CN113950507A - Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package - Google Patents

Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package Download PDF

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Publication number
CN113950507A
CN113950507A CN202080040277.0A CN202080040277A CN113950507A CN 113950507 A CN113950507 A CN 113950507A CN 202080040277 A CN202080040277 A CN 202080040277A CN 113950507 A CN113950507 A CN 113950507A
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resin
resin composition
group
mass
radical polymerizable
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松村优佑
中村昭文
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DIC Corp
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DIC Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/14Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00Layered products comprising a layer of paper or cardboard
    • B32B29/02Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022Non-woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/245Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using natural fibres
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/0353Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/101Glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • C08J2475/08Polyurethanes from polyethers

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Textile Engineering (AREA)
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  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin composition which can exert stress relaxation effect caused by low elastic modulus under the condition of maintaining the heat resistance of the resin and has more excellent copper foil adhesion. The resin composition of the present invention comprises a resin (A) having a radical polymerizable group, a thermoplastic resin (B), and a radical polymerization initiator (C), wherein the resin (A) having a radical polymerizable group comprises 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-separated structure.

Description

Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package
Technical Field
The present invention relates to a resin composition, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor package.
Background
Radical polymerizable resins have a good balance among mechanical strength, chemical durability, electrical characteristics, and the like, and are widely used in industrial fields such as buildings, machines, automobiles, ships, and semiconductors. As such a radical polymerizable resin composition, for example, a laminate 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 at a specific ratio and curing the resin composition has been proposed (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2001/072879
Disclosure of Invention
Problems to be solved by the invention
However, the conventional radical polymerizable resin composition has insufficient adhesion to a copper foil having low surface roughness used for a copper-clad laminate, and has a problem of residual stress due to a difference in linear expansion coefficient between the copper foil and the resin portion, and thus there may be a problem in warpage of the laminate, a decrease in adhesion reliability at the copper foil/resin interface, and occurrence of cracks. The present invention has been made in view of the above circumstances, and an object thereof is 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 which has more excellent copper foil adhesiveness.
Means for solving the problems
The resin composition of the present invention comprises a resin (A) having a radical polymerizable group, a thermoplastic resin (B), and a radical polymerization initiator (C), wherein the resin (A) having a radical polymerizable group comprises 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-separated structure.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the resin composition of the present invention, a resin composition having more excellent copper foil adhesiveness can be provided while exhibiting a stress relaxation effect due to a low elastic modulus while maintaining the heat resistance of the resin.
Detailed Description
The resin composition of the present invention comprises a resin (a) having a radical polymerizable group, a thermoplastic resin (B), and a radical polymerization initiator (C).
The resin (a) having a radical polymerizable group may include one or two or more kinds of resins as long as it has a radical polymerizable group (group having an ethylenically unsaturated bond) in a molecule. Examples of the resin (a) having a radical polymerizable group include vinyl ester resins, unsaturated polyester resins, and polyphenylene ether resins having a radical polymerizable group.
The vinyl ester resin is preferably a reactant of an epoxy resin and an unsaturated carboxylic acid.
The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. As the epoxy resin, one or two or more kinds may be used, and for example, there may be mentioned: bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, and the like.
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: and unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid.
The vinyl ester resin is preferably a (meth) acrylic acid adduct of an epoxy resin.
The vinyl ester resin preferably has a number average molecular weight of 500 or more, more preferably 1,000 or more, and preferably 5,000 or less, more preferably 3,000 or less.
In the present invention, the number average molecular weight of the vinyl ester resin is a value measured as a converted value using polystyrene as a standard sample by a gel permeation chromatography (gel permeation chromatography) method.
The unsaturated polyester resin is preferably a dehydration condensation reactant of an unsaturated dicarboxylic acid or an anhydride thereof and a diol.
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-cyclohexene dicarboxylic acid.
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-propanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, and cyclohexanediol; alkylene oxide glycols such as diethylene glycol, dipropylene glycol, and triethylene glycol; and alkane diol adducts of bisphenol compounds (e.g., bisphenol a).
The unsaturated polyester resin is preferably a dehydration condensation product of an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid and a diol.
The number average molecular weight of the unsaturated polyester resin is preferably 500 or more, more preferably 1,000 or more, and preferably 5,000 or less, more preferably 3,000 or less.
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.
The polyphenylene ether resin has at least one radical polymerizable group. Examples of the radical polymerizable group include a vinyl group and an allyl group. 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 species, and the repeating order of each structural unit is not particularly limited.
[ solution 1]
Figure BDA0003382379240000031
[ formula (1) wherein Ar is1、Ar2、Ar3Each independently represents an optionally substituted aromatic hydrocarbon group, in Ar1、Ar2、Ar3At least one of the above groups has a radical polymerizable group added thereto. L is1、L2Each independently represents a single bond or a hydrocarbon group. n represents an integer of 1 or more, and when n is 2 or more, the constitutional units in parentheses to which n is added may be the same or different.]
As Ar1、Ar2The aromatic hydrocarbon group includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group.
As Ar3The aromatic hydrocarbon group includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenylene group and biphenylene group.
As said Ar3The aromatic hydrocarbon group may have a substituent, and examples thereof include: an alkyl group having 1 to 9 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, a 1-methylpentyl group, a 1-ethylpentyl group, etc.; cycloalkyl groups having 1 to 9 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; alkenyl groups having 2 to 9 carbon atoms such as vinyl, allyl, isopropenyl, butenyl, and the like; an alkynyl group having 2 to 9 carbon atoms such as a propynyl group or a butynyl group; an aromatic hydrocarbon group having 1 to 9 carbon atoms such as a phenyl group; a group having 1 to 9 carbon atoms, which is composed of one or more of these groups; halogen atoms such as fluorine atom and chlorine atom; a cyano group; a hydroxyl group; alkenyl groups having 2 to 6 carbon atoms such as vinyl groups and allyl groups; a C1-6 halogenated alkyl group such as a trifluoromethyl group; substituted amino groups such as dimethylamino group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; an alkoxy group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms such as a methoxymethoxy group or a methoxyethoxy group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like; a nitro group; and aryl groups such as phenyl, 4-chlorophenyl and naphthyl.
As L1、L2Examples of the hydrocarbon group include: alkanediyl having 1 to 20 carbon atoms such as methylene, ethylene, propanediyl and hexanediyl; cyclopropanediyl; cyclohexanediyl cycloalkanediyl having 3 to 20 carbon atoms; vinylidene group: an alkylene diyl group having 2 to 20 carbon atoms such as an isopropanediyl group: an alkynediyl group having 2 to 20 carbon atoms such as a propinylene group; and an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenylene group and a 2, 6-naphthylene group. In the present invention, the aromatic hydrocarbon group includes a hydrocarbon group containing an aromatic ring.
In the polyphenylene ether resin, a radical polymerizable group is preferably added to Ar1And Ar2At least one of (1).
The number average molecular weight of the polyphenylene ether resin is preferably 500 or more, more preferably 1,000 or more, and preferably 5,000 or less, more preferably 3,000 or less.
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.
In the resin (a) having a radical polymerizable group, the total content of the vinyl ester resin, the unsaturated polyester resin, and the polyphenylene ether resin having a 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.
The thermoplastic resin (B) includes at least one selected from the group consisting of a polyester polyol (B1) and a polyurethane polyol (B2).
The polyester polyol (B1) is a polymer having an ester bond in a molecular chain, and has two or more hydroxyl groups in one molecule. The number of hydroxyl groups in the polyester polyol is two or more, and preferably five or less, and more preferably four or less per molecule.
Examples of the polyester polyol (B1) 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 epsilon-caprolactone; a polyester polyol obtained by reacting (adding) a lactone compound with at least one member selected from the group consisting of a polyether polyol, a polyester polyol and a polycarbonate polyol and/or a low-molecular-weight polyol used for producing the polyester polyol as an initiator; and copolyester polyols of these.
As the low molecular weight polyol used for producing the polyester polyol (B1), polyols having a molecular weight of 50 or more and 300 or less can be used, and examples thereof include: aliphatic polyols having 2 to 6 carbon atoms (diols or trifunctional or higher polyols) 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, and glycerol; 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 used for producing 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 acid anhydrides or ester-forming derivatives of the above-mentioned aliphatic polycarboxylic acids and aromatic polycarboxylic acids.
As the lactone compound, one or two or more kinds may be used, and for example: delta-valerolactone, beta-methyl-delta-valerolactone, epsilon-caprolactone, alpha-methyl-epsilon-caprolactone, beta-methyl-epsilon-caprolactone, gamma-methyl-epsilon-caprolactone, beta-dimethyl-epsilon-caprolactone, delta-dimethyl-epsilon-caprolactone, 3, 5-trimethyl-epsilon-caprolactone, heptalactone (7-heptalactone)), dodecalactone (12-dodecalactone)), and the like.
The lactone compound has an addition rate of 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, based on 100 parts by mass of the total of the 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.
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.
The number average molecular weight of the polyester polyol (B1) can be calculated based on the hydroxyl value. The hydroxyl value may be determined according to Japanese Industrial Standards (JIS) K1557-1: 2007, measurement was carried out.
The polyurethane polyol (B2) is a polymer having at least a urethane bond in a molecular chain, and has two or more hydroxyl groups in one molecule. The number of hydroxyl groups in the polyester polyol is two or more, and preferably five or less, and more preferably four or less per molecule.
The polyurethane polyol (B2) is preferably a reaction product of a polyol compound (a) and a polyisocyanate compound (B).
As the polyol compound (a), one or two or more kinds may be used, and it is preferable to include a polymer polyol. The polymer polyol includes polyether polyol, polyester polyol, polycarbonate polyol, and the like, and preferably includes at least one selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol, and preferably includes at least polyester polyol.
The polyether polyol is preferably a polyoxyalkylene-based polyol, and examples thereof include polyether polyols obtained by ring-opening polymerization of a cyclic ether such as an alkylene oxide using one or two or more compounds having two or more active hydrogen atoms as an initiator, if necessary.
The cyclic ether preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. The hydrogen atom contained in the cyclic ether may be substituted with a halogen atom. As the cyclic ether, one or two or more kinds may be used, and for example, there may be mentioned: ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, alkylated tetrahydrofuran, and the like.
As the initiator, one or two or more kinds may be used, and for example, there may be mentioned: 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, water, etc.; and compounds having three or more active hydrogen atoms such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, hexanetriol, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, pentaerythritol, saccharides, and the like.
As the polyester polyol, the same compound as described as the polyester polyol (B1) can be used.
Examples of the polycarbonate polyol include: a reactant of a carbonate and a polyol; a reactant of phosgene (phosgene) with bisphenol A, etc.
Examples of the carbonate include: methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonates, diphenyl carbonate, and the like.
Examples of the polyol which can be reacted with the carbonate include: a polyol exemplified as the low molecular weight polyol; 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.).
The functional number of the polymer polyol is preferably 2 or more and 5 or less.
The number average molecular weight of the polymer polyol is preferably 300 or more, more preferably 500 or more, further preferably 700 or more, and preferably 10,000 or less, more preferably 7,000 or less, further preferably 5,000 or less.
The number average molecular weight of the polymer polyol can be calculated based on the hydroxyl value. The hydroxyl value can be determined according to JIS K1557-1: 2007, measurement was carried out.
As the polyisocyanate compound (b), one or two or more species can be used, and examples thereof include: 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, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylene diisocyanate, and tetramethylxylene diisocyanate.
The number of isocyanate groups contained in each molecule of the polyisocyanate compound (b) is 2 or more, and preferably 5 or less, and more preferably 3 or less.
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.
The hydroxyl value of the polyurethane polyol (B2) is preferably 11mgKOH/g or more, more preferably 16mgKOH/g or more, still more preferably 23mgKOH/g or more, and preferably 225mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 112mgKOH/g or less.
The number average molecular weight of the polyurethane polyol (B2) is 500 or more, more preferably 1000 or more, still more preferably 1500 or more, particularly preferably 2000 or more, and preferably 10000 or less, more preferably 7000 or less, still more preferably 5000 or less.
The number average molecular weight of the polyurethane polyol (B2) can be calculated based on the hydroxyl value. The hydroxyl value can be determined according to JIS K1557-1: 2007, measurement was carried out.
The solubility parameters of the polyester polyol (B1) and the polyurethane polyol (B2) are 9 (cal/cm)3)0.5Above, preferably 9.1 (cal/cm)3)0.5Above, more preferably9.4(cal/cm3)0 . 5Above, more preferably 9.9 (cal/cm)3)0.5Above, and preferably 13 (cal/cm)3)0.5Hereinafter, more preferably 11 (cal/cm)3)0.5More preferably 10.5 (cal/cm) or less3)0.5The following. If 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 hardened product.
The solubility parameters of the polyester polyol (B1) and the polyurethane polyol (B2) can be determined as a weighted average value based on the solubility parameters of units derived from each compound used as a raw material of the polyester polyol (B1) and the polyurethane polyol (B2) calculated by the method of fedos (Fedors) (Polymer Engineering and Science, 1974, vol.14, No.2) and based on the mass-based ratio of units derived from each compound.
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, still more preferably 95% by mass or more, and preferably 100% by mass or less.
The glass transition temperature of the thermoplastic resin (B) is preferably-100 ℃ or higher, more preferably-80 ℃ or higher, even more preferably-70 ℃ or higher, and preferably 50 ℃ or lower, more preferably 40 ℃ or lower, even more preferably 30 ℃ or lower. 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 ℃ or higher, more preferably-80 ℃ or higher, even more preferably-70 ℃ or higher, and preferably 50 ℃ or lower, more preferably-40 ℃ or lower, even more preferably-30 ℃ or lower. Further, when the thermoplastic resin (B) contains two or more resins, it is preferable that the glass transition temperature of each of the two or more resins is within the above range.
The number average molecular weight of the thermoplastic resin (B) is preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more, and preferably 30,000 or less, more preferably 20,000 or less, and even more 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 even more preferably 1,500 or more, and preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. When the thermoplastic resin (B9) contains two or more resins, the glass transition temperature of each of the two or more resins is preferably within the above range.
The thermoplastic resin (B) preferably has a solubility parameter of 9.0 (cal/cm)3)0.5Above, more preferably 9.7 (cal/cm)3)0.5Above, more preferably 9.5 (cal/cm)3)0.5Above, and preferably 10.5 (cal/cm)3)0.5More preferably 10.4 (cal/cm) or less3)0.5More preferably 10.2 (cal/cm) or less3)0 . 5The following.
The solubility parameter of the thermoplastic resin (B) can be determined as a weighted average value based on the method of Fedors (Polymer Engineering and Science, 1974, vol.14, No.2) and the solubility parameters and mass fractions of the components contained as the thermoplastic resin (B).
The content of the thermoplastic resin (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, with respect to 100 parts by mass of the resin (a) having a radical polymerizable group.
One or two or more kinds of the radical polymerization initiator (C) may be used, and examples thereof include a peroxide initiator and an azo initiator.
As the peroxide initiator, there can be mentioned: benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5, 5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, and the like.
As the azo initiator, there can be mentioned: 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane 1-carbonitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2' -azobis (2-methylpropionate), 4' -azobis (4-cyanovaleric acid), 2' -azobis (2-hydroxymethylacrylonitrile), 2' -azobis [2- (2-imidazolin-2-yl) propane ], and the like.
The content of the radical polymerization initiator (C) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin (a) having a radical polymerizable group.
The resin composition may further include a radical polymerizable monomer (D). The radical polymerizable monomer (D) includes compounds having one or more radical polymerizable groups, and specifically includes: 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; aromatic vinyl compounds such as (meth) acrylamide, (meth) acrylonitrile and other nitrogen-containing (meth) acrylic acid monomers, styrene, vinyl toluene, 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.
When the radically 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 preferably 80 parts by mass or less, more preferably 70 parts by mass or less, per 100 parts by mass of the resin (a) having a radically polymerizable group.
The resin composition may contain other additives (E) in addition to the resin (a) having a radical polymerizable group, the thermoplastic resin (B), and the radical polymerization initiator (C).
As the other additives, there may be mentioned: inorganic particles; an antioxidant; light stabilizers such as hindered amine light stabilizers; an ultraviolet absorber; a retarder; a release agent; other thermoplastic resins; softeners and plasticizers such as paraffin-based processing oils, naphthene-based processing oils, aromatic-based processing oils, paraffins, organopolysiloxanes, and mineral oils; a flame retardant; a silane coupling agent; an emulsifier; conductive particles; an antistatic agent; an organic fiber; 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, metal whiskers and the like; a low shrinkage agent; a colorant; an extender pigment; a thixotropy imparting agent; organic phosphorus compounds such as phosphites, phosphonites, and phosphates; leveling agent; surfactants, and the like.
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.
The resin composition of the present invention is obtained by mixing a resin (a) having a radical polymerizable group, a thermoplastic resin (B), a radical polymerization initiator, and optionally a radical polymerizable monomer (D) or other additives (E), and a cured product can be obtained by radical polymerization. The radical polymerization may be thermal polymerization or polymerization by an active energy ray. The shape of the cured product may be a laminate, a casting, an adhesive layer, a coating, a film, a composite (impregnated substrate) impregnated into a reinforcing substrate, or the like, and the composite (impregnated substrate) may be a prepreg as a semi-cured product.
The hardened substance of the resin composition forms a phase separation structure. When the resin (a) having a radical polymerizable group, the thermoplastic resin (B), and the radical polymerization initiator (C) are mixed, it is preferable that these components and other components used as necessary form a uniform phase, and a mechanism of forming a phase separation structure in the cured product is not clear, but it is presumed as follows. That is, it is considered that as the polymerization of the radical polymerizable group (a) proceeds, the molecular weight of the polymer derived from the resin (a) having a radical polymerizable group becomes large, and the mobility of the entire system is limited. As a result, the compatibility of the polymer derived from the resin (a) having a radical polymerizable group with the thermoplastic resin (B) is lowered, and phase separation (phase separation structure formation) occurs.
The phase separation structure may be any of an island-in-sea structure and a co-continuous structure. The presence or absence of phase separation in the cured product can be confirmed by: when the fracture surface of the hardened material is observed by an Atomic Force Microscope (AFM), two phases having different elastic moduli form a sea portion and an island portion, or a co-continuous structure.
In the phase separation structure, the short diameter of the phase having a low elastic modulus is, for example, 500nm or less, preferably 200nm or less, more preferably 100nm or less, and is, for example, 1nm or more, preferably 10nm or more.
As the reinforcing base material, a glass fiber nonwoven fabric, a glass fiber woven fabric, a paper base material, or the like can be used.
A laminate obtained by laminating the impregnated substrates is also included in the technical scope of the present invention. The laminate is preferably one having 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 laminate in which glass fiber woven fabric, glass fiber nonwoven fabric, and paper substrate are laminated in this order from the surface). Examples of the laminate include a laminate obtained by laminating metal foils (for example, copper foils) on both outer sides of the laminate as necessary, and then heating and curing the laminate of the metal foils and the impregnated substrate while compressing the laminate.
The resin composition of the present invention may be used in the following applications: semiconductor sealing materials, printed wiring board materials, resin casting materials, adhesives, semiconductor packages, and the like. Among these applications, in the application to an insulating material for a printed wiring board or an electronic circuit board, the insulating material is used as an insulating material for a so-called electronic component built-in substrate in which passive components such as a capacitor and active components such as an IC chip are embedded in a substrate. Among them, the material is preferably used for a printed wiring board material or the like in terms of characteristics such as high heat resistance, low thermal expansion, and solvent solubility.
Examples
The present invention will be described in more detail with reference to examples.
Synthesis example 1 Synthesis of polyester resin A
779.1 parts by mass of bisphenol a type glycol ether ("PANDEX (trademark) MB-601", 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") were charged into the reactor, and temperature rise 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 and a number average molecular weight of 3,040.
Synthesis example 2 Synthesis of polyester resin B
886.9 parts by mass of bisphenol A type glycol ether ("BA-P13U diol", manufactured by Nippon emulsifier Co., Ltd.), 109.4 parts by mass of iPA, and 33.3 parts by mass of SebA were charged into a reaction apparatus, 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 15.5 and a number average molecular weight of 7,240.
Synthesis example 3 Synthesis of polyester resin C
430.9 parts by mass of 3-methyl-1, 5-pentanediol and 692.4 parts by mass of SebA were charged into the reaction apparatus, and heating and stirring were started. Then, the internal temperature was increased to 220 ℃, 0.03 part by mass of TiPT was added thereto, and the mixture was reacted at 220 ℃ for 12 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 15.0 and a number average molecular weight of 4,488.
[ Synthesis example 4 ] Synthesis of urethane resin A
1,000.0 parts by mass of polytetramethylene glycol (PTMG-1000, manufactured by Mitsubishi chemical corporation) was charged into the reaction apparatus, and 128.8 parts by mass of toluene diisocyanate (manufactured by SKC polyurethane, manufactured by Mitsubishi chemical corporation, Kom Nit (Cosmonate) (trademark) T-80) was charged. Then, the reaction was continued for 10 hours after the temperature was raised to 80 ℃ as an external temperature, thereby synthesizing a urethane resin A.
The obtained urethane resin had a hydroxyl value of 28.0 and a number average molecular weight of 4,010.
[ example 1]
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 vessel and stirred until they were compatible. 1.25 parts by mass of a polymerization initiator (manufactured by Nichigan oil Co., Ltd. "Percumyl (trademark) H-80") was added thereto, and after stirring, vacuum defoaming was performed to obtain the vinyl ester resin composition (X1) of the present invention.
The vinyl ester resin composition was poured into a casting plate having a rubber partition wall of 2mm thickness sandwiched by glass plates at room temperature, and was thermally cured at 100 ℃ for 1 hour and then at 170 ℃ for 2 hours. The fracture surface of the obtained cured product was observed by an Atomic Force Microscope (AFM), and it was confirmed that the sea portion and the island portion were formed.
[ example 2 ]
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 (polyester resin a) having OH groups at both ends obtained in synthesis example 1 was used. As a result of observation of the fracture surface of the obtained cured product by an Atomic Force Microscope (AFM) in the same manner as in example 1, it was confirmed that two phases having different elastic moduli form a co-continuous structure.
[ example 3 ]
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. As a result of observation of the fracture surface of the obtained cured product by an Atomic Force Microscope (AFM) in the same manner as in example 1, it was confirmed that two phases having different elastic moduli form a co-continuous structure.
[ 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 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. As a result of observation of the fracture surface of the obtained cured product by an Atomic Force Microscope (AFM) in the same manner as in example 1, it was confirmed that two phases having different elastic moduli formed a sea portion and an island portion.
[ example 5 ]
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. As a result of observation of the fracture surface of the obtained cured product by an Atomic Force Microscope (AFM) in the same manner as in example 1, it was confirmed that two phases having different elastic moduli formed a sea portion and an island portion.
[ comparative example 1]
In a mixing vessel, 1.25 parts by mass of a polymerization initiator (Percumyl (trademark) H-80, manufactured by Nichigan Co., Ltd.) was added to 100 parts by mass of a vinyl ester resin (CE-330-IM, manufactured by DIC Co., Ltd.) as an epoxy resin, and after stirring, vacuum defoaming was performed to obtain the vinyl ester resin composition (Y1) of the present invention.
The vinyl ester resin composition was poured into a casting plate having a rubber partition wall of 2mm thickness sandwiched by glass plates at room temperature, and was thermally cured at 100 ℃ for 1 hour and then at 170 ℃ for 2 hours. The fracture surface of the obtained cured product was observed by an Atomic Force Microscope (AFM), and no phase separation structure was observed.
[ comparative example 2 ]
A 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 (polyester resin a) obtained in synthesis example 1 was replaced by 10 parts by mass of a polyester having OH groups at both ends (trade name, OD-X-2921 ", hydroxyl value 208, and number average molecular weight 540), manufactured by DIC corporation. The fracture surface of the obtained cured product was observed by an Atomic Force Microscope (AFM) in the same manner as in comparative example 1, but no phase separation structure was observed.
[ comparative example 3 ]
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 ("SB-20", number average molecular weight 350), manufactured by oka corporation, was used instead of 10 parts by mass of the polyester (polyester resin a) having OH groups at both terminals obtained in synthesis example 1. The fracture surface of the obtained cured product was observed by an Atomic Force Microscope (AFM) in the same manner as in comparative example 1, but no phase separation structure was observed.
[ evaluation methods of glass transition temperature (Tg) and storage elastic modulus (E') ]
The vinyl ester resin compositions obtained in examples and comparative examples were poured into a casting plate having a rubber partition wall of 2mm thickness sandwiched between glass plates at room temperature, and thermally cured at 100 ℃ for 1 hour and then at 170 ℃ for 2 hours. The obtained 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 tan. delta., the temperature at which tan. delta. is the maximum is measured as the glass transition temperature (Tg, unit:. degree. C.).
In addition, the storage elastic modulus (E') at 25 ℃ was measured.
Measurement equipment: dynamic viscoelasticity measuring apparatus (SII Nanotechnology, Inc.)
The model is as follows: DMA6100
Measurement temperature range: 0 ℃ to 300 DEG C
Temperature rise rate: 5 ℃/min
Frequency: 1Hz
Measurement mode: bending of
The evaluation criteria for heat resistance are as follows.
Very good: the glass transition temperature is more than 145 DEG C
O: the glass transition temperature is more than 130 ℃ and less than 145 DEG C
X: the glass transition temperature is less than 130 DEG C
The storage modulus of elasticity was evaluated as follows.
Very good: 3,00MPa or less
O: more than 3,000MPa and 3,200MPa or less
X: over 3,200MPa
[ method for evaluating copper foil adhesion ]
The vinyl ester resin compositions obtained in examples and comparative examples were poured into a casting plate having a rubber partition wall of 2mm thickness sandwiched between glass plates having copper foils attached to one surfaces thereof at room temperature, and were heat-cured at 100 ℃ for 1 hour and then at 170 ℃ for 2 hours. The obtained 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 automatic tester (Autograph) (Shimadzu corporation, Ltd.)
The model is as follows: AG-1
Test speed: 50mm/m
The copper foil adhesiveness was evaluated as follows.
Very good: peel strength of 2.0N/cm or more
O: peel strength of 1.5N/cm or more and less than 2.0N/cm
X: peeling strength less than 1.5N/cm
The results are shown in table 1.
[ Table 1]
Figure BDA0003382379240000161
Examples 1 to 5 are examples of the present invention, and the copper foil has good adhesiveness, elastic modulus and heat resistance. Comparative example 1 is an example in which the cured product did not undergo phase separation, and the copper foil adhesion and elastic modulus were poor.

Claims (10)

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 radical polymerizable group comprises a vinyl ester resin, an unsaturated polyester resin or a polyphenylene ether resin having a radical polymerizable group,
the thermoplastic resin (B) contains at least one selected from the group consisting of polyester polyols and polyurethane polyols,
the hardened substance 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 from-100 ℃ to 50 ℃.
3. The resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) has a number average molecular weight of 500 or more and 10,000 or less.
4. Tree according to any of claims 1 to 3A fat composition, wherein the thermoplastic resin (B) has a solubility parameter of 9 (cal/cm)3)0.5Above and 13 (cal/cm)3)0.5The 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 having the resin composition as claimed in any one of claims 1 to 4, and a reinforced substrate impregnated with the resin composition.
7. A prepreg which is a semi-cured product of the substrate impregnated with the composition according to claim 6.
8. A laminate having the intrusion-containing substrate of claim 6.
9. A printed wiring board having the intrusion-containing base material according to claim 6.
10. A semiconductor package having the printed wiring board as claimed in claim 9.
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