosetting composition is preferably in a compatible state before the thermosetting reaction, but the thermosetting resin (a) and the modified resin (C) are phase-separated after the thermosetting reaction. In the phase-separated state after the thermosetting reaction, the reaction product of the thermosetting resin (a) and the thermosetting agent (B) preferably forms sea portions, and the modified resin (C) forms island portions, thereby forming 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 also form a co-continuous structure. It is considered that the modified resin (C) is uniformly dispersed in the mixture of the thermosetting resin (a) and the thermosetting agent (B) by being in a compatible state before the thermosetting reaction, and that the chemical and mechanical properties of the modified resin (C) itself are maintained by phase separation of the reaction product of the thermosetting resin (a) and the thermosetting agent (B) and the modified resin (C) after the thermosetting reaction, so that the domain (domain) of the modified resin (C) can be uniformly dispersed in the reaction product of the thermosetting resin (a) and the thermosetting agent (B) in the cured product obtained, whereby a cured product having both excellent heat resistance and copper foil adhesion can be provided.

The presence or absence of phase separation in the cured product was confirmed by the presence or absence of cloudiness in the cured product and the presence of sea and island portions when the fracture surface of the cured product was observed by an atomic force microscope (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, and preferably 60 parts by mass or less, more preferably 45 parts by mass or less, based on 100 parts by mass of the thermosetting resin (a). Further, the content may be 35 parts by mass or less, and further 15 parts by mass or less, particularly 10 parts by mass or less.

The thermosetting composition of the present invention may further contain an inorganic filler (D). By including the inorganic filler (D), the thermal expansion coefficient of the insulating layer can be further reduced. As the inorganic filler, one or two or more kinds may be used, and examples thereof include: silica (fused silica, crystalline silica, etc.), silicon nitride, aluminum oxide, clay minerals (talc, clay, etc.), mica powder, aluminum hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc., preferably silica, more preferably fused silica. The shape of the silica may be any of crushed and spherical, and is preferably spherical from the viewpoint of increasing the amount to be blended and suppressing the melt viscosity of the thermosetting composition.

In particular, when the thermosetting composition of the present invention is used for a semiconductor sealing material (preferably, a semiconductor sealing material for high heat conduction for power transistors and power integrated circuits (integrated circuit, IC)), silica (fused silica and crystalline silica are preferable, and crystalline silica is preferable), alumina, and silicon nitride are preferable.

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, particularly preferably 80% by mass or more, and preferably 95% by mass or less, still more preferably 90% by mass or less. When the content of the inorganic filler is increased, flame retardancy, wet heat resistance and weld cracking resistance are easily improved, and the thermal expansion coefficient is easily reduced.

The thermosetting composition of the present invention may further comprise a flame retardant (E). The flame retardant (E) is preferably a non-halogen system substantially free of halogen atoms. As the flame retardant (E), one or two or more kinds may be used, and examples thereof include: phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like.

As the phosphorus flame retardant, one or two or more kinds may be used, and examples thereof include: inorganic nitrogen-containing phosphorus compounds such as ammonium phosphates, e.g., red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; general organic phosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-and phosphorus-containing compounds include: and cyclic organophosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene=10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene=10-oxide, 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene=10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

In the case of using the phosphorus flame retardant, hydrotalcite, magnesium hydroxide, a boron compound, zirconia, a black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, and the like may be used in combination with the phosphorus flame retardant.

The red phosphorus is preferably subjected to a surface treatment, and examples of the surface treatment method include: (i) A method of 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) A method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. and a thermosetting resin such as a phenol resin; (iii) And a method in which a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide is double-coated with a thermosetting resin such as a phenol resin.

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

Examples of the triazine compound include: melamine, acetoguanamine, benzoguanamine, melamine dicyandiamide (mellon), melam (melam), succinylguanidine, ethylenedi-melamine (ethylene dimelamine), melamine polyphosphate, triguanidine, and the like, and further, for example, may be mentioned: (i) Amino triazine sulfate compounds such as guanyl melamine sulfate, melem sulfate, melam sulfate and the like; (ii) Cocondensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol and melamine such as melamine, benzoguanamine, acetoguanamine and formylguanidine, and formaldehyde; (iii) A mixture of the cocondensate of (ii) and a phenol resin such as a phenol formaldehyde condensate; (iv) Further modifying the above (ii) and (iii) with tung oil, isomerized linseed oil, etc.

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

The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the thermosetting composition, and the degree of desired flame retardancy, and is preferably in the range of 0.05 to 10 parts by mass, particularly preferably in the range of 0.1 to 5 parts by mass, based on 100 parts by mass of the entire thermosetting composition in which the epoxy resin, the curing agent, the non-halogen-based flame retardant, other fillers or additives, and the like are blended.

The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include: silicone oils, silicone rubbers, silicone resins, and the like.

As the inorganic flame retardant, one or two or more kinds may be used, and examples thereof include: 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; 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 of aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.; boron compounds such as zinc borate, zinc metaborate, barium metaborate, boric acid, borax, etc.; hippri (Ceepree) (Bokusui Brown), hydrated glass SiO ₂ -MgO-H ₂ O、PbO-B ₂ O ₃ Of ZnO-P system ₂ O ₅ MgO series, P ₂ O ₅ -B ₂ O ₃ PbO-MgO system, P-Sn-O-F system, and PbO-V system ₂ O ₅ -TeO ₂ Of Al series ₂ O ₃ -H ₂ Low melting point glass such as O-based glass and lead borosilicate glass.

Examples of the organometallic salt flame retardant include: ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, and compound formed by ionic bonding or coordination bonding of metal atom and aromatic compound or heterocyclic compound.

The thermosetting composition of the present invention may further contain an organic solvent (F). The thermosetting composition containing the organic solvent (F) can reduce the viscosity, and is particularly suitable for the production of printed wiring boards.

As the organic solvent (F), one or two or more kinds may 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; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ethyldiglycol acetate, and carbitol acetate; a carbitol solvent such as cellosolve, methyl cellosolve, butyl carbitol, etc.; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

In particular, when the thermosetting composition of the present invention is used for a printed wiring board, the organic solvent (F) is preferably: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propylene glycol monomethyl ether; an acetate solvent such as propylene glycol monomethyl ether acetate or ethyldiglycol acetate; carbitol solvents such as methyl cellosolve; amide solvents such as dimethylformamide, and the like.

In the case where the thermosetting composition of the present invention is used for a build-up film, the organic solvent (F) is preferably: ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

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

The thermosetting composition of the present invention may further contain conductive particles. The inclusion of conductive particles is suitable for use as a conductive paste, and is thus suitable for anisotropic conductive materials.

The thermosetting composition of the present invention may further contain rubber, filler, etc. Suitable for a laminate film by containing rubber, filler, etc.

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

The thermosetting composition of the present invention is obtained by mixing the above-mentioned components, and can be cured by heat to form a cured product. Examples of the shape of the cured product include a laminate, a cast product, an adhesive layer, a coating film, and a film (film).

The use of the thermosetting composition of the present invention includes: semiconductor sealing materials, printed wiring board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, adhesive films for build-up, and the like. Among these applications, the insulating material for printed wiring boards, insulating materials for electronic circuit boards, and adhesive films for build-up layers can be used as insulating materials for so-called substrates for electronic component mounting in which passive components such as capacitors and active components such as IC chips are mounted in substrates. Among these, the adhesive film is preferably used for a printed wiring board material or an adhesive film for build-up layer in terms of characteristics such as high heat resistance and solvent solubility.

As a method for producing a semiconductor sealing material from the thermosetting composition of the present invention, it can be obtained by sufficiently melt-mixing the thermosetting resin (a), the thermosetting agent (B), the modified resin (C) and, if necessary, the components until they become uniform, using an extruder, a kneader, a roll or the like, if necessary.

When the thermosetting composition of the present invention is used for a semiconductor sealing material, a semiconductor package can be molded, specifically, a semiconductor device as a molded article can be obtained by casting the composition, molding the composition using a transfer molding machine, an injection molding machine, or the like, and further heating the molded article at 50 to 200 ℃ for 2 to 10 hours.

In addition, when a printed circuit board is manufactured using the thermosetting composition of the present invention, there is a method of impregnating a reinforcing base material with the thermosetting composition and laminating a copper foil to perform thermocompression bonding. As the reinforcing substrate, there may be mentioned: paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass felt, glass gauze, and the like. More specifically, first, the thermosetting composition is heated (preferably 50 to 170 ℃ C. Depending on the kind of the organic solvent (F)), whereby a prepreg as a cured product can be obtained. In the prepreg, the resin content is preferably 20 mass% or more and 60 mass% or less. Then, the prepreg is laminated and laminated with copper foil, and the laminate is thermally bonded at 170 ℃ to 300 ℃ for 10 minutes to 3 hours under a pressure of 1MPa to 10MPa, thereby obtaining the target printed circuit board.

In the case of using the thermosetting composition of the present invention as a conductive paste, examples thereof include: a method of preparing a composition for anisotropic conductive film by dispersing conductive particles (fine conductive particles) in the thermosetting composition; a method for producing a paste resin composition for circuit connection or an anisotropic conductive adhesive which is liquid at room temperature.

As a method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting composition of the present invention, for example, a method of applying the thermosetting composition to a wiring substrate on which a circuit is formed by using a spray method, a curtain coating method, or the like, and then curing the composition is used. Then, if necessary, a predetermined through hole is formed, and then the surface is treated with a roughening agent, and then washed with hot water to form irregularities, and then a plating treatment of a metal such as copper is performed. The plating method is preferably electroless plating or electrolytic plating treatment, and the roughening agent may be: oxidizing agents, bases, organic solvents, and the like. Such operations are repeated as necessary, and the resin insulating layer and the conductor layer of the predetermined circuit pattern are alternately laminated, whereby a laminated substrate can be obtained. Wherein the opening of the through hole is performed after the formation of the outermost resin insulation layer. The build-up substrate may be produced by heat-pressing a resin-coated copper foil, which is obtained by semi-curing the thermosetting composition on a copper foil, to a wiring substrate on which a circuit is formed at 170 to 300 ℃, thereby omitting the step of forming a roughened surface and plating.

As a method for producing a build-up film from the thermosetting composition of the present invention, for example, a method of forming a resin composition layer by applying the thermosetting composition of the present invention to a support film and producing a build-up film for a multilayer printed wiring board can be mentioned.

When the thermosetting composition of the present invention is used for a build-up film, it is important that the film is softened under the temperature conditions (usually 70 to 140 ℃) at which the film is laminated in a vacuum lamination method, and the film exhibits fluidity (resin flow) in which resin filling can be performed in via holes (via holes) or through holes (through holes) existing in the circuit board while laminating the circuit board, and in order to exhibit such characteristics, it is preferable to prepare the respective components.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1mm to 0.5mm, and the depth is usually 0.1mm to 1.2mm, and it is usually preferable to fill the resin in the above-mentioned range. In the case of laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.

As for the method of manufacturing the adhesive film described above, specifically, it can be manufactured by: after preparing the thermosetting composition of the present invention in the form of a varnish, the composition in the form of a varnish is applied to the surface of the support film (Y), and then the organic solvent is dried by heating, blowing hot air, or the like, to form the layer (X) of the thermosetting composition.

The thickness of the layer (X) formed 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 μm to 70 μm, the thickness of the resin composition layer is preferably 10 μm to 100 μm.

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

The support film and the protective film may be: polyolefin such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter sometimes simply referred to as "PET (polyethylene terephthalate)"); polyesters such as polyethylene naphthalate; a polycarbonate; polyimide; and release paper, copper foil, aluminum foil, and other metal foils. The support film and the protective film may be subjected to a matting treatment, a corona treatment, and a mold release treatment.

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

The support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heat curing. When the support film (Y) is peeled off after the adhesive film is heat-cured, adhesion of dirt and the like in the curing step can be prevented. In the case of peeling after curing, the support film is usually subjected to a mold release treatment in advance.

Then, regarding the method of manufacturing a multilayer printed wiring board using the adhesive film obtained in the above manner, for example, after peeling the protective film in the case where the layer (X) is protected by the protective film, the layer (X) is laminated on one side or both sides of the circuit substrate in direct contact with the circuit substrate, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous type using a roll. Before lamination, the adhesive film and the circuit board may be heated (preheated) as needed.

The conditions for lamination are preferably such that the pressure bonding temperature (lamination temperature) is preferably 70℃to 140℃and the pressure bonding pressure is preferably 1kgf/cm ² ～11kgf/cm ² (9.8×10 ⁴ N/m ² ～107.9×10 ⁴ N/m ² ) And the lamination is performed under reduced pressure of 20mmHg (26.7 hPa) or less.

The method for obtaining the cured product of the present invention may be a method for curing a general thermosetting composition, and the heating temperature conditions may be appropriately selected according to the type or use of the curing agent to be combined, for example, and the composition obtained by the method may be heated at a temperature ranging from about 20 to 300 ℃.

Examples (example)

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

Synthesis example 1 Synthesis of polyester polyol 1

The reaction apparatus was charged with 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, and heating and stirring were started.

Then, after the internal temperature was raised to 220 ℃, 0.03 parts by mass of tetraisopropyl titanate (Tetraisopropyl titanate, tiPT) was charged, and a condensation reaction was performed at 220℃for 30 hours to synthesize a polyester polyol 1 (abbreviated as PEs 1).

The hydroxyl number of the PEs1 obtained was 16.0 and the number average molecular weight was 7,000.

Synthesis example 2 Synthesis of polyester polyol 2

The reaction apparatus was charged with 169.5 parts by mass of diethylene glycol, 82.1 parts by mass of neopentyl glycol, 217.3 parts by mass of 1, 6-hexanediol and 740.5 parts by mass of adipic acid, and the temperature was raised and stirring was started.

Then, the internal temperature was raised to 220℃and 0.03 parts by mass of TiPT was charged, followed by condensation reaction at 220℃for 30 hours, to thereby synthesize polyester polyol 2 (abbreviated as PEs 2).

The hydroxyl number of the PEs2 obtained was 20.4 and the number average molecular weight was 5,500.

Synthesis example 3 Synthesis of polyester polyol 3

The reaction apparatus was charged with 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, and the temperature was raised and stirring was started.

Then, the internal temperature was raised to 220℃and 0.03 parts by mass of TiPT was charged, followed by condensation reaction at 220℃for 20 hours, to thereby synthesize polyester polyol 3 (abbreviated as PEs 3).

The hydroxyl number of the PEs3 obtained was 56.1 and the number average molecular weight was 2,000.

Synthesis example 4 Synthesis of polyester polyol 4

The reaction apparatus was charged with 527.6 parts by mass of 1, 6-hexanediol and 572.4 parts by mass of phthalic anhydride, and the temperature was raised and stirring was started.

Then, the internal temperature was raised to 220℃and 0.1 part by mass of TiPT was charged, followed by condensation reaction at 220℃for 20 hours, to thereby synthesize polyester polyol 4 (abbreviated as PEs 4).

The hydroxyl number of the PEs4 obtained was 56.1 and the number average molecular weight was 2,000.

Synthesis example 5 Synthesis of polyester polyol 5

577.9 parts by mass of neopentyl glycol and 623.2 parts by mass of adipic acid were charged into the reaction apparatus, and the temperature was raised and stirring was started.

Then, the internal temperature was raised to 220℃and 0.03 parts by mass of TiPT was charged, followed by condensation reaction at 220℃for 15 hours, to thereby synthesize polyester polyol 5 (abbreviated as PEs 5).

The hydroxyl number of the PEs5 obtained was 112.2 and the number average molecular weight was 1,000.

Synthesis example 6 Synthesis of polyester polyol 6

538.7 parts by mass of neopentyl glycol and 659.4 parts by mass of adipic acid were charged into the reaction apparatus, and the temperature was raised and stirring was started.

Then, the internal temperature was raised to 220℃and 0.03 parts by mass of TiPT was charged, followed by condensation reaction at 220℃for 20 hours, to thereby synthesize polyester polyol 6 (abbreviated as PEs 6).

The hydroxyl number of the PEs6 obtained was 56.1 and the number average molecular weight was 2,000.

Synthesis example 7 Synthesis of urethane resin 1

To the reaction apparatus, 1,000 parts by mass of the PEs1 obtained in Synthesis example 1 were charged 28.6 parts by mass of 4,4' -diphenylmethane diisocyanate (trademark; manufactured by Tosoh Co., ltd., "Milliodate" MT, hereinafter abbreviated to MDI). Then, after the internal temperature was raised to 120 ℃, the reaction was continued for 5 hours to synthesize urethane resin 1 (C1).

The hydroxyl number of the urethane resin obtained was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was-50 ℃.

Synthesis example 8 Synthesis of urethane resin 2

1,000 parts by mass of PEs1 obtained in Synthesis example 1 was charged into a reaction apparatus, and 10.7 parts by mass of MDI was charged. Then, after the internal temperature was raised to 120 ℃, the reaction was continued for 5 hours to synthesize urethane resin 2 (C2).

The hydroxyl number of the urethane resin obtained was 11.2, the number average molecular weight was 10,000, and the glass transition temperature was-54 ℃.

Synthesis example 9 Synthesis of urethane resin 3

To the reaction apparatus, 1,000 parts by mass of the PEs1 obtained in Synthesis example 1 was charged, and 32.1 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and then the reaction was continued for 5 hours to synthesize urethane resin 3 (C3).

The hydroxyl number of the urethane resin obtained was 11.2, the number average molecular weight was 70,000, and the glass transition temperature was-49 ℃.

Synthesis example 10 Synthesis of urethane resin 4

1,000 parts by mass of PEs1 obtained in Synthesis example 1 were charged into a reaction apparatus, and 21.5 parts by mass of 1, 3-xylylene diisocyanate (trademark; manufactured by Sanyo chemical Co., ltd., "Takenate) 500" was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 10 hours to synthesize urethane resin 4 (C4).

The hydroxyl number of the urethane resin obtained was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was-53 ℃.

Synthesis example 11 Synthesis of urethane resin 5

1,000 parts by mass of PEs1 obtained in Synthesis example 1 was charged into a reaction apparatus, and 19.2 parts by mass of hexamethylene diisocyanate (trademark; manufactured by Tosoh Co., ltd., "HDI") was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 10 hours to synthesize urethane resin 5 (C5).

The hydroxyl number of the urethane resin obtained was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was-54 ℃.

Synthesis example 12 Synthesis of urethane resin 6

1,000 parts by mass of PEs1 obtained in Synthesis example 1 was charged into a reaction apparatus, and 19.9 parts by mass of toluene diisocyanate (trademark; manufactured by Mitsui chemical Co., ltd., "Cosmonate) T-80" was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 6 (C6).

The hydroxyl number of the urethane resin obtained was 3.2, the number average molecular weight was 35,000, and the glass transition temperature was-51 ℃.

Synthesis example 13 Synthesis of urethane resin 7

1,000 parts by mass of PEs2 obtained in Synthesis example 2 was charged into the reaction apparatus, and 36.4 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 7 (C7).

The hydroxyl number of the urethane resin obtained was 4.0, the number average molecular weight was 28,000, and the glass transition temperature was-49 ℃.

Synthesis example 14 Synthesis of urethane resin 8

1,000 parts by mass of PEs3 obtained in Synthesis example 3 was charged into a reaction apparatus, and 106.3 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 8 (C8).

The hydroxyl number of the urethane resin obtained was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was-46 ℃.

Synthesis example 15 Synthesis of urethane resin 9

1,000 parts by mass of PEs4 obtained in Synthesis example 4 was charged into a reaction apparatus, and 106.3 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 9 (C9).

The hydroxyl value of the urethane resin obtained was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was-7 ℃.

Synthesis example 16 Synthesis of urethane resin 10

To the reaction apparatus, 1,000 parts by mass of the PEs5 obtained in Synthesis example 5 was charged, and 151.4 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and then the reaction was continued for 5 hours to synthesize urethane resin 10 (C10).

The hydroxyl number of the urethane resin obtained was 37.4, the number average molecular weight was 3,000, and the glass transition temperature was-40 ℃.

Synthesis example 17 Synthesis of urethane resin 11

To the reaction apparatus, 1,000 parts by mass of PEs5 obtained in Synthesis example 5 was charged, and 222.6 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and then the reaction was continued for 5 hours to synthesize urethane resin 11 (C11).

The hydroxyl number of the urethane resin obtained was 9.4, the number average molecular weight was 12,000, and the glass transition temperature was-29 ℃.

Synthesis example 18 Synthesis of urethane resin 12

To the reaction apparatus, 1,000 parts by mass of PEs6 obtained in Synthesis example 6 was charged, and 59.5 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize the urethane resin 12 (C12).

The hydroxyl number of the urethane resin obtained was 28.1, the number average molecular weight was 4,000, and the glass transition temperature was-41 ℃.

Synthesis example 19 Synthesis of urethane resin 13

To the reaction apparatus, 1,000 parts by mass of PEs6 obtained in Synthesis example 6 was charged, and 106.3 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 13 (C13).

The hydroxyl number of the urethane resin obtained was 8.0, the number average molecular weight was 14,000, and the glass transition temperature was-36 ℃.

Synthesis example 20 Synthesis of urethane resin 14

1,000 parts by mass of a polycarbonate polyol (trademark; manufactured by Asahi chemical Co., ltd., "Duranol) T5652", having a number average molecular weight of 2000) produced from 1, 5-pentanediol and 1, 6-hexanediol was added to the reaction apparatus, and 93.8 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 14 (C14).

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

Synthesis example 21 Synthesis of urethane resin 15

A polycarbonate polyol (trademark; manufactured by Asahi chemical Co., ltd., "Duranol) T5651", having a number average molecular weight of 2000) made of 1, 5-pentanediol and 1, 6-hexanediol was added to the reaction apparatus, and 200 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 15 (C15).

The hydroxyl number of the urethane resin obtained was 18.7, the number average molecular weight was 6,000, and the glass transition temperature was-38 ℃.

Synthesis example 22 Synthesis of urethane resin 16

A polycarbonate polyol (trademark; manufactured by Asahi chemical Co., ltd., "Duranol) G3450J", having a number average molecular weight of 800) made of 1, 3-propanediol and 1, 4-butanediol was added to the reaction apparatus, and 250 parts by mass of MDI was charged. Then, the internal temperature was raised to 120℃and the reaction was continued for 5 hours to synthesize urethane resin 16 (C16).

The hydroxyl number of the urethane resin obtained was 22.4, the number average molecular weight was 5,000, and the glass transition temperature was-9 ℃.

[ example 1 ]

In a mixing vessel, 61.5 parts by mass of a polyhydroxynaphthalene type epoxy resin (trademark; manufactured by Dielson (DIC) Co., ltd., "Ai Bike parts by mass (EPICLON) HP-4700", abbreviated as "A1" in the table), and a novolak type phenol resin (trademark; manufactured by Dielson (DIC) Co., ltd., "Pi Nuolei t (PHENOLITE) TD-2131", abbreviated as "B1" in the table) were blended, and the resultant urethane resin 1 (C1) 10 parts by mass, obtained in Synthesis example 7, were stirred at an internal temperature of 130℃until they were compatible. 0.3 part by mass of 2-ethyl-4-methylimidazole as a hardening accelerator was added, followed by stirring for 20 seconds and vacuum defoaming, whereby a thermosetting composition as the thermosetting composition of the present invention was obtained.

[ example 2 and example 3 ]

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

[ example 4 to example 15 ]

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

[ example 16-example 18 ]

A thermosetting composition was obtained in the same manner as in example 1 except that 10 parts by mass of the urethane resin 1 (C1) was blended and 5 parts by mass of the urethane resins (C14 to C16) described in the table were blended.

[ example 19 ]

85.4 parts by mass (solid content: 42.7 parts by mass) of a 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin and an active ester resin (trademark; manufactured by Dielsen (DIC) Co., ltd.), "Ai Bike (EPICLON) HPC-8000-65T", abbreviated as "B2" in the table) 88.2 parts by mass (65% toluene solution, solid content: 57.3 parts by mass) as a hardener were prepared in a mixing vessel, and 5 parts by mass of the urethane resin 1 (C1) obtained in Synthesis example 7 were stirred at 130℃under reduced pressure until they were compatible. 0.5 parts by mass of 4-dimethylaminopyridine as a hardening accelerator was added, and after stirring for 20 seconds, vacuum defoaming was performed, thereby obtaining a thermosetting composition as the thermosetting composition of the present invention.

Comparative example 1

In a mixing vessel, 61.5 parts by mass of polyhydroxynaphthalene type epoxy resin A1.5 parts by mass of a hardener and 38.5 parts by mass of a novolak type phenol resin B1.5 parts by mass of a hardener were prepared, and stirred at an internal temperature of 130℃until they were compatible. 0.3 part by mass of 2-ethyl-4-methylimidazole as a hardening accelerator was added thereto, followed by stirring for 20 seconds and vacuum deaeration, whereby the thermosetting composition of the present invention was obtained.

Comparative example 2

85.4 parts by mass (solid content 42.7 parts by mass) of a 50% methyl ethyl ketone solution of polyhydroxynaphthalene type epoxy resin A1 as an epoxy resin and 88.2 parts by mass (65% toluene solution, solid content 57.3 parts by mass) of an active ester resin B2 as a hardener were prepared in a mixing vessel, and the mixture was stirred at 130℃under reduced pressure while desolvation until the mixture was compatible. 0.5 parts by mass of 4-dimethylaminopyridine as a hardening accelerator was added, and after stirring for 20 seconds, vacuum defoaming was performed, thereby obtaining a thermosetting composition as the thermosetting composition of the present invention.

The thermosetting composition obtained was evaluated as follows. The solubility parameter of the modified resin (C) used in each thermosetting composition is shown in the table together with the results.

[ method for evaluating copper foil adhesion ]

The thermosetting compositions obtained in examples and comparative examples were flowed into a casting plate formed by sandwiching a 1mm thick rubber spacer between glass plates each having copper foil adhered to one side thereof at 130℃and thermally cured at 175℃for 5 hours. The cured product obtained was cut into a size of 10mm wide by 60mm long, and the 90℃peel strength (N/cm) was measured using a peel tester.

Measurement device: shimadzu Aote Gu Lafu (Autograph) (manufactured by Shimadzu corporation)

Model: AG-1

Test speed: 50mm/min

[ method for evaluating Heat resistance ]

The heat resistance was evaluated by the glass transition temperature. Specifically, the thermosetting compositions obtained in examples and comparative examples were flowed into a casting plate made of a rubber spacer having a thickness of 1mm sandwiched by glass plates at 130 ℃ and thermally cured at 175 ℃ for 5 hours. The cured product obtained was cut into a size of 10mm wide by 55mm long, and the storage elastic modulus (E ') and the loss elastic modulus (E') were measured under the following conditions.

When E'/E "is tan delta, the temperature at which tan delta is maximum is measured as the glass transition temperature (unit;. Degree. C.). The Tg of the thermosetting compositions obtained in examples and comparative examples was evaluated as 1 of the glass transition temperature, and the difference between the Tg of the thermosetting compositions obtained in examples and comparative examples and the Tg of the thermosetting composition when no modified resin was added was evaluated as 2 of the glass transition temperature.

Measurement device: dynamic viscoelasticity tester (manufactured by Seiko electronic nanotechnology (SII Nanotechnology) Co., ltd.)

Model: DMA6100

Measuring temperature range: 0-300 DEG C

Heating rate: 5 ℃/min

Frequency: 1Hz

Measurement mode: stretching

TABLE 1

TABLE 2

TABLE 3

Examples 1 to 19, which are thermosetting compositions of the present invention, exhibited excellent heat resistance and copper foil adhesion in the cured product obtained. On the other hand, comparative examples 1 to 2 are examples containing no modified resin (C), and the copper foil adhesion is poor.

Claims

1. A thermosetting composition comprising a thermosetting resin (A), a thermosetting agent (B) and a modified resin (C), characterized in that,

the modified resin (C) is a urethane resin having an isocyanate group content of 0mol/kg and prepared from a polyol (C1) and a polyisocyanate (C2),

the modified resin (C) has a glass transition temperature of-100 ℃ to 50 ℃,

the modified resin (C) has a number average molecular weight of 4,000 to 100,000,

the content of the modified resin (C) is 0.1 to 60 parts by mass based on 100 parts by mass of the thermosetting resin (A).

2. The thermosetting composition according to claim 1, wherein the polyol (c 1) comprises a polyester polyol and/or a polycarbonate polyol.

3. The thermosetting composition according to claim 2, wherein the polyester polyol comprises an aliphatic diol as a raw material.

4. The thermosetting composition according to claim 1, wherein the modified resin (C) has a solubility parameter of 9.7 (cal/cm ³ ) ^0.5 Above and 12.0 (cal/cm) ³ ) ^0.5 The following is given.

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

6. A cured product comprising the thermosetting composition according to claim 1.

7. A semiconductor sealing material comprising the thermosetting composition according to claim 1.

8. A prepreg comprising the thermosetting composition according to claim 1 and a reinforcing substrate impregnated with the thermosetting composition.

9. A circuit board comprising the thermosetting composition according to claim 1, and a copper foil.

10. A build-up film comprising the cured product of the thermosetting composition according to claim 1 and a base film.