CN111527152A - Thermosetting composition, thermosetting resin modifier, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-up film - Google Patents

Thermosetting composition, thermosetting resin modifier, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-up film Download PDF

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CN111527152A
CN111527152A CN201880084417.7A CN201880084417A CN111527152A CN 111527152 A CN111527152 A CN 111527152A CN 201880084417 A CN201880084417 A CN 201880084417A CN 111527152 A CN111527152 A CN 111527152A
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松村优佑
中村昭文
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Abstract

The present invention addresses the problem of providing a thermosetting composition, a thermosetting resin modifier, a cured product thereof, a semiconductor sealing material, a prepreg, a circuit board, and an build-up film, which can achieve good copper foil adhesion, elastic modulus, heat resistance, and toughness in a well-balanced manner in the cured product obtained therefrom. The present invention uses a thermosetting composition comprising a thermosetting resin, a thermosetting agent, and a modified resin, wherein the modified resin is a thermoplastic resin having at least 1 selected from a hydroxyl group and a carboxyl group, the modified resin has a glass transition temperature of-100 ℃ or higher and 50 ℃ or lower, and the modified resin has a number average molecular weight of 600 or higher and 50,000 or lower.

Description

Thermosetting composition, thermosetting resin modifier, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-up film
Technical Field
The present invention relates to a thermosetting composition, a thermosetting resin modifier, a cured product thereof, and a semiconductor sealing material, a prepreg, a circuit board, and a build-up film obtained using the same.
Background
Thermosetting resins are used as sealing materials for protecting semiconductor devices such as capacitors, diodes, transistors, and thyristors, and integrated circuits such as ICs and LSIs. With the miniaturization and thinning of electronic parts, printed wiring boards are required to have higher densities and higher integrations, and along with this, semiconductor sealing materials are required to have low thermal expansion properties and the like.
As the semiconductor sealing material, a thermosetting resin composition containing an aromatic amine compound, an aliphatic amine compound, a siloxane compound, and a maleimide compound has been proposed (for example, see patent document 1). Further, a resin composition containing a cyanate ester resin and a naphthalene ether type epoxy resin has been proposed (for example, see patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-178991
Patent document 2: japanese patent laid-open publication No. 2016-006187
Disclosure of Invention
Problems to be solved by the invention
However, according to the studies of the present inventors, a cured product formed from a conventional thermosetting resin composition has good low thermal expansion properties, but good copper foil adhesion, elastic modulus, heat resistance, and toughness cannot be achieved with a sufficient balance.
The present invention addresses the problem of providing a thermosetting composition, a thermosetting resin modifier, a cured product thereof, a semiconductor sealing material, a prepreg, a circuit board, and an build-up film, which can achieve good copper foil adhesion, elastic modulus, heat resistance, and toughness in a well-balanced manner in the cured product obtained therefrom.
Means for solving the problems
The present invention uses a thermosetting composition comprising a thermosetting resin, a thermosetting agent, and a modified resin, wherein the modified resin is a thermoplastic resin having at least 1 selected from a hydroxyl group and a carboxyl group, the modified resin has a glass transition temperature of-100 ℃ or higher and 50 ℃ or lower, and the modified resin has a number average molecular weight of 600 or higher and 50,000 or lower.
Effects of the invention
The thermosetting composition of the present invention can provide a cured product thereof having excellent heat resistance, copper foil adhesion, and toughness.
Drawings
FIG. 1 is an atomic force microscope image of a fracture surface of a cured product of example 1.
FIG. 2 is an atomic force microscope image of a fracture surface of a cured product of example 2.
FIG. 3 is an atomic force microscope image of a fracture surface of a cured product of example 3.
FIG. 4 is an atomic force microscope image of a fracture surface of a cured product of example 4.
FIG. 5 is an atomic force microscope image of a fracture surface of a cured product of comparative example 1.
FIG. 6 is an atomic force microscope image of a fracture surface of a cured product of comparative example 2.
Detailed Description
The thermosetting composition of the present invention comprises a thermosetting resin (a), a thermosetting agent (B), and a modified resin (C). The thermosetting composition may contain an inorganic filler (D), and may further contain a flame retardant (E).
Examples of the thermosetting resin (a) include an epoxy resin, a resin containing a benzoxazine structure, a maleimide resin, a vinylbenzyl compound, an acrylic compound, and a copolymer of styrene and maleic anhydride, and preferably at least an epoxy resin is contained.
As the above-mentioned epoxy resin, 1 or 2 or more 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 oxynaphthalene compounds (1, 6-diglycidyl oxynaphthalene, 2, 7-diglycidyl oxynaphthalene, 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-condensation novolac type epoxy resin, naphthol-cresol co-condensation novolac type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, phenol novolac type epoxy resin, and the like, An aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resin, a biphenyl linear phenol resin-type epoxy resin, a naphthalene skeleton-containing epoxy resin such as 1, 1-bis (2, 7-diglycidyloxy-1-naphthyl) alkane, a phosphorus-modified epoxy resin obtained by introducing a phosphorus atom into these various epoxy resins, and the like.
Among them, as the above epoxy resin, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins are particularly preferable from the viewpoint of obtaining cured products excellent in heat resistance; naphthol linear phenol type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation linear phenol type epoxy resin, naphthol-cresol co-condensation linear phenol type epoxy resin containing a naphthalene skeleton; crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthene type epoxy resin; and alkoxy group-containing aromatic ring-modified phenol novolac epoxy resins (compounds obtained by connecting a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring with formaldehyde).
In the thermosetting resin (a), the content of the epoxy resin is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, with the upper limit being 100% by mass.
The maleimide resin may be 1 or 2 or more species, and examples thereof include resins represented by any of the following structural formulae.
[ chemical formula 1]
Figure BDA0002558035030000031
[ in the formula (1), R1Represents an organic group having a valence of a1, R2And R3Each 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 formula 2]
Figure BDA0002558035030000041
[ in the formula (2), R4、R5And R6Each 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, L1And L2Each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group having 6 to 15 carbon atoms in which a saturated hydrocarbon group and an aromatic hydrocarbon group are combined. a3, a4 and a5 are each independently an integer of 1 to 3, and n is an integer of 0 to 10.]
The content of the thermosetting resin (a) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, preferably 99% by mass or less, and more preferably 98% by mass or less in the nonvolatile components of the thermosetting composition.
The thermosetting agent (B) may be any compound that can react with the thermosetting resin (a) by heating to cure the thermosetting composition, and 1 or 2 or more kinds of compounds may 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 1 selected from an active ester resin, a phenol resin and a cyanate resin.
Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF3Amine complexes, guanidine derivatives, etc.
Examples of the amide compound include dicyandiamide and polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine.
The active ester resin is not particularly limited, and compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are generally preferably used. The above 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. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a 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 a halide thereof. Examples of the phenol compound or 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, phloroglucinol, benzenetriol, dicyclopentadiene-phenol addition type resins, and the like.
Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
Examples of the phenol resin include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins (Xyloc resins (japanese national standard: ザイロック colophony)), naphthol aralkyl resins, tris (hydroxyphenyl) methane resins, tetrakis (hydroxyphenyl) ethane resins, naphthol novolac resins, naphthol-phenol cocondensed novolac resins, naphthol-cresol cocondensed novolac resins, biphenyl-modified phenol resins (polyphenol hydroxyl group-containing compounds obtained by connecting phenol nuclei with a dimethylene group), phenol resins having a naphthalene skeleton, biphenyl-modified naphthol resins (polynaphthol compounds obtained by connecting phenol nuclei with a dimethylene group), aminotriazine-modified phenol resins (polyphenol hydroxyl group-containing compounds obtained by connecting phenol nuclei with melamine, benzoguanamine, or the like), and the like, Polyhydric phenolic hydroxyl group-containing resins such as alkoxy group-containing aromatic ring-modified phenol novolac resins (polyhydric phenolic hydroxyl group-containing compounds obtained by connecting a phenol nucleus and an alkoxy group-containing aromatic ring with formaldehyde), bisphenol compounds such as bisphenol a and bisphenol F, and biphenyl compounds such as biphenyl and tetramethylbiphenyl; tris (hydroxyphenyl) methane, tetrakis (hydroxyphenyl) ethane; dicyclopentadiene-phenol addition reaction type resins, phosphorus-modified phenol compounds obtained by introducing a phosphorus atom into these various phenolic hydroxyl group-containing compounds, and the like.
The cyanate ester resin may be used in 1 kind or 2 kinds or more, and examples thereof include 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 thioether type cyanate ester resin, phenylene ether type cyanate ester resin, naphthyl ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol F type cyanate ester resin, naphthol-cresol co-condensed novolac cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin cyanate ester resins, biphenyl-modified novolac cyanate ester resins, anthracene-type cyanate ester resins, and the like.
Among these cyanate ester resins, in particular, in order to obtain a cured product excellent in heat resistance, it is preferable to use a bisphenol a type cyanate ester resin, a bisphenol F type cyanate ester resin, a bisphenol E type cyanate ester resin, a polyhydroxynaphthalene type cyanate ester resin, a naphthalene ether type cyanate ester resin, or a novolac type cyanate ester resin, and in order to obtain a cured product excellent in dielectric characteristics, a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable.
The thermosetting resin composition of the present invention may further contain a curing accelerator (B1). The curing accelerator (B1) may be used in 1 or 2 or more types, and examples thereof include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, lewis acids, and amine complex salts. In particular, when used as a semiconductor sealing material, triphenylphosphine is preferable as the phosphorus compound, and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.
The thermosetting composition of the present invention may further contain a maleimide compound (B2). However, the maleimide compound (B2) is different from the above maleimide resin. As the maleimide compound (B2), 1 or 2 or more species can 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; bismaleimides 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, and bis (3, 5-diethyl-4-maleimidophenyl) methane.
Among these, as the maleimide compound (B2), bismaleimides are preferable in terms of improving the heat resistance of the cured product, and 4,4' -diphenylmethane bismaleimide, 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 preferable.
When the maleimide compound (B2) is used, the amine compound, the phenol compound, the acid anhydride compound, the imidazole compound, an organic metal salt, and the like may be contained, if necessary.
The modified resin (C) is a thermoplastic resin having at least 1 selected from a hydroxyl group and a carboxyl group, and preferably has a hydroxyl group.
The hydroxyl value of the modified resin (C) is preferably not less than 10mgKOH/g, more preferably not less than 15mgKOH/g, still more preferably not less than 18mgKOH/g, preferably not more than 200mgKOH/g, more preferably not more than 150mgKOH/g, and still more preferably not more than 120 mgKOH/g.
The number of at least 1 (preferably, hydroxyl group) selected from the group consisting of a hydroxyl group and a carboxyl group contained in the modified resin (C) is preferably 2 or more, preferably 6 or less, more preferably 4 or less, further preferably 3 or less, and particularly preferably 2 per 1 molecule.
The modified resin (C) is preferably at least 1 selected from a polyester resin and a polyurethane resin, and more preferably a polyester resin.
The polyester resin may be 1 or 2 or more, and examples thereof include polyester resins obtained by reacting a polyhydric alcohol with a polycarboxylic acid; a polyester resin obtained by ring-opening polymerization of a cyclic ester compound; and polyester resins obtained by copolymerizing these.
As the polyhydric alcohol used for the production of the polyester resin, 1 or 2 or more species can be used, and examples thereof include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, and 1, 3-butanediol; alicyclic polyols such as cyclohexanedimethanol; aromatic polyhydric alcohols such as bisphenol a and bisphenol F; and polyols obtained by modifying the above polyols having an aromatic structure with alkylene oxide.
Among these, the polyol having an alicyclic structure, the polyol having an aromatic structure, and the polyol obtained by modifying the polyol having an aromatic structure with alkylene oxide are preferable, and the polyol obtained by modifying the polyol having an aromatic structure with alkylene oxide is more preferable.
The molecular weight of the polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, and further preferably 700 or less.
In the present specification, the number average molecular weight means a value calculated based on the hydroxyl value.
Examples of the alkylene oxide used for modifying 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 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, based on 1 mole of the polyol having an aromatic structure.
The polycarboxylic acid may be used in 1 or 2 or more species, 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 naphthalenedicarboxylic acid; anhydrides and esters thereof.
Among them, aliphatic polycarboxylic acids are preferably contained. The content of the aliphatic polycarboxylic acid is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 100 mol% or less of the total amount of the polycarboxylic acids.
The polycarboxylic acid preferably includes an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid. The content ratio of the aromatic polycarboxylic acid to the aliphatic polycarboxylic acid is preferably 1/99 or more, more preferably 30/70 or more, further preferably 50/50 or more, preferably 99/1 or less, more preferably 90/10 or less, and further preferably 85/15 or less on a molar basis.
The content ratio of the polyhydric alcohol to the polycarboxylic acid (polyhydric alcohol/polycarboxylic acid) used for producing the polyester resin is preferably 20/80 or more, more preferably 30/70 or more, further preferably 40/60 or more, preferably 99/1 or less, more preferably 90/10 or less, and further preferably 85/15 or less on a mass basis.
As the cyclic ester compound, 1 or 2 or more can be used, and examples thereof include γ -butyrolactone, γ -valerolactone, -caprolactone, -methylhexanolactone, -ethylcaprolactone, -propylcaprolactone, 3-penten-4-lactone, 12-dodecalactone (Japanese text: 12- ドデカノリド), and γ -dodecalactone.
The content of the alkylene oxide unit having 4 or more carbon atoms contained in the polyester resin is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less.
The polyester resin can be produced, for example, by reacting the polyhydric alcohol with the polycarboxylic acid. The reaction temperature is preferably 190 ℃ or higher, more preferably 200 ℃ or higher, preferably 250 ℃ or lower, and more preferably 240 ℃ or lower. The reaction time is preferably 1 hour or more and 100 hours or less.
In the above reaction, a catalyst may be allowed to coexist, and 1 or 2 or more types of the catalyst 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 catalysts such as p-toluenesulfonic acid.
The amount of the catalyst is preferably 0.0001 part by mass or more, more preferably 0.0005 part by mass or more, preferably 0.01 part by mass or less, and more preferably 0.005 part by mass or less, per 100 parts by mass of the total of the polyhydric alcohol and the polycarboxylic acid.
The polyurethane resin is a reaction product of a polyol and a polyisocyanate, and has a hydroxyl group at a terminal.
Examples of the polyol used for producing the polyurethane resin include polyether polyol, polyester polyol, and polycarbonate polyol.
The polyether polyol is obtained by addition polymerization (ring-opening polymerization) of alkylene oxide using 1 or 2 or more species of a compound having 2 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, and aconite sugar; tricarboxylic acids such as aconitic acid, trimellitic acid, hemimellitic acid, and the like; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2, 3-propanetrithiol, and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
The polyether polyol is preferably polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran with the initiator.
Examples of the polyester polyol include a polyester polyol obtained by esterification of a low molecular weight polyol (for example, a polyol having a molecular weight of 50 to 300) with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone; and copolymerized polyester polyols thereof.
Examples of the low molecular weight polyol include aliphatic polyols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 1, 3-butanediol, and polyols having a molecular weight of 50 to 300 inclusive; polyols containing alicyclic structures such as 1, 4-cyclohexanediol and cyclohexanedimethanol; and aromatic structure-containing polyols such as bisphenol compounds such as bisphenol a and bisphenol F and alkylene oxide adducts thereof.
Examples of the polycarboxylic acid 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 acid anhydrides and ester-forming derivatives of the above aliphatic polycarboxylic acids and aromatic polycarboxylic acids.
Examples of the polycarbonate polyol include reaction products of a carbonate and a polyol; a reaction product of phosgene with bisphenol A or the like, and the like.
Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate, and the like.
Examples of the polyol which can be reacted with the carbonate include the polyols exemplified as the low molecular weight polyol; high molecular weight polyols (number average molecular weight of 500 to 5,000) such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.).
The number average molecular weight of the polyol used for producing the polyurethane resin is preferably 500 or more, more preferably 700 or more, preferably 3,000 or less, and more preferably 2,000 or less.
The polyisocyanate may be used in 1 or 2 or more types, and examples thereof include aromatic polyisocyanates such as 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate (Japanese text: クルードジフェニルメタンジイソシアネート), phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and polyisocyanates containing an alicyclic structure such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
The equivalent ratio [ isocyanate group/hydroxyl group ] of the hydroxyl group of the polyol to the isocyanate group of the polyisocyanate used in the production of the polyurethane resin is preferably 0.1 or more, more preferably 0.2 or more, preferably 0.9 or less, and more preferably 0.7 or less on a molar basis.
The polyurethane resin can be produced by reacting a polyol used in the production of the polyurethane resin with a polyisocyanate. When the terminal of the obtained polyurethane resin is an isocyanate group, a chain extender having a hydroxyl group may be further reacted.
The chain extender having a hydroxyl group may be used in 1 or 2 or more species, and examples thereof include glycol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, and the like; phenol compounds such as bisphenol a, 4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfone, hydrogenated bisphenol a, and hydroquinone; water, and the like.
The solubility parameter of the modified resin (C) is preferably 9.0 (cal/cm)3)0.5Above, more preferably 9.7 (cal/cm)3)0.5Above, preferably 10.5 (cal/cm)3)0.5More preferably 10.3 (cal/cm) or less3)0.5The following.
The difference in solubility parameter between the mixture of the thermosetting resin (A) and the thermosetting agent (B) and the modified resin (C) (the mixture-modified resin (C)) is preferably-2 (cal/cm)3)0 . 5Above, more preferably-1.5 (cal/cm)3)0.5Above, it is more preferably-1 (cal/cm)3)0.5Above, still more preferably 0 (cal/cm)3)0.5Above, 0.2 (cal/cm) is particularly preferable3)0 . 5Above, preferably 2 (cal/cm)3)0.5Hereinafter, more preferably 1.5 (cal/cm)3)0.5Hereinafter, more preferably 0.8 (cal/cm)3)0.5The following. It is considered that the mixture (including the substance in the reaction process) is compatible with the modified resin (C) before the thermosetting because the difference in solubility parameters between the mixture and the modified resin (C) is in a proper range, and the mixture (including the substance in the reaction process) is less compatible with the modified resin (C) with the thermosetting (i.e., the reaction between the thermosetting resin (a) and the thermosetting agent (B)), and the reaction product of the thermosetting resin (a) and the thermosetting agent (B) can be separated from the modified resin (C) after the thermosetting.
The solubility parameter of the mixture can be determined by calculating the solubility parameter of each compound contained in the thermosetting resin (a) and the thermal curing agent (B) by the method of Fedors (Polymer engineering and Science,1974, vol.14, No.2) and by calculating the weighted average value of the ratio of each compound based on the mass basis. The solubility parameter of the modified resin (C) can be obtained by calculating the solubility parameter of units derived from each compound used as a raw material of the modified resin (C) by the Fedors method and calculating the solubility parameter as a weighted average value based on the mass-based ratio of the units derived from each compound.
The glass transition temperature of the modified resin (C) is-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 500 or more, preferably 1,000 or more, more preferably 1,500 or more, and 50,000 or less, preferably 30,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less.
The number average molecular weight of the modified resin (C) can be calculated based on the functional group value.
The modified resin (C) (epoxy resin modifier) preferably contains at least 1 resin selected from polyester resins and polyurethane resins, has a hydroxyl group, has a glass transition temperature of-100 ℃ or higher and 50 ℃ or lower, and has a number average molecular weight of 600 or higher and 50,000 or lower.
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 resin (B) preferably forms sea portions and the modified resin (C) preferably forms island portions, thereby forming a sea-island phase-separated structure. The reaction product of the thermosetting resin (a) and the thermosetting agent (B) and the modified resin (C) may form a co-continuous structure. It is considered that the modified resin (C) can be uniformly dispersed in the mixture of the thermosetting resin (a) and the thermosetting agent (B) by being in a compatible state before the thermosetting reaction, and on the other hand, the chemical/mechanical properties of the modified resin (C) itself can be maintained by separating the reaction product of the thermosetting resin (a) and the thermosetting agent (B) from the modified resin (C) after the thermosetting reaction, and therefore, in the obtained cured product, the region of the modified resin (C) can be uniformly dispersed in the reaction product of the thermosetting resin (a) and the thermosetting agent (B), and a cured product having more excellent heat resistance, adhesiveness, and toughness can be provided.
The presence or absence of phase separation in the cured product can be confirmed by the presence or absence of cloudiness in the cured product and the presence of a sea portion and an island portion at the fracture surface of the cured product when observed by an Atomic Force Microscope (AFM).
The content of the modified resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, preferably 60 parts by mass or less, and more preferably 45 parts by mass or less, based on 100 parts by mass of the thermosetting resin (a). The content may be 35 parts by mass or less, further 15 parts by mass or less, and particularly 10 parts by mass or less.
The thermosetting composition of the present invention may further contain an inorganic filler (D), and the inclusion of the inorganic filler (D) can further reduce the thermal expansion coefficient of the insulating layer. The inorganic filler may be 1 or 2 or more, and examples thereof include silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, aluminum hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc., preferably silica, and more preferably fused silica. The shape of the silica may be either a crushed shape or a spherical shape, and is preferably a spherical shape from the viewpoint of suppressing the melt viscosity of the thermosetting composition while increasing the blending amount.
In particular, when the thermosetting composition of the present invention is used for a semiconductor sealing material (preferably, a high thermal conductivity semiconductor sealing material for power transistors and power ICs), silica (for example, fused silica or crystalline silica, preferably crystalline silica), alumina, and silicon nitride are preferable.
The content of the inorganic filler in the thermosetting composition is preferably 0.2% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, still further 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. When the content of the inorganic filler is increased, flame retardancy, moist heat resistance and solder crack resistance are easily improved, and the thermal expansion coefficient is easily decreased.
The thermosetting composition of the present invention may further contain a flame retardant (E). The flame retardant (E) is preferably a non-halogen flame retardant containing substantially no halogen atom. The flame retardant (E) may be 1 or 2 or more, and examples thereof include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants.
The phosphorus flame retardant may be used in 1 or 2 or more types, and examples thereof include inorganic nitrogen-containing phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amides; phosphoric ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds (Japanese text: ホスホラン compounds), examples of the organic phosphorus-containing compound include general-purpose organic phosphorus-containing compounds such as organic nitrogen-containing phosphorus compounds, and further include cyclic organic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and organic phosphorus compounds such as derivatives obtained by reacting these with compounds such as epoxy resins and phenol resins.
When the above-mentioned phosphorus flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, and the like can 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 include (i) a method of performing a covering treatment 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 performing a covering treatment with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide and a thermosetting resin such as a phenol resin; (iii) and a method of coating a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide with a thermosetting resin such as a phenol resin.
Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine compounds, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. 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, cyanuramide (Japanese text: メロン), melam (Japanese text: メラム), succinylguanamine, ethylenedimelamine, melamine polyphosphate, and triguanamine, and further include, for example, (i) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, (ii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol, melamine, benzoguanamine, acetoguanamine (Japanese text: アセトグアナミン), melamine and formaldehyde, (iii) mixtures of phenol-formaldehyde condensates and co-condensates of (ii), phenol-formaldehyde condensates, and mixtures of phenol-formaldehyde condensates of (iii), (iv) And (ii) and (iii) further modified with tung oil, isomerized linseed oil, or the like.
Specific examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.
The amount of the nitrogen-based flame retardant to be blended may be appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the thermosetting composition, and the desired degree of flame retardancy, and for example, is preferably 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, based on 100 parts by mass of the thermosetting composition after all of the epoxy resin, the curing agent, the non-halogen-based flame retardant, the other filler, and the additive 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 oil, silicone rubber, and silicone resin.
The inorganic flame retardant may be used in 1 or 2 or more species, 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, and the like; boron compounds such as zinc borate, zinc metaborate, barium metaborate, boric acid, and borax; CEEPRE (Bokusui Brown corporation), hydrated glass SiO2-MgO-H2O、PbO-B2O3Is of ZnO-P series2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-O-F system, PbO-V system2O5-TeO2System, Al2O3-H2Low melting point glasses such as O-based and lead borosilicate-based glasses.
Examples of the organic metal salt-based flame retardant include ferrocene, acetylacetone metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, compounds obtained by ionic bonding or coordinate bonding of aromatic compounds or heterocyclic compounds to metal atoms, and the like.
The thermosetting composition of the present invention may further contain an organic solvent (F). When the thermosetting composition contains the organic solvent (F), the viscosity can be reduced, and the composition is particularly suitable for the production of a printed circuit board.
As the organic solvent (F), 1 or 2 or more kinds can be used, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as propylene glycol monomethyl ether; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl diethylene glycol acetate, carbitol acetate, and the like; carbitol solvents such as cellosolve, methyl cellosolve, butyl carbitol and the like; 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 a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; ether solvents such as propylene glycol monomethyl ether; acetate solvents such as propylene glycol monomethyl ether acetate and ethyl diethylene glycol acetate; carbitol solvents such as methyl cellosolve; amide solvents such as dimethylformamide, and the like.
When the thermosetting composition of the present invention is used for a build-up film, the organic solvent (F) is preferably a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like; carbitol solvents such as cellosolve, butyl carbitol and the like; 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, 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. By containing the conductive particles, the conductive paste can be used as a conductive paste, and is suitable for an anisotropic conductive material.
The thermosetting composition of the present invention may further contain a rubber, a filler, and the like. By containing rubber and filler, it becomes suitable for film formation.
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 can be obtained by mixing the above-mentioned components, and can be cured by heat to obtain a cured product. Examples of the shape of the cured product include a laminate, an injection molded product, an adhesive layer, a coating film, and a film.
Examples of applications of the thermosetting composition of the present invention include a semiconductor sealing material, a printed wiring board material, a resin molding material, an adhesive, an interlayer insulating material for a build-up substrate, and an adhesive film for build-up. Among the above applications, the insulating material for a printed wiring board, an insulating material for an electronic circuit board, and an adhesive film for build-up, can be used as an insulating material for a so-called electronic component-embedded substrate in which passive components such as a capacitor and active components such as an IC chip are embedded in a substrate. Among them, they are preferably used for a material for a printed wiring board and an adhesive film for build-up, because of their characteristics such as high heat resistance, low swelling property and solvent solubility.
The method for producing a semiconductor sealing material from the thermosetting composition of the present invention can be obtained by sufficiently melt-mixing the thermosetting resin (a), the thermosetting agent (B), the modified resin (C), and the components used as necessary until the components become uniform, using an extruder, a kneader, a roll mixer, or the like as necessary.
When the thermosetting composition of the present invention is used for a semiconductor encapsulating material, semiconductor encapsulation molding can be performed, and specifically, the composition can be injection molded or molded using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ℃ for 2 to 10 hours to obtain a semiconductor device as a molded product.
In addition, a method of manufacturing a printed circuit board using the thermosetting composition of the present invention includes a method of impregnating a reinforcing base material with the curable composition and laminating a copper foil and performing thermocompression bonding. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth (Japanese text: ガラスロービング cloth). More specifically, first, the thermosetting composition is heated (preferably 50 to 170 ℃ C. depending on the type of the organic solvent (F)), whereby a prepreg can be obtained as a cured product. In the prepreg, the content of the resin is preferably 20 mass% or more and 60 mass% or less. Then, the prepreg is laminated, a copper foil is laminated, and the laminated prepreg is heated and pressed at 170 to 300 ℃ under a pressure of 1 to 10MPa for 10 minutes to 3 hours to obtain a desired printed circuit board.
When the thermosetting composition of the present invention is used as a conductive paste, there may be mentioned, for example, a method of preparing a composition for an anisotropic conductive film by dispersing conductive particles (fine conductive particles) in the thermosetting composition; a paste resin composition for circuit connection which is liquid at room temperature and an anisotropic conductive adhesive are obtained.
As a method for obtaining the interlayer insulating material for a buildup substrate from the thermosetting composition of the present invention, for example, a method in which the thermosetting composition is applied to a wiring substrate having a circuit formed thereon by using a spin coating method, a curtain coating method or the like, and then cured. Thereafter, if necessary, a predetermined through hole portion or the like is formed, and then the surface is treated with a roughening agent, and then the surface is washed with hot water to form irregularities, and then plating treatment is performed with a metal such as copper. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations may be sequentially repeated as desired to form resin insulation layers and conductor layers of predetermined circuit patterns by alternately increasing the layers, thereby obtaining a build-up substrate. Wherein the opening of the through hole portion is performed after the outermost resin insulation layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the thermosetting composition on a copper foil can be pressed and heated at 170 to 300 ℃ onto a wiring substrate on which a circuit is formed, thereby forming a roughened surface and omitting a plating process to prepare a build-up substrate.
The method for producing a build-up film from the thermosetting composition of the present invention includes, for example, a method in which a build-up film for a multilayer printed wiring board is produced by applying the thermosetting composition of the present invention onto a support film to form a resin composition layer.
When the thermosetting composition of the present invention is used as a build-up film, it is important that the film is softened under the temperature conditions for lamination in the vacuum lamination method (usually 70 to 140 ℃), and the circuit board is laminated while exhibiting fluidity (resin fluidity) of a via hole (japanese text: ビアホール) or a via hole filling resin that can be present in the circuit board.
The through-hole of the multilayer printed wiring board is usually 0.1 to 0.5mm in diameter and 0.1 to 1.2mm in depth, and it is usually preferable that the through-hole can be filled with a resin within this range. When both surfaces of the circuit board are laminated, it is desirable that about 1/2 of the through hole is filled.
Specifically, the method for producing the adhesive film described above can be produced by preparing the thermosetting composition of the present invention in the form of varnish, applying the varnish-like composition to the surface of the support film (Y), and drying the organic solvent by heating, blowing hot air, or the like to form the layer (X) of the thermosetting composition.
The thickness of the layer (X) to be formed is usually not less than the thickness of the conductor layer, and the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70, and therefore, the thickness of the resin composition layer is preferably 10 to 100.
The layer (X) in the present invention may be protected by a protective film described later. The protective film can prevent adhesion and scratching of dust and the like on the surface of the resin composition layer.
Examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; a polycarbonate; a polyamide; further examples thereof include release paper; and metal foils such as copper foil and aluminum foil. The support film and the protective film may be subjected to matting treatment, corona treatment, or release treatment.
The thickness of the support film is not particularly limited, but is usually 10 to 150 a, and preferably 25 to 50 a. The thickness of the protective film is preferably 1 to 40 inches.
The support film (Y) may be laminated with a circuit board or may be peeled off after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is cured by heating, adhesion of dust and the like in the curing step can be prevented. When peeling is performed after curing, the support film is usually subjected to a mold release treatment in advance.
Next, in the case of using the adhesive film obtained as described above to manufacture a multilayer printed wiring board, for example, in the case of protecting the layer (X) with a protective film, the protective film is peeled off and then laminated on one surface or both surfaces of the circuit board by, for example, a vacuum lamination method so that the layer (X) is in direct contact with the circuit board. The lamination method may be a batch method or a continuous method using a roll. Before lamination, the adhesive film and the circuit board may be heated (preheated) as necessary.
Is laminatedThe pressure bonding temperature (laminating temperature) is preferably 70 to 140 ℃ and the pressure bonding pressure is preferably 1 to 11kgf/cm2(9.8×104～107.9×104N/m2) The lamination is preferably performed under reduced pressure of 20mmHg (26.7hPa) or less.
The method for obtaining the cured product of the present invention may be a method for curing a general thermosetting composition, and for example, the heating temperature condition may be appropriately selected depending on the kind and use of the curing agent to be combined, and the composition obtained by the above method may be heated at a temperature in the range of about 20 to 300 ℃.
Examples
The present invention will be described in more detail below with reference to examples.
Synthesis example 1 Synthesis of polyester resin A
A reaction apparatus was charged with 779.1 parts by mass of bisphenol A type glycol ether (trade name: HYPROX MDB-561, manufactured by DIC corporation), 132.9 parts by mass of isophthalic acid (hereinafter referred to as "iPA") and 40.4 parts by mass of sebacic acid (hereinafter referred to as "SebA"), and heating and stirring were started.
Then, the internal temperature was increased to 230 ℃, 0.10 part by mass of TiPT was added thereto, and the mixture was reacted at 230 ℃ for 24 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 36.9, a number average molecular weight of 3,040 and a glass transition temperature of-14 ℃.
Synthesis example 2 Synthesis of polyester resin B
395.6 parts by mass of ethylene glycol and 838.8 parts by mass of adipic acid were charged into the reactor, and heating and stirring were started.
Then, the internal temperature was increased to 220 ℃, 0.03 parts by mass of TiPT was added thereto, and the mixture was reacted at 220 ℃ for 24 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 56.2 and a number average molecular weight of 2,000, and showed no glass transition temperature.
[ Synthesis example 3] Synthesis of urethane resin A
1000.0 parts by mass of polytetramethylene glycol (trade name: PTMG-1000, manufactured by Mitsubishi chemical corporation) was charged into the reaction apparatus, and 128.8 parts by mass of toluene diisocyanate (trade name: COSMONATE-80, manufactured by Mitsubishi chemical SKC polyurethane Co., Ltd.) was charged. Subsequently, the temperature of the outside was raised to 80 ℃ and the reaction was continued for 10 hours to synthesize a urethane resin A.
The obtained urethane resin had a hydroxyl value of 28.0, a number average molecular weight of 4,010, and a glass transition temperature of-22 ℃.
[ example 1]
In a mixing vessel, 80 parts of an o-cresol novolac epoxy resin (trade name: EPICLON N-680, manufactured by DIC), 20 parts of a bisphenol A epoxy resin (trade name: EPICLON 850-S, manufactured by DIC), 50 parts of a novolac phenolic resin (trade name: Phenolate TD-2131, manufactured by DIC) as a curing agent, and 30 parts of the polyester having OH groups at both ends obtained in Synthesis example 1 were mixed and stirred at an internal temperature of 130 ℃ until compatible. 1 part of triphenylphosphine as a curing accelerator was added thereto, and the mixture was stirred for 20 seconds and then vacuum-defoamed to obtain an epoxy resin composition (X1) as a thermosetting composition of the present invention.
[ examples 2 and 3]
Epoxy resin compositions (X2) and (X3) as thermosetting compositions of the present invention were obtained in the same manner as in example 1 except that 45 parts by mass (example 2) and 60 parts by mass (example 3) of the polyester having OH groups at both ends (polyester resin a) obtained in synthesis example 1 were used.
[ example 4]
An epoxy resin composition (X4) as a thermosetting composition of the present invention was obtained in the same manner as in example 1 except that 30 parts by mass of the OH group both terminal polyurethane (urethane resin a) obtained in synthesis example 3 was used in place of 30 parts by mass of the OH group both terminal polyester (polyester resin a) obtained in synthesis example 1.
Comparative example 1
In a mixing vessel, 80 parts of o-cresol novolac epoxy resin (trade name: EPICLON-680, manufactured by DIC), 20 parts of bisphenol A epoxy resin (trade name: EPICLON 850-S, manufactured by DIC), and 50 parts of novolac phenol resin (trade name: Phenolate TD-2131, manufactured by DIC) as a curing agent were mixed and stirred at an internal temperature of 130 ℃ until compatible. 1 part of triphenylphosphine as a curing accelerator was added thereto, and the mixture was stirred for 20 seconds and then vacuum-defoamed to obtain an epoxy resin composition (Y1) of the present invention.
Comparative example 2
An epoxy resin composition (Y2) was obtained in the same manner as in example 1 except that 30 parts by mass of the polyester having OH groups at both ends (polyester resin a) obtained in synthesis example 2 was used in place of 30 parts by mass of the polyester having OH groups at both ends (polyester resin a) obtained in synthesis example 1.
The obtained epoxy resin compositions (X1) to (X4), (Y1) and (Y2) were evaluated as follows. The results are shown in table 1 together with the solubility parameters of the modified resin (C) used in each epoxy resin composition.
[ method for evaluating adhesion of copper foil ]
The epoxy resin compositions obtained in examples and comparative examples were poured into an injection-molded plate having a spacer made of rubber and having a thickness of 2mm sandwiched between glass plates having copper foils attached to one surfaces thereof at 130 ℃ and thermally cured at 175 ℃ for 5 hours. The resulting cured product was cut into a size of 10mm in width by 60mm in length, and the 90 ° peel strength was measured using a peel tester.
Measurement equipment: shimadzu AUTOGRAPH (product of Shimadzu corporation)
The model is as follows: AG-1
Test speed: 50mm/m
[ methods for evaluating glass transition temperature (Tg) and storage elastic modulus (E') ]
The epoxy resin compositions obtained in examples and comparative examples were poured into an injection-molded plate having a spacer made of rubber and having a thickness of 2mm sandwiched between glass plates at 130 ℃ and thermally cured at 175 ℃ for 5 hours. The resulting cured product was cut into a size of 5mm in width by 55mm in length, and the storage elastic modulus (E') and the loss elastic modulus (E ") were measured under the following conditions.
When E '/E' is defined as tan E, the temperature at which tan becomes maximum is defined as the glass transition temperature (Tg, unit:. degree. C.) and is measured.
In addition, the storage elastic modulus (E') at 25 ℃ was measured.
Measurement equipment: dynamic viscoelasticity measuring apparatus (SII Nano Technology, manufactured by SII Nano Technology Co., Ltd.)
The model is as follows: DMA6100
Measurement temperature range: 0 ℃ to 300 DEG C
Temperature rise rate: 5 ℃ per minute
Frequency: 1Hz
Measurement mode: bending of
[ method for evaluating fracture toughness ]
The epoxy resin compositions obtained in examples and comparative examples were poured into an injection-molded plate having a 4mm thick rubber spacer sandwiched between glass plates at 130 ℃ and thermally cured at 175 ℃ for 5 hours.
The resulting cured product was cut into pieces having a width of 13mm × and a length of 80mm × and a thickness of 4mm, processed according to ASTM D5045-93(ISO 13586), and subjected to fracture toughness (unit: MPa · m)0.5) The measurement of (1).
The notch (scale) of the test piece before the test was formed by placing the blade edge of the razor against the test piece and applying an impact to the blade edge of the razor with a hammer.
When the resin composition of the present invention is used as a semiconductor sealing material, the microscopic fracture toughness is often required to be improved, and the degree of the macroscopic fracture toughness evaluated by the present evaluation method may not be required, and the toughness improvement effect may be exhibited at a content lower than the content of the modified resin (C) in the present example.
Measurement equipment: shimadzu AUTOGRAPH (product of Shimadzu corporation)
The model is as follows: AG-X plus
Test speed: 10 mm/min
And (3) marking distance: 50mm
[ Table 1]
Figure BDA0002558035030000221
The epoxy resin compositions (X1) to (X4) of examples 1 to 4 are the thermosetting compositions of the present invention, and the resulting cured products thereof exhibit excellent heat resistance, copper foil adhesion, and toughness. On the other hand, comparative example 1 is an example containing no modified resin (C), and the copper foil adhesion and toughness were poor. Comparative example 2 is an example using a resin having no glass transition temperature, and any of the adhesion, heat resistance and toughness of the copper foil is poor.

Claims (11)

1. A thermosetting composition characterized by comprising a thermosetting resin, a thermosetting agent and a modified resin,
the modified resin is a thermoplastic resin having at least 1 selected from the group consisting of a hydroxyl group and a carboxyl group,
the glass transition temperature of the modified resin is-100 ℃ to 50 ℃,
the modified resin has a number average molecular weight of 600 or more and 50,000 or less.
2. The thermosetting composition according to claim 1,
the modified resin is at least 1 selected from polyester resin and polyurethane resin.
3. The thermosetting composition according to claim 1 or 2,
the modified resin has a hydroxyl value of 2mgKOH/g or more and 350mgKOH/g or less.
4. The thermosetting composition according to any one of claims 1 to 3,
the content of the modified resin is 0.1 to 60 parts by mass with respect to 100 parts by mass of the thermosetting resin.
5. The thermosetting composition according to any one of claims 1 to 4,
the modified resin has a solubility parameter of 9.0 (cal/cm)3)0.5Above and 10.5 (cal/cm)3)0 . 5The following.
6. An epoxy resin modifier characterized by being at least 1 resin selected from the group consisting of polyester resins and polyurethane resins and,
has a hydroxyl group, and has a hydroxyl group,
a glass transition temperature of-100 ℃ or higher and 50 ℃ or lower,
the number average molecular weight is 600 or more and 50,000 or less.
7. A cured product of the thermosetting composition according to any one of claims 1 to 5.
8. A semiconductor sealing material comprising the thermosetting composition according to any one of claims 1 to 5.
9. A prepreg which is a semi-cured product of an impregnated substrate having the thermosetting composition according to any one of claims 1 to 5 and a reinforcing substrate.
10. A circuit board comprising a copper foil and a sheet-like form of the thermosetting composition according to any one of claims 1 to 5.
11. A build-up film comprising a cured product of the thermosetting composition according to any one of claims 1 to 5 and a substrate film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114174422A (en) * 2019-08-23 2022-03-11 Dic株式会社 Resin composition, semiconductor sealing material using same, and dipping base material, circuit board, build-up film, prepreg, carbon fiber composite material, solder resist, dry film, and printed wiring board

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202110995A (en) * 2019-07-08 2021-03-16 日商Ｄｉｃ股份有限公司 Resin composition, prepreg, laminated plate, multilayer printed wiring board, and semiconductor package
JP7338413B2 (en) 2019-11-11 2023-09-05 味の素株式会社 resin composition
JP7287348B2 (en) 2020-05-28 2023-06-06 味の素株式会社 resin composition
JP7337462B2 (en) * 2020-06-15 2023-09-04 信越化学工業株式会社 epoxy resin composition
JP2023062672A (en) 2021-10-21 2023-05-08 Dic株式会社 Thermosetting composition, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-up film

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999051660A1 (en) * 1998-03-31 1999-10-14 Nippon Zeon Co., Ltd. Polyester, process for producing the same, and application thereof as polymer modifier
JP2002047445A (en) * 2000-08-02 2002-02-12 Sumika Bayer Urethane Kk Coating material composition and coated steel sheet made by using the same
JP2002179998A (en) * 2000-12-13 2002-06-26 Sumika Bayer Urethane Kk Coating composition and coated steel sheet using the same
JP2004131553A (en) * 2002-10-09 2004-04-30 Yokohama Tlo Co Ltd Epoxy resin composition
CN101125979A (en) * 2006-08-18 2008-02-20 无锡市雅丽涂料有限公司 Thermosetting fluorine-carbon resin for metal coiled material and coating thereof
WO2008143085A1 (en) * 2007-05-17 2008-11-27 Nitto Denko Corporation Epoxy resin composition for semiconductor encapsulation and semiconductor device obtained by using the same
CN101381510A (en) * 2007-09-07 2009-03-11 帝人化成株式会社 Thermoplastic resin compositions
CN103228703A (en) * 2010-12-16 2013-07-31 旭化成电子材料株式会社 Curable resin composition
US20150337125A1 (en) * 2014-05-23 2015-11-26 Albemarle Corporation Brominated Flame Retardants and their use in Thermoplastic and Thermosetting Flammable Materials
CN105324439A (en) * 2013-06-28 2016-02-10 三井化学株式会社 Molding resin composition
WO2017073309A1 (en) * 2015-10-27 2017-05-04 Ｄｉｃグラフィックス株式会社 Low-temperature baking-adapted resist ink
WO2017195304A1 (en) * 2016-05-11 2017-11-16 日立化成株式会社 Liquid resin composition for encapsulation and electronic component/device

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000063638A (en) 1998-08-24 2000-02-29 Showa Electric Wire & Cable Co Ltd Damping material
JP2009138116A (en) 2007-12-07 2009-06-25 Daicel Chem Ind Ltd Cation-polymerizable resin composition and cured material thereof
JP5547376B2 (en) 2008-03-19 2014-07-09 関西ペイント株式会社 Rust preventive paint composition
EP2145924A1 (en) 2008-07-18 2010-01-20 Sika Technology AG Reaction products based on amphiphilic block copolymers and use thereof as impact modifiers
TWI540170B (en) 2009-12-14 2016-07-01 Ajinomoto Kk Resin composition
TWI694109B (en) 2013-06-12 2020-05-21 日商味之素股份有限公司 Resin composition
JP6819062B2 (en) 2016-03-28 2021-01-27 昭和電工マテリアルズ株式会社 Thermosetting resin composition, prepreg using it, film with resin, laminated board, printed wiring board and semiconductor package, and imide resin and its manufacturing method.
JP6904125B2 (en) 2017-07-18 2021-07-14 味の素株式会社 Resin composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999051660A1 (en) * 1998-03-31 1999-10-14 Nippon Zeon Co., Ltd. Polyester, process for producing the same, and application thereof as polymer modifier
JP2002047445A (en) * 2000-08-02 2002-02-12 Sumika Bayer Urethane Kk Coating material composition and coated steel sheet made by using the same
JP2002179998A (en) * 2000-12-13 2002-06-26 Sumika Bayer Urethane Kk Coating composition and coated steel sheet using the same
JP2004131553A (en) * 2002-10-09 2004-04-30 Yokohama Tlo Co Ltd Epoxy resin composition
CN101125979A (en) * 2006-08-18 2008-02-20 无锡市雅丽涂料有限公司 Thermosetting fluorine-carbon resin for metal coiled material and coating thereof
WO2008143085A1 (en) * 2007-05-17 2008-11-27 Nitto Denko Corporation Epoxy resin composition for semiconductor encapsulation and semiconductor device obtained by using the same
CN101381510A (en) * 2007-09-07 2009-03-11 帝人化成株式会社 Thermoplastic resin compositions
CN103228703A (en) * 2010-12-16 2013-07-31 旭化成电子材料株式会社 Curable resin composition
CN105324439A (en) * 2013-06-28 2016-02-10 三井化学株式会社 Molding resin composition
US20150337125A1 (en) * 2014-05-23 2015-11-26 Albemarle Corporation Brominated Flame Retardants and their use in Thermoplastic and Thermosetting Flammable Materials
WO2017073309A1 (en) * 2015-10-27 2017-05-04 Ｄｉｃグラフィックス株式会社 Low-temperature baking-adapted resist ink
WO2017195304A1 (en) * 2016-05-11 2017-11-16 日立化成株式会社 Liquid resin composition for encapsulation and electronic component/device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DUMONT, DAVID 等: "Interdiffusion of thermoplastics and epoxy resin precursors: investigations using experimental and molecular dynamics methods", 《POLYMER INTERNATIONAL》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114174422A (en) * 2019-08-23 2022-03-11 Dic株式会社 Resin composition, semiconductor sealing material using same, and dipping base material, circuit board, build-up film, prepreg, carbon fiber composite material, solder resist, dry film, and printed wiring board
CN114174422B (en) * 2019-08-23 2024-04-30 Dic株式会社 Resin composition and use thereof

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