Resin composition and cured product thereof, impregnated substrate, prepreg, laminate, printed wiring board, and semiconductor package

Abstract

The invention provides a resin composition, a cured product of the resin composition, an impregnated base material, a prepreg, a laminated plate, a printed wiring board and a semiconductor package, wherein the resin composition can exert a stress relaxation effect caused by low elasticity modulus while maintaining the heat resistance of the resin, and meanwhile, the copper foil sealing property is more excellent; the cured product of the resin composition is impregnated base material, the prepreg, the laminated plate, the printed wiring board and the semiconductor package. This resin composition contains (A) a resin having a radical polymerizable group, (B) a thermoplastic resin, and (C) a radical polymerization initiator, and is characterized in that: the resin having a radical polymerizable group (A) contains a vinyl ester resin, an unsaturated polyester resin, or a polyphenylene ether resin having a radical polymerizable group; the thermoplastic resin (B) comprises at least one selected from the group consisting of a polyester polyol and a polyurethane polyol, and a cured product of the resin composition forms a phase separation structure.

Description

[0001] The present invention is a divisional application of the invention patent application with application number 202080040277.0 filed on July 2, 2020 and invention name “Impregnated substrate, prepreg, laminate, printed wiring board and semiconductor package”. Technical Field

[0002] The present invention relates to a resin composition and a cured product thereof, an impregnated substrate, a prepreg, a laminate, a multilayer printed wiring board and a semiconductor package. Background Art

[0003] Radical polymerizable resins have a good balance of mechanical strength, chemical durability, electrical properties, etc., and are widely used in industrial fields such as construction, machinery, automobiles, ships, semiconductors, etc. As such a radical polymerizable resin composition, for example, a laminated board is proposed, which is obtained by impregnating a fiber-reinforced layer with a thermosetting resin composition containing a radical polymerizable resin, a thermoplastic resin, a radical polymerizable monomer, and an inorganic filler in a specific ratio and curing the resulting layer (see Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2001 / 072879 Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, the conventionally known free radical polymerizable resin composition has insufficient adhesion to the copper foil with low surface roughness used in the copper clad laminate, and there is also a problem of residual stress caused by the difference in linear expansion coefficient between the copper foil and the resin part, which sometimes causes problems in warping of the laminate, reduction in adhesion reliability at the copper foil / resin interface, and generation of cracks. The present invention has been made in view of the above circumstances, and its subject is to provide a resin composition that exhibits a stress relaxation effect due to a low elastic modulus while maintaining the heat resistance of the resin and has better adhesion to the copper foil.

[0009] Technical means of solving problems

[0010] The resin composition of the present invention comprises a resin (A) having a free radical polymerizable group, a thermoplastic resin (B), and a free radical polymerization initiator (C), wherein the resin (A) having a free radical polymerizable group comprises a vinyl ester resin, an unsaturated polyester resin, or a polyphenylene ether resin having a free radical polymerizable group, and the thermoplastic resin (B) comprises at least one selected from the group consisting of a polyester polyol and a polyurethane polyol, and a cured product of the resin composition forms a phase separation structure.

[0011] Effects of the Invention

[0012] By using the resin composition of the present invention, it is possible to provide a resin composition which exhibits a stress relaxation effect due to a low elastic modulus while maintaining the heat resistance of the resin and has further excellent copper foil adhesion. DETAILED DESCRIPTION

[0013] The resin composition of the present invention contains a resin (A) having a radical polymerizable group, a thermoplastic resin (B), and a radical polymerization initiator (C).

[0014] The resin (A) having a free radical polymerizable group may be any resin having a free radical polymerizable group (a group having an ethylenically unsaturated bond) in the molecule, and may include one or more resins. Examples of the resin (A) having a free radical polymerizable group include vinyl ester resins, unsaturated polyester resins, and polyphenylene ether resins having a free radical polymerizable group.

[0015] The vinyl ester resin is preferably a reaction product of an epoxy resin and an unsaturated carboxylic acid.

[0016] As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferred. As the epoxy resin, one or more kinds of epoxy resins can be used, for example, bisphenol epoxy resins, phenylene ether epoxy resins, naphthylene ether epoxy resins, biphenyl epoxy resins, triphenylmethane epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol novolac epoxy resins, naphthol novolac epoxy resins, naphthol-phenol co-decanoic acid novolac epoxy resins, naphthol-cresol co-decanoic acid novolac epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, etc. can be listed.

[0017] The unsaturated carboxylic acid is a compound having one carboxyl group and one or more ethylenically unsaturated groups in one molecule, and examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid.

[0018] The vinyl ester resin is preferably a (meth)acrylic acid adduct of an epoxy resin.

[0019] The number average molecular weight of the vinyl ester resin is preferably 500 or more, more preferably 1,000 or more, and is preferably 5,000 or less, more preferably 3,000 or less.

[0020] In the present invention, the number average molecular weight of the vinyl ester resin is a value measured by gel permeation chromatography as a converted value using polystyrene as a standard sample.

[0021] The unsaturated polyester resin is preferably a dehydration condensation product of an unsaturated dicarboxylic acid or an anhydride thereof and a diol.

[0022] Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid.

[0023] The diol may be any compound having two hydroxyl groups in one molecule, and examples thereof include alkane diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and cyclohexanediol; oxyalkane diols such as dioxyethylene glycol, dipropylene glycol, and triethylene glycol; and alkane diol adducts of bisphenol compounds (such as bisphenol A).

[0024] The unsaturated polyester resin is preferably a dehydration condensation product of an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, or mesaconic acid and a diol.

[0025] The number average molecular weight of the unsaturated polyester resin is preferably 500 or more, more preferably 1,000 or more, and is preferably 5,000 or less, more preferably 3,000 or less.

[0026] In the present invention, the number average molecular weight of the unsaturated polyester resin is a value measured by gel permeation chromatography as a converted value using polystyrene as a standard sample.

[0027] The polyphenylene ether resin has at least one free radical polymerizable group. Examples of the free radical polymerizable group include vinyl and allyl groups. The polyphenylene ether resin is preferably represented by the following formula (1). In the polyphenylene ether resin, each structural unit may include one or more than two structural units, and the repetition order of each structural unit is not particularly limited.

[0028] [Chemistry 1]

[0029]

[0030] [In formula (1), Ar 1 ,Ar 2 ,Ar 3 Each independently represents an aromatic hydrocarbon group which may have a substituent, and in Ar 1 ,Ar 2 ,Ar 3 A free radical polymerizable group is added to at least one of L 1 , L 2 Each independently represents a single bond or a hydrocarbon group. n represents an integer greater than 1, and when n is greater than 2, the structural units in parentheses to which n is attached may be the same or different.]

[0031] As Ar 1 ,Ar 2 Examples of the aromatic hydrocarbon group represented include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl and naphthyl.

[0032] As Ar 3 Examples of the aromatic hydrocarbon group represented by include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenylene and biphenylene.

[0033] As the Ar 3 The substituents that the aromatic hydrocarbon group represented may have include: alkyl groups having 1 to 9 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 1-methylpentyl, 1-ethylpentyl, etc.; cycloalkyl groups having 1 to 9 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; alkenyl groups having 2 to 9 carbon atoms, such as vinyl, allyl, isopropenyl, butenyl, etc.; alkynyl groups having 2 to 9 carbon atoms, such as propynyl and butynyl, etc.; aromatic hydrocarbon groups having 1 to 9 carbon atoms, such as phenyl, etc.; and carbon atoms formed by combining one or more of these groups. a group having 1 to 9 atoms; a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a hydroxyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group such as a dimethylamino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an alkoxy group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; a nitro group; an aryl group such as a phenyl group, a 4-chlorophenyl group, and a naphthyl group; and the like.

[0034] As L 1 , L 2Examples of the hydrocarbon groups represented include: alkane diyl groups having 1 to 20 carbon atoms, such as methylene, ethylene, propane diyl, and hexane diyl; cyclopropane diyl groups; cycloalkane diyl groups having 3 to 20 carbon atoms, such as cyclohexane diyl groups; vinylene groups; alkene diyl groups having 2 to 20 carbon atoms, such as isopropane diyl groups; alkyne diyl groups having 2 to 20 carbon atoms, such as propynylene groups; aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenylene and 2,6-naphthylene groups, etc. In the present invention, the aromatic hydrocarbon groups are assumed to include hydrocarbon groups containing aromatic rings.

[0035] In the polyphenylene ether resin, the radical polymerizable group is preferably added to Ar 1 and Ar 2 at least one of .

[0036] The number average molecular weight of the polyphenylene ether resin is preferably 500 or more, more preferably 1,000 or more, and is preferably 5,000 or less, more preferably 3,000 or less.

[0037] In the present invention, the number average molecular weight of the polyphenylene ether resin is a value measured by gel permeation chromatography as a converted value using polystyrene as a standard sample.

[0038] In the resin (A) having a free radical polymerizable group, the total content of the vinyl ester resin, the unsaturated polyester resin and the polyphenylene ether resin having a free radical polymerizable group is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and the upper limit is 100% by mass.

[0039] The thermoplastic resin (B) includes at least one selected from the group consisting of polyester polyol (B1) and polyurethane polyol (B2).

[0040] The polyester polyol (B1) is a polymer having an ester bond in the molecular chain and having two or more hydroxyl groups in one molecule. The number of hydroxyl groups in the polyester polyol is two or more, preferably five or less, and more preferably four or less per molecule.

[0041] Examples of the polyester polyol (B1) include: polyester polyols obtained by esterifying a low molecular weight polyol (e.g., a polyol having a molecular weight of 50 to 300) with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone; polyester polyols obtained by reacting (adding) a lactone compound with one or more selected from the group consisting of polyether polyols, polyester polyols, and polycarbonate polyols and / or a low molecular weight polyol used in the production of the polyester polyol as an initiator; copolyester polyols thereof, and the like.

[0042] As the low molecular weight polyol used in the production of the polyester polyol (B1), a polyol having a molecular weight of about 50 to 300 can be used, for example: aliphatic polyols (diols or trifunctional or higher polyols) having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, trimethylolpropane, glycerol, etc.; polyols containing an alicyclic structure such as 1,4-cyclohexanediol and cyclohexanedimethanol; polyols containing an aromatic structure such as bisphenol compounds such as bisphenol A and bisphenol F and alkylene oxide adducts thereof, etc.

[0043] Examples of the polycarboxylic acid used in the production of the polyester polyol (B1) 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 anhydride- or ester-forming derivatives of the aliphatic polycarboxylic acids and aromatic polycarboxylic acids.

[0044] As the lactone compound, one or more kinds can be used, for example, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, β-dimethyl-ε-caprolactone, δ-dimethyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, enantholactone (7-heptanolide), dodecanolactone (12-dodecanolide), etc. can be used.

[0045] The addition rate of the lactone compound is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 200% by mass or less, more preferably 100% by mass or less, relative to a total of 100 parts by mass of one or more selected from the group consisting of the polyether polyol, the polyester polyol, and the polycarbonate polyol and / or the low molecular weight polyol.

[0046] The number average molecular weight of the polyester polyol (B1) is preferably 600 or more, more preferably 1000 or more, and even more preferably 1500 or more, and is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 10,000 or less.

[0047] The number average molecular weight of the polyester polyol (B1) can be calculated based on the hydroxyl value. The hydroxyl value can be measured in accordance with Japanese Industrial Standards (JIS) K 1557-1:2007.

[0048] The polyurethane polyol (B2) is a polymer having at least a urethane bond in the molecular chain and having two or more hydroxyl groups in one molecule. The number of hydroxyl groups in the polyester polyol is two or more, preferably five or less, and more preferably four or less per molecule.

[0049] The polyurethane polyol (B2) is preferably a reaction product of a polyol compound (a) and a polyisocyanate compound (b).

[0050] As the polyol compound (a), one or more kinds can be used, preferably including polymer polyols. As the polymer polyols, polyether polyols, polyester polyols, polycarbonate polyols, etc. can be listed, preferably including at least one selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols, and preferably including at least polyester polyols.

[0051] The polyether polyol is preferably a polyoxyalkylene polyol, and examples thereof include polyether polyols obtained by ring-opening polymerization of cyclic ethers such as alkylene oxides using one or two or more compounds having two or more active hydrogen atoms as an initiator as necessary.

[0052] The number of carbon atoms of the cyclic ether is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4. The hydrogen atoms contained in the cyclic ether may be substituted by halogen atoms. As the cyclic ether, one or more types may be used, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, alkylated tetrahydrofuran, etc.

[0053] As the initiator, one or more than one may be used, for example, compounds having two active hydrogen atoms such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and water; compounds having three or more active hydrogen atoms such as glycerol, diglycerol, trimethylolethane, trimethylolpropane, hexanetriol, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, pentaerythritol, and carbohydrates; and the like.

[0054] As the polyester polyol, the same compounds as those described as the polyester polyol (B1) can be used.

[0055] Examples of the polycarbonate polyol include a reaction product of a carbonate and a polyol; a reaction product of phosgene and bisphenol A, and the like.

[0056] Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, and diphenyl carbonate.

[0057] Examples of the polyol that can react with the carbonate include the polyols exemplified as the low molecular weight polyols, and high molecular weight polyols (weight average molecular weight of 500 to 5,000) such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.).

[0058] The polymer polyol preferably has a functionality of 2 or more and 5 or less.

[0059] The number average molecular weight of the polymer polyol is preferably 300 or more, more preferably 500 or more, and further preferably 700 or more, and is preferably 10,000 or less, more preferably 7,000 or less, and further preferably 5,000 or less.

[0060] The number average molecular weight of the polymer polyol can be calculated based on the hydroxyl value. The hydroxyl value can be measured in accordance with JIS K1557-1:2007.

[0061] As the polyisocyanate compound (b), one or more kinds can be used, for example, polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylene diisocyanate, and tetramethylxylene diisocyanate.

[0062] The number of isocyanate groups contained in one molecule of the polyisocyanate compound (b) is 2 or more, preferably 5 or less, and more preferably 3 or less.

[0063] The equivalent ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate compound (b) to the hydroxyl group contained in the polyol compound (a1) is preferably 0.1 or more, more preferably 0.2 or more, and is preferably 0.9 or less, more preferably 0.8 or less, and particularly preferably 0.7 or less.

[0064] The hydroxyl value of the polyurethane polyol (B2) is preferably 11 mgKOH / g or more, more preferably 16 mgKOH / g or more, and even more preferably 23 mgKOH / g or more, and is preferably 225 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 112 mgKOH / g or less.

[0065] The number average molecular weight of the polyurethane polyol (B2) is 500 or more, more preferably 1000 or more, further preferably 1500 or more, particularly preferably 2000 or more, and is preferably 10000 or less, more preferably 7000 or less, further preferably 5000 or less.

[0066] The number average molecular weight of the polyurethane polyol (B2) can be calculated based on the hydroxyl value. The hydroxyl value can be measured in accordance with JIS K 1557-1:2007.

[0067] The solubility parameter of the polyester polyol (B1) and the polyurethane polyol (B2) is 9 (cal / cm 3 ) 0.5 Above, preferably 9.1 (cal / cm 3 ) 0.5 More preferably, 9.4 (cal / cm 3 ) 0.5 More preferably, 9.9 (cal / cm 3 ) 0.5 Above, and preferably 13 (cal / cm 3 ) 0.5 Below, more preferably 11 (cal / cm 3 ) 0.5 Below, more preferably 10.5 (cal / cm 3 ) 0.5 When the solubility parameters of the polyester polyol (B1) and the polyurethane polyol (B2) are within the above ranges, phase separation is easily induced in the obtained cured product.

[0068] The solubility parameters of the polyester polyol (B1) and the polyurethane polyol (B2) can be calculated based on the method of Fedors (Polymer Engineering and Science, 1974, vol. 14, No. 2) to obtain the solubility parameters of the units derived from the respective compounds used as raw materials for the polyester polyol (B1) and the polyurethane polyol (B2) as a weighted average value based on the ratio of the mass basis of the units derived from the respective compounds.

[0069] In the thermoplastic resin (B), the total content of the polyester polyol (B1) and the polyurethane polyol (B2) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and is preferably 100% by mass or less.

[0070] The glass transition temperature of the thermoplastic resin (B) is preferably -100°C or higher, more preferably -80°C or higher, and further preferably -70°C or higher, and is preferably 50°C or lower, more preferably 40°C or lower, and further preferably 30°C or lower. In addition, when the thermoplastic resin (B) contains two or more resins, the weighted average of the glass transition temperatures of the respective resins is preferably -100°C or higher, more preferably -80°C or higher, and further preferably -70°C or higher, and is preferably -50°C or lower, more preferably -40°C or lower, and further preferably -30°C or lower. Furthermore, when the thermoplastic resin (B) contains two or more resins, it is preferred that the glass transition temperature of each of the two or more resins is within the above range.

[0071] The number average molecular weight of the thermoplastic resin (B) is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more, and is preferably 30,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less. When the thermoplastic resin (B) contains two or more resins, the weighted average of the number average molecular weights of the respective resins is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more, and is preferably 30,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less. In addition, when the thermoplastic resin (B) contains two or more resins, it is preferred that the number average molecular weight of each of the two or more resins is within the above range.

[0072] The solubility parameter of the thermoplastic resin (B) is preferably 9.0 (cal / cm 3 ) 0.5 More preferably, 9.7 (cal / cm 3 ) 0.5 More preferably, 9.5 (cal / cm 3 ) 0.5 Above, and preferably 10.5 (cal / cm 3 ) 0.5 Below, more preferably 10.4 (cal / cm 3 ) 0.5 Below, more preferably 10.2 (cal / cm 3 ) 0.5 the following.

[0073] The solubility parameter of the thermoplastic resin (B) can be determined as a weighted average based on the solubility parameter and mass fraction of each component contained in the thermoplastic resin (B) according to the method of Fedors (Polymer Engineering and Science, 1974, vol. 14, No. 2).

[0074] The content of the thermoplastic resin (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less, relative to 100 parts by mass of the resin (A) having a free radical polymerizable group.

[0075] The radical polymerization initiator (C) may be used alone or in combination of two or more, and examples thereof include peroxide initiators and azo initiators.

[0076] Examples of the peroxide initiator include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0077] Examples of the azo initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethacrylonitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0078] The content of the radical polymerization initiator (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more, relative to 100 parts by mass of the resin (A) having a radical polymerizable group, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less.

[0079] The resin composition may further include a radical polymerizable monomer (D). Examples of the radical polymerizable monomer (D) include compounds having one or more radical polymerizable groups, specifically, unsaturated fatty acids such as (meth)acrylic acid; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, glycidyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; nitrogen-containing (meth)acrylic monomers such as (meth)acrylamide and (meth)acrylonitrile; aromatic vinyl compounds such as styrene, vinyltoluene, divinylbenzene, and p-tert-butylstyrene; and polyfunctional (meth)acrylic monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0080] When the radical polymerizable monomer (D) is contained, the content thereof is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, based on 100 parts by mass of the resin (A) having a radical polymerizable group.

[0081] The resin composition may contain other additives (E) in addition to the resin having a radical polymerizable group (A), the thermoplastic resin (B), and the radical polymerization initiator (C).

[0082] Examples of the other additives include inorganic particles; antioxidants; light stabilizers such as hindered amine light stabilizers; ultraviolet absorbers; retarders; release agents; other thermoplastic resins; softeners and plasticizers such as paraffin-based processing oils, cycloparaffin-based processing oils, aromatic processing oils, organic polysiloxanes, mineral oils, etc.; flame retardants; silane coupling agents; emulsifiers; conductive particles; antistatic agents; organic fibers; organic fillers such as resin particles and rubber; inorganic fillers such as pigments such as iron oxide; reinforcing agents such as glass fibers, carbon fibers, and metal whiskers; low shrinkage agents; colorants; body pigments; thixotropy imparting agents; organic phosphorus compounds such as phosphites, phosphonates, and phosphates; leveling agents; surfactants, etc.

[0083] In the resin composition, the content of the other additive (E) is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and may be 0% by mass.

[0084] The resin composition of the present invention is obtained by mixing a resin (A) having a free radical polymerizable group, a thermoplastic resin (B), a free radical polymerization initiator (C), and a free radical polymerizable monomer (D) or other additives (E) used as needed, and a cured product can be obtained by free radical polymerization. Free radical polymerization can be thermal polymerization or polymerization using active energy lines. As the shape of the cured product, laminates, castings, adhesive layers, coatings, films, composites impregnated in a reinforcing substrate (impregnated substrates), etc. can be listed, and the composite (impregnated substrate) can also be a prepreg as a semi-cured product.

[0085] The cured product of the resin composition forms a phase separation structure. When the resin (A) having a free radical polymerizable group, the thermoplastic resin (B), and the free radical polymerization initiator (C) are mixed, it is preferred that these components and other components used as needed form a uniform phase. The mechanism for forming a phase separation structure in the cured product is not clear, but it is speculated as follows. That is, it is believed that as the polymerization of the free radical polymerizable group (A) proceeds, the molecular weight of the polymer derived from the resin (A) having a free radical polymerizable group increases, and the mobility of the entire system is limited. As a result, the compatibility of the polymer derived from the resin (A) having a free radical polymerizable group and the thermoplastic resin (B) decreases, thereby phase separation occurs (forming a phase separation structure).

[0086] The phase separation structure may be a sea-island structure or a co-continuous structure. The presence or absence of phase separation in the hardened material can be confirmed by observing the fracture surface of the hardened material using an atomic force microscope (AFM) to determine whether two phases with different elastic moduli form a sea portion and an island portion, or form a co-continuous structure.

[0087] In the phase separation structure, the minor diameter of the phase with a low elastic modulus is, for example, 500 nm or less, preferably 200 nm or less, more preferably 100 nm or less, and, for example, 1 nm or more, preferably 10 nm or more.

[0088] As the reinforcing substrate, glass fiber nonwoven fabric, glass fiber woven fabric, paper substrate, etc. can be used.

[0089] The laminated body formed by stacking the impregnated substrate is also included in the technical scope of the present invention. As the laminated body, for example, it is preferred to have three or more layers of the impregnated substrate, and the reinforcing substrate in each layer is preferably different between the layers (for example, a composite laminated board stacked in the order of glass fiber woven fabric, glass fiber non-woven fabric, and paper substrate from the surface). Examples include a laminated body obtained by stacking metal foil (such as copper foil, etc.) on both sides of the laminated body as needed, and then compressing and heating the laminated body of the metal foil and the impregnated substrate.

[0090] As the purpose of the resin composition of the present invention, it is possible to cite: semiconductor sealing materials, printed wiring board materials, resin casting materials, adhesives, semiconductor packages, etc. In the above-mentioned purposes, in the use of printed wiring board or electronic circuit substrate insulating materials, it can be used as an insulating material for so-called electronic component built-in substrates for embedding passive parts such as capacitors or active parts such as IC chips into substrates. Among them, in terms of characteristics such as high heat resistance, low thermal expansion, and solvent solubility, it is preferably used for printed wiring board materials, etc.

[0091] Example

[0092] Hereinafter, the present invention will be described in more detail with reference to examples.

[0093] [Synthesis Example 1] Synthesis of polyester resin A

[0094] 779.1 parts by mass of bisphenol A type glycol ether (manufactured by DIC Corporation, "PANDEX (trademark) MB-601"), 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") were added to the reaction apparatus, and heating and stirring were started. Then, after the internal temperature was raised to 230°C, 0.10 parts by mass of TiPT was added, and the reaction was carried out at 230°C for 24 hours to synthesize a polyester resin.

[0095] The obtained polyester resin had a hydroxyl value of 36.9 and a number average molecular weight of 3,040.

[0096] [Synthesis Example 2] Synthesis of polyester resin B

[0097] 886.9 parts by mass of bisphenol A type diol ether (manufactured by Nippon Emulsifier Co., Ltd., "BA-P13U diol"), 109.4 parts by mass of iPA, and 33.3 parts by mass of SebA were added to the reaction apparatus, and heating and stirring were started. Then, after the internal temperature was raised to 230°C, 0.10 parts by mass of TiPT was added, and the reaction was carried out at 230°C for 24 hours to synthesize a polyester resin.

[0098] The obtained polyester resin had a hydroxyl value of 15.5 and a number average molecular weight of 7,240.

[0099] [Synthesis Example 3] Synthesis of Polyester Resin C

[0100] 430.9 parts by mass of 3-methyl-1,5-pentanediol and 692.4 parts by mass of SebA were added to the reaction apparatus, and heating and stirring were started. Then, after the internal temperature was raised to 220° C., 0.03 parts by mass of TiPT was added, and the reaction was carried out at 220° C. for 12 hours to synthesize a polyester resin.

[0101] The obtained polyester resin had a hydroxyl value of 15.0 and a number average molecular weight of 4,488.

[0102] [Synthesis Example 4] Synthesis of urethane resin A

[0103] 1,000.0 parts by mass of polytetramethylene glycol (manufactured by Mitsubishi Chemical Co., Ltd., "PTMG-1000") and 128.8 parts by mass of toluene diisocyanate (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., "Cosmonate (trademark) T-80") were added to the reaction apparatus. Then, the temperature was raised to an external temperature of 80°C, and the reaction was continued for 10 hours to synthesize urethane resin A.

[0104] The hydroxyl value of the obtained urethane resin was 28.0 and the number average molecular weight was 4,010.

[0105] [Example 1]

[0106] 100 parts by mass of a vinyl ester resin (manufactured by DIC Corporation, "Epiclon (trademark) CE-330-IM") as an epoxy resin and 10 parts by mass of the polyester having OH groups at both ends obtained in Synthesis Example 1 were mixed in a mixing container and stirred until they were compatible. 1.25 parts by mass of a polymerization initiator (manufactured by NOF Corporation, "Percumyl (trademark) H-80") was added, stirred, and vacuum degassing was performed to obtain a vinyl ester resin composition (X1) of the present invention.

[0107] The vinyl ester resin composition was poured into a casting plate at room temperature, and heat-cured at 100° C. for 1 hour, and then heat-cured at 170° C. for 2 hours. The casting plate was formed by sandwiching a 2 mm thick rubber partition between glass plates. The fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and it was confirmed that a sea portion and an island portion were formed.

[0108] [Example 2]

[0109] An epoxy resin composition (X2) as a thermosetting composition of the present invention was obtained in the same manner as in Example 1 except that 20 parts by mass of the polyester having OH groups at both ends (polyester resin A) obtained in Synthesis Example 1 was used. In the same manner as in Example 1, the fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and it was confirmed that two phases having different elastic moduli formed a co-continuous structure.

[0110] [Example 3]

[0111] An epoxy resin composition (X3) as a thermosetting composition of the present invention was obtained in the same manner as in Example 1, except that 10 parts by mass of the polyester having OH groups at both ends (polyester resin B) obtained in Synthesis Example 2 was used instead of 10 parts by mass of the polyester having OH groups at both ends (polyester resin A) obtained in Synthesis Example 1. In the same manner as in Example 1, the fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and it was confirmed that two phases having different elastic moduli formed a co-continuous structure.

[0112] [Example 4]

[0113] 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 10 parts by mass of the polyester having OH groups at both ends (polyester resin C) obtained in Synthesis Example 3 was used instead of 10 parts by mass of the polyester having OH groups at both ends (polyester resin A) obtained in Synthesis Example 1. In the same manner as in Example 1, the fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and it was confirmed that two phases having different elastic moduli formed a sea portion and an island portion.

[0114] [Example 5]

[0115] An epoxy resin composition (X5) as a thermosetting composition of the present invention was obtained in the same manner as in Example 1, except that 10 parts by mass of the polyurethane (urethane resin A) having OH groups at both ends obtained in Synthesis Example 4 was used instead of 10 parts by mass of the polyester (polyester resin A) having OH groups at both ends obtained in Synthesis Example 1. In the same manner as in Example 1, the fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and it was confirmed that two phases having different elastic moduli formed a sea portion and an island portion.

[0116] [Comparative Example 1]

[0117] In a mixing container, 1.25 parts by mass of a polymerization initiator (manufactured by NOF Corporation, "Percumyl (trademark) H-80") is added to 100 parts by mass of a vinyl ester resin (manufactured by DIC Corporation, "Epiclon (Trademark) CE-330-IM") as an epoxy resin, and after stirring, vacuum degassing is performed to obtain the vinyl ester resin composition (Y1) of the present invention.

[0118] The vinyl ester resin composition was poured into a casting plate at room temperature, and heat-cured at 100° C. for 1 hour and then at 170° C. for 2 hours. The casting plate was formed by sandwiching a 2 mm thick rubber partition wall between glass plates. The fracture surface of the obtained cured product was observed by atomic force microscopy (AFM), and no phase separation structure was observed.

[0119] [Comparative Example 2]

[0120] The vinyl ester resin composition (Y2) of the present invention was obtained in the same manner as in Example 1 except that 10 parts by mass of a polyester having OH groups at both ends (manufactured by DIC Corporation, "Polylitte (trademark) OD-X-2921", hydroxyl value 208, number average molecular weight 540) was used instead of 10 parts by mass of the polyester having OH groups at both ends (polyester resin A) obtained in Synthesis Example 1. The fracture surface of the obtained cured product was observed by atomic force microscopy (AFM) in the same manner as in Comparative Example 1, but no phase separation structure was observed.

[0121] [Comparative Example 3]

[0122] A vinyl ester resin composition (Y3) of the present invention was obtained in the same manner as in Example 1, except that 10 parts by mass of carboxylic acid-terminated polybutadiene (manufactured by Okamoto Oil Manufacturing Co., Ltd., "SB-20", number average molecular weight 350) was used instead of 10 parts by mass of the polyester having OH groups at both ends (polyester resin A) obtained in Synthesis Example 1. The fracture surface of the obtained cured product was observed by atomic force microscopy (AFM) in the same manner as in Comparative Example 1, but no phase separation structure was observed.

[0123] [Evaluation method of glass transition temperature (Tg) and storage elastic modulus (E')]

[0124] The vinyl ester resin compositions obtained in the examples and comparative examples were poured into a casting plate at room temperature, and heat-cured at 100°C for 1 hour and then at 170°C for 2 hours. The casting plate was formed by sandwiching a 2 mm thick rubber partition wall between glass plates. The obtained cured product was cut into a size of 5 mm wide × 55 mm long, and the storage elastic modulus (E') and loss elastic modulus (E") were measured under the following conditions.

[0125] When E' / E" is defined as tan δ, the temperature at which tan δ is maximum is measured as the glass transition temperature (Tg, unit: °C).

[0126] In addition, the storage elastic modulus (E') at 25°C was measured.

[0127] Measuring equipment: Dynamic viscoelasticity measuring machine (manufactured by SII Nanotechnology Co., Ltd.)

[0128] Model: DMA6100

[0129] Measuring temperature range: 0℃~300℃

[0130] Heating rate: 5℃ / min

[0131] Frequency: 1Hz

[0132] Measurement mode: bending

[0133] The evaluation criteria for heat resistance are as follows.

[0134] ◎: Glass transition temperature is above 145°C

[0135] ○: Glass transition temperature is 130°C or higher and less than 145°C

[0136] ×: Glass transition temperature is less than 130°C

[0137] The evaluation criteria for the storage elastic modulus are as follows.

[0138] ◎:3,00MPa or less

[0139] ○: More than 3,000 MPa and less than 3,200 MPa

[0140] ×: more than 3,200 MPa

[0141] [Evaluation method of copper foil adhesion]

[0142] The vinyl ester resin compositions obtained in the examples and comparative examples were poured into a casting plate at room temperature, wherein a 2 mm thick rubber partition was sandwiched between glass plates with copper foil on one side, and then heat cured at 100°C for 1 hour and then heat cured at 170°C for 2 hours. The obtained cured product was cut into a size of 10 mm wide x 60 mm long, and the 90° peel strength was measured using a peel tester.

[0143] Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation)

[0144] Model:AG-1

[0145] Test speed: 50mm / min

[0146] The evaluation criteria for copper foil adhesion are as follows.

[0147] ◎: Peel strength is 2.0N / cm or more

[0148] ○: Peel strength is 1.5 N / cm or more and less than 2.0 N / cm

[0149] ×: Peel strength is less than 1.5 N / cm

[0150] Table 1 shows the results.

[0151] [Table 1]

[0152]

[0153] Examples 1 to 5 are examples of the present invention, and the copper foil adhesion, elastic modulus, and heat resistance are good. Comparative Example 1 is an example in which the cured product does not undergo phase separation, and the copper foil adhesion and elastic modulus are poor.

Claims

1. A resin composition comprising a resin (A) having a radical polymerizable group, a thermoplastic resin (B), and a radical polymerization initiator (C), The resin (A) having a free radical polymerizable group comprises a vinyl ester resin, an unsaturated polyester resin or a polyphenylene ether resin having a free radical polymerizable group. The thermoplastic resin (B) comprises at least one selected from the group consisting of polyester polyol and polyurethane polyol. The cured product of the resin composition forms a phase separation structure.

2. The resin composition according to claim 1, wherein The glass transition temperature of the thermoplastic resin (B) is -100°C or higher and 50°C or lower.

3. The resin composition according to claim 1 or 2, wherein The number average molecular weight of the thermoplastic resin (B) is 500 or more and 10,000 or less.

4. The resin composition according to any one of claims 1 to 3, wherein The solubility parameter of the thermoplastic resin (B) is 9 (cal / cm 3 ) 0.5 Above and 13(cal / cm 3 ) 0.5 the following.

5. A cured product of a resin composition, wherein: The resin composition is the resin composition according to any one of claims 1 to 4. 6 . An impregnated substrate comprising the resin composition according to claim 1 , and a reinforcing substrate impregnated with the resin composition.

7. A prepreg which is a semi-cured product of the impregnated base material according to claim 6.

8. A laminate comprising the impregnated base material according to claim 6.

9. A printed wiring board comprising the impregnated substrate according to claim 6.

10. A semiconductor package comprising the printed wiring board according to claim 9.

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