Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08L79/085—Unsaturated polyimide precursors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered 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
  • B32B15/08—Layered 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 synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
  • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
  • H10W70/69—Insulating materials thereof

Definitions

• This disclosure relates to resin compositions, prepregs, laminates, metal-clad laminates, printed wiring boards, and semiconductor packages.
• halogen-based flame retardants containing halogens such as bromine have been used as flame retardants for resin compositions used in electronic components such as printed wiring boards and semiconductor encapsulants.
• halogen-free products that do not use conventional bromine-based flame retardants containing halogens have been introduced.
• Halogen-free means that no halogen atoms are contained or that the content is extremely small.
• the Japan Electronics Packaging and Circuits Association specifies that the content of chlorine (Cl) and bromine (Br) in halogen-free copper-clad laminates for printed wiring boards is 900 ppm or less, respectively, and the total content is 1,500 ppm or less.
• halogen-free flame retardants such as phosphorus-based flame retardants such as phosphazene compounds, phosphate ester compounds, and phosphate ester amide compounds, have been proposed as alternative flame retardants to halogen-containing compounds (see, for example, Patent Document 1).
• the present disclosure aims to provide a resin composition containing an acrylic polymer, which is a combustible component, that has excellent flame retardancy while maintaining good adhesive strength with copper foil and desmear resistance. It also aims to provide a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a semiconductor package manufactured using the resin composition.
• the present disclosure includes the following embodiments [1] to [12].
• a resin composition comprising (A) an acrylic polymer, (B) a thermosetting resin, and (C) an inorganic filler surface-treated with a silane coupling agent, The resin composition further contains (D) a silane coupling agent.
• Mw weight average molecular weight
• the content of the (A) component is 1 to 50 parts by mass per 100 parts by mass of the total amount of the (A) component and the (B) component.
• the component (B) comprises at least one selected from the group consisting of an epoxy resin, a polyimide resin, a maleimide compound, a phenolic resin, a modified polyphenylene ether resin, a bismaleimide triazine resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, and a melamine resin.
• a prepreg comprising a substrate and the resin composition according to any one of [1] to [7] above or a semi-cured product of the resin composition.
• a laminate comprising at least one selected from the group consisting of a cured product of the resin composition according to any one of [1] to [7] above and a cured product of the prepreg according to [8] above.
• a metal-clad laminate comprising a metal foil and at least one selected from the group consisting of a cured product of the resin composition described in any one of [1] to [7] above and a cured product of the prepreg described in [8] above.
• a printed wiring board comprising one or more selected from the group consisting of a cured product of the resin composition according to any one of [1] to [7] above, a cured product of the prepreg according to [8] above, the laminate according to [9] above, and the metal-clad laminate according to [10] above.
• a semiconductor package comprising the printed wiring board according to [11] above and a semiconductor element.
• the present disclosure aims to provide a resin composition containing an acrylic polymer, which is a combustible component, that has excellent flame retardancy while maintaining good adhesive strength with copper foil and desmear resistance. Furthermore, it is possible to provide prepregs, laminates, metal-clad laminates, printed wiring boards, and semiconductor packages manufactured using the resin composition.
• the upper or lower limit of the numerical range may be replaced with the values shown in the examples.
• the lower and upper limits of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range.
• the numerical values AA and BB at both ends are included in the numerical range as the lower and upper limits, respectively.
• the description "10 or more” means 10 and a numerical value exceeding 10, and the same applies when the numerical values are different.
• the description "10 or less” means 10 and a numerical value less than 10, and the same applies when the numerical values are different.
• each component and material exemplified in this disclosure may be used alone or in combination of two or more types.
• the content of each component in the resin composition means the total amount of the multiple substances present in the resin composition, unless otherwise specified.
• solid content refers to components in a resin composition other than the organic solvent described below, and components that are liquid at room temperature around 25° C. are also considered to be solid content.
• the expression "containing XX” described in the present disclosure may mean containing XX in a reacted state if XX is capable of reacting, or may simply contain XX as it is, or may include both of these aspects. Additionally, any combination of the descriptions in this disclosure is also included in this embodiment.
• One aspect of the present embodiment is a resin composition containing (A) an acrylic polymer (hereinafter, sometimes referred to as “component (A)”), (B) a thermosetting resin (hereinafter, sometimes referred to as “component (B)”), and (C) an inorganic filler surface-treated with a silane coupling agent (hereinafter, sometimes referred to as “component (C)”), and further containing (D) a silane coupling agent (hereinafter, sometimes referred to as “component (D)”).
• component (A) an acrylic polymer
• component (B) a thermosetting resin
• component (C) an inorganic filler surface-treated with a silane coupling agent
• component (D) silane coupling agent
• the resin composition of the present embodiment contains an acrylic polymer as component (A), thereby improving low elasticity and flexibility.
• the acrylic polymer is a polymer having a (meth)acrylic acid ester as a monomer, but is not limited to a polymer having an acrylic acid ester as a monomer.
• “(meth)acrylic acid” refers to both "acrylic acid” and “methacrylic acid”, and either one can be selected.
• the acrylic polymer can also be said to be an acrylic polymer containing structural units derived from (meth)acrylic acid esters, and is preferably an acrylic polymer containing structural units derived from (meth)acrylic acid esters represented by the following general formula (A1).
• R A1 represents a hydrogen atom or a methyl group
• R A2 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
• R A1 may be either a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• the number of carbon atoms in the alkyl group represented by R A2 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 2 to 10.
• Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group.
• the alkyl group may have a substituent. Examples of the substituent of the alkyl group include a cycloalkyl group, a hydroxyl group, a halogen, an oxygen-containing hydrocarbon group, and a nitrogen-containing cyclic group.
• the total number of carbon atoms in the cycloalkyl-substituted alkyl group is preferably 6 to 13, and more preferably 7 to 10.
• Examples of the cycloalkyl-substituted alkyl group include a norbornylmethyl group and a tricyclodecylethyl group.
• the number of carbon atoms in the cycloalkyl group represented by R is preferably 6 to 13, and more preferably 7 to 10.
• Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, an isobornyl group, and an adamantyl group.
• the cycloalkyl group is preferably a norbornyl group, a tricyclodecanyl group, or an isobornyl group.
• the number of carbon atoms in the aryl group represented by R A2 is preferably 6 to 13, and more preferably 6 to 10.
• Examples of the aryl group include a phenyl group and a nonylphenyl group.
• the number of carbon atoms in the aralkyl group represented by R A2 is preferably from 7 to 15, and more preferably from 7 to 11.
• Examples of the aralkyl group include a benzyl group and a 4-methylbenzyl group.
• component (A) examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0(2,6)]dec-8-yl (meth)acrylate, isodecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, allyl (meth)acrylate, norbornylmethyl (meth)acrylate, tricyclodecylethyl (meth)acrylate
• the (A) component is not particularly limited, but is preferably an acrylic polymer having a crosslinkable functional group.
• the acrylic polymer having a crosslinkable functional group include a copolymer of a (meth)acrylic acid ester and a copolymerizing monomer having a crosslinkable functional group (hereinafter, sometimes simply referred to as a "crosslinkable copolymerizing monomer").
• the crosslinkable copolymerizing monomer preferably has one or more crosslinkable functional groups selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a vinyl group, and an epoxy group.
• the crosslinkable functional group is preferably one or more selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, and an epoxy group, and from the viewpoint of low moisture absorption and solder heat resistance, an epoxy group is more preferable.
• the crosslinkable copolymerizable monomer is preferably a compound having a double bond.
• the crosslinkable copolymerization monomers include monomers having a carboxy group such as acrylic acid and methacrylic acid; monomers having an epoxy group such as glycidyl acrylate and glycidyl methacrylate; monomers having a hydroxyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; monomers having an amino group such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; monomers having an amide group such as acrylamide, methacrylamide, dimethylacrylamide, and dimethylmethacrylamide; and monomers having a nitrile group such as acrylonitrile.
• monomers having a carboxy group such as acrylic acid and methacrylic acid
• monomers having an epoxy group such as glycidyl acrylate and glycidyl methacrylate
• monomers having a carboxy group monomers having an epoxy group, monomers having a hydroxyl group, and monomers having an amino group are preferred, and from the viewpoint of low moisture absorption and solder heat resistance, monomers having an epoxy group are more preferred, and glycidyl acrylate and glycidyl methacrylate are even more preferred.
• component (A) may be a copolymer of a polymerizable monomer selected from the group consisting of N-vinylpyrrolidone acrylate, N-vinylpyrrolidone methacrylate, N-acryloylmorpholine, N-methacryloylmorpholine, aromatic vinyl compounds, N-substituted maleimide compounds, and (meth)acrylic acid esters other than those represented by the general formula (A1) above, and a (meth)acrylic acid ester.
• a polymerizable monomer selected from the group consisting of N-vinylpyrrolidone acrylate, N-vinylpyrrolidone methacrylate, N-acryloylmorpholine, N-methacryloylmorpholine, aromatic vinyl compounds, N-substituted maleimide compounds, and (meth)acrylic acid esters other than those represented by the general formula (A1) above, and a (meth)acrylic acid ester.
• the amount of the (meth)acrylic acid ester used is preferably 70 to 99.5 parts by mass, more preferably 80 to 98 parts by mass, and even more preferably 90 to 97 parts by mass, per 100 parts by mass of the total amount of the (meth)acrylic acid ester and the crosslinkable copolymerizable monomer.
• the amount of the crosslinkable copolymer monomer used is preferably 0.5 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 20 parts by mass, based on 100 parts by mass of the total amount of the (meth)acrylic acid ester and the crosslinkable copolymer monomer. By setting the amount within such a range, solder heat resistance, adhesive strength with metal foil, insulation reliability, etc. tend to be further improved.
• the total content of the (meth)acrylic acid ester and the crosslinkable copolymerizable monomer is preferably 80 mass% or more, more preferably 90 mass% or more, and even more preferably 95 mass% or more, and may be 100 mass%.
• the epoxy equivalent is preferably 1,000 to 18,000 g/eq, more preferably 2,000 to 15,000 g/eq, even more preferably 3,000 to 10,000 g/eq, and particularly preferably 3,500 to 7,000.
• the epoxy equivalent is equal to or greater than the lower limit, the dimensional stability of the substrate tends to be maintained, and when it is equal to or less than the upper limit, the decrease in the glass transition temperature of the cured product is suppressed, and the solder heat resistance of the substrate tends to be improved.
• the epoxy equivalent of the component (A) can be adjusted by appropriately adjusting the copolymerization ratio when glycidyl (meth)acrylate is copolymerized with another monomer copolymerizable therewith.
• acrylic polymers having epoxy groups include, for example, "HTR-860” (product name, manufactured by Nagase ChemteX Corporation, epoxy equivalent 2,900 g/eq), "Teisan Resin SG-P3" (product name, manufactured by Nagase ChemteX Corporation, epoxy equivalent 4,761 to 14,285 g/eq, weight average molecular weight 350,000 to 850,000), and "KH-CT-865" (product name, manufactured by Resonac Corporation, epoxy equivalent 3,300 g/eq).
• HTR-860 product name, manufactured by Nagase ChemteX Corporation, epoxy equivalent 2,900 g/eq
• Teisan Resin SG-P3 product name, manufactured by Nagase ChemteX Corporation, epoxy equivalent 4,761 to 14,285 g/eq, weight average molecular weight 350,000 to 850,000
• KH-CT-865" product name, manufactured by Resonac Corporation, epoxy equivalent 3,300 g/eq
• the weight average molecular weight (Mw) of the (A) component is preferably 50,000 to 1,500,000, and from the viewpoint of improving low elasticity and elongation, more preferably 100,000 to 1,300,000, and may be 100,000 to 1,100,000, 100,000 to 950,000, or 300,000 to 1,100,000, 500,000 to 1,000,000, or 700,000 to 1,000,000. If the weight average molecular weight of the (A) component is the lower limit or more, the (A) component and the (B) component tend to be not completely compatible with each other and a phase separation structure tends to be formed, and if it is the upper limit or less, it tends to be easily dissolved in a solvent and has excellent handleability and dispersibility.
• the component (A) may be a combination of two or more types having different weight average molecular weights.
• the weight average molecular weight is a value measured by gel permeation chromatography (GPC) analysis and means a standard polystyrene equivalent value.
• GPC analysis can be performed using tetrahydrofuran (THF) as a dissolving solution.
• THF tetrahydrofuran
• the component (A) may be in a powder form or a liquid form at 25°C. From the viewpoints of solubility in organic solvents and dispersibility of the acrylic polymer in the resin composition, it is preferable that the component (A) be in a liquid form at 25°C.
• the component (A) may be used alone or in combination of two or more types.
• the content of the (A) component in the resin composition of this embodiment is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 3 to 45 parts by mass, even more preferably 5 to 40 parts by mass, particularly preferably 10 to 35 parts by mass, and most preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total amount of the (A) and (B) components. If the content of the (A) component is equal to or more than the lower limit, the properties of the (A) component tend to be easily exhibited, and if the content is equal to or less than the upper limit, the adhesive strength to the metal foil and heat resistance tend to be excellent.
• Thermosetting resin examples include epoxy resins, polyimide resins, maleimide compounds, phenolic resins, modified polyphenylene ether resins, bismaleimide triazine resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, etc.
• the epoxy resins and maleimide compounds are preferred as the component (B).
• the component (B) may be used alone or in combination of two or more types.
• epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule.
• epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.
• Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton, and each of the above types of epoxy resins is further classified into bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; alicyclic epoxy resins such as dicyclopentadiene type epoxy resins; aliphatic chain epoxy resins; novolac type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, and biphenyl aralkyl novolac type epoxy resins; stilbene type epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthol novolac type epoxy resins and naphthol aralkyl type epoxy resins; biphenyl type epoxy resins; xylylene type epoxy resins;
• the weight average molecular weight of the epoxy resin may be 200 to 1,000, or 300 to 900.
• the epoxy resin tends to have excellent solder heat resistance, and when the weight average molecular weight is equal to or less than the upper limit, the epoxy resin tends to have low elasticity and flexibility.
• the epoxy equivalent of the epoxy resin may be 150 to 500 g/eq, 150 to 450 g/eq, or 150 to 300 g/eq.
• the maleimide compound preferably includes at least one selected from the group consisting of maleimide compounds (b1) having two or more N-substituted maleimide groups [hereinafter, may be simply referred to as "maleimide compound (b1)” or “component (b1)”.] and derivatives thereof.
• the component (B) includes at least one selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof.
• the above-mentioned “derivative” may be an addition reaction product of a maleimide compound (b1) having two or more N-substituted maleimide groups with an amine compound such as a diamine compound described later.
• the maleimide compound (b1) is not particularly limited as long as it has two or more N-substituted maleimide groups.
• Specific examples of the maleimide compound (b1) include aromatic maleimide compounds such as bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; and aliphatic maleimide compounds such as 1,6-bismaleimido-(2,2,4-trimethyl)hexane and pyrophosphate binder type long chain alkyl bismaleimide.
• aromatic maleimide compounds are preferred as the maleimide compound (b1), aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide are even more preferred.
• maleimide compound (b1) a compound represented by the following general formula (B1-1) is preferred.
• X b1 represents a divalent organic group.
• Examples of the divalent organic group represented by X b1 in the above general formula (B1-1) include groups represented by the following general formulas (B1-2), (B1-3), (B1-4) and (B1-5).
• R b1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• n b1 represents an integer of 0 to 4. * represents a bonding position.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
• As the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
• n b1 represents an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, and more preferably 0. When n b1 is an integer of 2 or more, multiple R b1 may be the same or different.
• R b2 and R b3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X b2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (B1-3-1).
• n b2 and n b3 each independently represent an integer of 0 to 4. * represents a bonding position.
• the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b2 and R b3 is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in the above general formula (B1-2).
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc.
• the alkylene group an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc.
• an isopropylidene group is preferable.
• n b2 and n b3 each represent an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 or 2 is more preferable.
• each of the multiple R b2 may be the same or different.
• n b3 is an integer of 2 or more, each of the multiple R b3 may be the same or different.
• the divalent group represented by formula (B1-3-1) and represented by X b2 is as follows.
• R b4 and R b5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X b3 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n b4 and n b5 each independently represent an integer of 0 to 4. * represents a bonding position.
• the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b4 and R b5 is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in general formula (B1-2) above.
• Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b3 include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b2 in the above general formula (B1-3).
• n b4 and n b5 each represent an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable.
• n b4 is an integer of 2 or more
• each of the multiple R b4s may be the same or different.
• n b5 is an integer of 2 or more, each of the multiple R b5s may be the same or different.
• n b6 represents an integer of 1 to 10. * represents a bonding position.
• n b6 is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
• R b6 and R b7 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• n b7 represents an integer of 1 to 8. * represents a bonding position.
• n b7 represents an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.
• n b7 is an integer of 2 or more, each of the multiple R b6 may be the same or different, and each of the multiple R b7 may be the same or different.
• X b1 in the above general formula (B1-1) is preferably a divalent group represented by any of the following formulas (X b1 -1) to (X b1 -3), and more preferably a divalent group represented by the following formula (X b1 -3).
• the maleimide compound from the viewpoints of solubility in organic solvents, compatibility, adhesion to metal foils, and dielectric properties, a derivative of the maleimide compound (b1) is preferred.
• the derivative of the maleimide compound (b1) is preferably a modified maleimide compound (Z) [hereinafter, sometimes abbreviated as "modified maleimide compound (Z)” or “(Z) component)] having a structural unit derived from the maleimide compound (b1) and a structural unit derived from an amine compound (b2) having a primary amino group [hereinafter, sometimes abbreviated as "amine compound (b2)" or "(b2) component)].
• the resin composition of the present embodiment preferably contains the maleimide compound as component (B), and the maleimide compound is a modified maleimide compound having a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (b2) having a primary amino group.
• the structural unit derived from the component (b1) and the structural unit derived from the component (b2) contained in the modified maleimide compound (Z) may each be composed of one type or a combination of two or more types.
• the modified maleimide compound (Z) is preferably a compound having a structure represented by the following formula (B-1), which is formed by an addition reaction between a maleimide group in the component (b1) and a primary amino group in the component (b2). (* indicates the bond position to other structures.)
• the structural unit derived from component (b1) may be, for example, one or more selected from the group consisting of the group represented by the following general formula (B1-6) and the group represented by the following general formula (B1-7).
• the content of the structural unit derived from the (b1) component in the modified maleimide compound (Z) is not particularly limited, but is preferably 50 to 95 mass%, more preferably 70 to 92 mass%, and even more preferably 75 to 90 mass%. If the content of the structural unit derived from the (b1) component is within the above range, the dielectric properties tend to be good.
• the amine compound (b2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups.
• examples of the amine compound (b2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(
• the component (b2) is preferably an amine-modified siloxane compound having a primary amino group. That is, the modified maleimide compound (Z) is preferably a siloxane-modified maleimide compound (Z). In other words, the component (B) preferably contains a siloxane-modified maleimide compound.
• the amine compound (b2) is preferably a compound represented by the following general formula (B2-1):
• X b4 represents a divalent organic group.
• the component (b2) preferably contains an aromatic diamine compound in which X b4 in the above general formula (B2-1) is a divalent group represented by the following general formula (B2-2) [hereinafter sometimes abbreviated as "aromatic diamine compound (B2-2)"].
• R b11 and R b12 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom.
• X b5 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (B2-2-1) or (B2-2-2).
• n b8 and n b9 each independently represent an integer of 0 to 4. * represents a bonding position.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b11 and R b12 in general formula (B2-2) above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b5 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b5 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
• n b8 and n b9 each represent an integer of 0 to 4, and from the viewpoint of availability, preferably 0 or 1.
• n b8 or n b9 is an integer of 2 or more, a plurality of R b11 's or a plurality of R b12's may be the same or different.
• the divalent group represented by general formula (B2-2-1) and represented by X b5 in the above general formula (B2-2) is as follows.
• R b13 and R b14 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X b6 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n b10 and n b11 each independently represent an integer of 0 to 4. * represents a bonding position.
• the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b13 and R b14 in the above general formula (B2-2-1) is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b11 and R b12 in the above general formula (B2-2).
• the explanation for the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b6 is the same as the explanation for the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b5 in the above general formula (B2-2).
• n b10 and n b11 each represent an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable.
• n b10 is an integer of 2 or more
• multiple R b13 may be the same as or different from each other.
• n b11 is an integer of 2 or more
• multiple R b14 may be the same as or different from each other.
• the divalent group represented by general formula (B2-2-2) and represented by X b5 in the above general formula (B2-2) is as follows.
• R b15 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X b7 and X b8 each independently represent an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n b12 represents an integer of 0 to 4. * represents a bonding position.
• the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b15 in the above general formula (B2-2-2) is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b11 and R b12 in the above general formula (B2-2).
• Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b7 and X b8 include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b5 in general formula (B2-2) above.
• X b7 and X b8 are preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
• n b12 represents an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, and more preferably 0.
• R b15 may be the same or different.
• the component (b2) preferably contains an "amine-modified siloxane compound” in which X b4 in the above general formula (B2-1) contains a structural unit represented by the following general formula (B2-3).
• the component (b2) more preferably contains a "terminal amine-modified siloxane compound” in which X b4 in the above general formula (B2-1) contains a structural unit represented by the following general formula (B2-4).
• R b16 and R b17 each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. * indicates the bonding position.
• R b16 and R b17 are the same as those in the above general formula (B2-3), R b18 and R b19 each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, X b9 and X b10 each independently represent a divalent organic group, and n b13 represents an integer of 2 to 100. * represents a bonding position.
• Examples of the alkyl group having 1 to 5 carbon atoms represented by R b16 to R b19 in general formulae (B2-3) and (B2-4) above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
• the alkyl group an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
• Examples of the substituent on the phenyl group in the substituted phenyl group represented by R b16 to R b19 include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms.
• Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group.
• Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group.
• Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group.
• Examples of the divalent organic group represented by X b9 and X b10 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by combining these.
• Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, or a propylene group.
• Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms.
• alkynylene group examples include alkynylene groups having 2 to 10 carbon atoms.
• arylene group examples include arylene groups having 6 to 20 carbon atoms, such as a phenylene group or a naphthylene group.
• X b9 and X b10 are preferably an alkylene group or an arylene group, and more preferably an alkylene group.
• n b13 represents an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and still more preferably an integer of 5 to 30. When n b13 is an integer of 2 or greater, a plurality of R b16s or a plurality of R b17s may be the same or different.
• Examples of the structural unit derived from the component (b2) include one or more types selected from the group consisting of groups represented by the following general formula (B2-5) and groups represented by the following general formula (B2-6).
• X b4 is the same as X b4 in the above general formula (B2-1), and * indicates the bonding position.
• the content of the structural unit derived from component (b2) in the modified maleimide compound (Z) is not particularly limited, but is preferably 5 to 50 mass%, more preferably 8 to 30 mass%, and even more preferably 10 to 25 mass%. If the content of the structural unit derived from component (b2) is within the above range, the compound tends to have excellent low thermal expansion properties and dielectric properties, as well as good solder heat resistance, flame retardancy, and glass transition temperature.
• the total content of the structural units derived from the (b1) component and the structural units derived from the (b2) component in the modified maleimide compound (Z) is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and is particularly preferably 100% by mass (i.e., consisting only of structural units derived from the (b1) component and structural units derived from the (b2) component).
• the content ratio of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) in the modified maleimide compound (Z) is not particularly limited, but the equivalent ratio ( Ta1 / Ta2 ) of the total equivalent (Ta1) of the group derived from the maleimide group (including the maleimide group) derived from the component (b1) to the total equivalent (Ta2) of the group derived from the -NH2 group (including -NH2) of the component (b2) is preferably 0.05 to 10, more preferably 2 to 8. If the equivalent ratio (Ta1/Ta2) is within the above range, there is a tendency that the low thermal expansion property and the dielectric properties are excellent, and good solder heat resistance, flame retardancy, and glass transition temperature are obtained.
• the maleimide compound contains a compound represented by the following general formula (B-2).
• the component (Z) can be produced, for example, by reacting the components (b1) and (b2) in an organic solvent. Specifically, a reactor is charged with predetermined amounts of the components (b1), (b2), and, if necessary, other components, and the components (b1) and (b2) are subjected to a Michael addition reaction (hereinafter, sometimes referred to as a "pre-reaction") to obtain the modified maleimide compound (Z).
• a Michael addition reaction hereinafter, sometimes referred to as a "pre-reaction"
• the reaction conditions are not particularly limited, but from the viewpoint of obtaining good reactivity and workability while suppressing gelation, the reaction temperature is preferably 50 to 160°C, more preferably 90 to 140°C, and the reaction time is preferably 1 to 10 hours, more preferably 1 to 5 hours.
• reaction catalyst In the pre-reaction, a reaction catalyst may be used as necessary.
• reaction catalysts include acid catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazole-based compounds such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. There are no particular restrictions on the amount of the reaction catalyst, but it is, for example, 0.01 to 5 parts by mass per 100 parts by mass of the total amount of the (b1) and (b2) components.
• the organic solvent may be added or concentrated as necessary to adjust the solids concentration of the reaction raw materials and the viscosity of the reaction liquid.
• the solids concentration of the reaction raw materials is not particularly limited, but is preferably 10 to 90 mass%, and more preferably 20 to 80 mass%. If the solids concentration of the reaction raw materials is equal to or higher than the lower limit, a sufficient reaction rate is obtained, which tends to be advantageous in terms of production costs, and if it is equal to or lower than the upper limit, good solubility is obtained, stirring efficiency is improved, and gelation tends to be less likely.
• the weight average molecular weight (Mw) of the modified maleimide compound (Z) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.
• the content of the (B) component in the resin composition of this embodiment is preferably 50 to 99 parts by mass, more preferably 55 to 97 parts by mass, even more preferably 60 to 95 parts by mass, particularly preferably 65 to 90 parts by mass, and most preferably 70 to 90 parts by mass, relative to 100 parts by mass of the total amount of the (A) and (B) components. If the content of the (B) component is equal to or greater than the lower limit, the adhesive strength to the metal foil and the solder heat resistance tend to be excellent, and if the content is equal to or less than the upper limit, the characteristics of the (A) component tend to be easily exhibited.
• the resin composition of this embodiment further contains an inorganic filler surface-treated with a silane coupling agent as component (C).
• the (C) component can suppress the reduction of the effect of the (D) silane coupling agent contained in the resin composition of this embodiment by surface-treating the inorganic filler with a silane coupling agent.
• the (C) component is surface-treated with a silane coupling agent, so that the (D) silane coupling agent is suppressed from being used for surface treatment of the inorganic filler, and the effect of the (D) component is fully exerted.
• the (C) component preferably contains 80% by mass or more (preferably 90% by mass or more, including 100% by mass; the same applies below) of an inorganic filler in which 70% or more of the surface of the inorganic filler is treated with a silane coupling agent, more preferably contains 80% by mass or more of an inorganic filler in which 80% or more of the surface of the inorganic filler is treated with a silane coupling agent, even more preferably contains 80% by mass or more of an inorganic filler in which 90% or more of the surface of the inorganic filler is treated with a silane coupling agent, particularly preferably contains 80% by mass or more of an inorganic filler in which 98% or more of the surface of the inorganic filler is treated with a silane coupling agent, and most preferably contains 80% by mass or more of an inorganic filler in which 100% or more of the surface of the inorganic filler is treated with a silane coupling agent.
• component (C) examples include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), molybdic acid compounds (zinc molybdate, etc.), talc, aluminum borate, silicon carbide, etc.
• One type of component (C) may be used alone, or two or more types may be used in combination.
• silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred.
• examples of silica include precipitated silica and dry process silica.
• the precipitated silica is produced by a wet process and has a high water content.
• the dry process silica is produced by a dry process and contains almost no bound water.
• the dry process silica further includes crushed silica, fumed silica, fused silica, and the like.
• examples of the silane coupling agent used in the surface treatment of the inorganic filler include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and silicone oligomer coupling agents.
• aminosilane coupling agents, epoxysilane coupling agents, and phenylsilane coupling agents are preferred, aminosilane coupling agents and phenylsilane coupling agents are more preferred, and phenylsilane coupling agents are even more preferred.
• the silane coupling agents may be used alone or in combination of two or more.
• the average particle size of component (C) is preferably 0.1 to 2.5 ⁇ m, more preferably 0.2 to 1.5 ⁇ m, and even more preferably 0.3 to 0.8 ⁇ m. If the average particle size of component (C) is equal to or greater than the lower limit, the filler is easily dispersed in the resin varnish, and aggregation tends to be less likely to occur, whereas if the average particle size is equal to or less than the upper limit, sedimentation of component (C) in the resin varnish tends to be less likely to occur.
• the average particle size refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method or the like.
• the content of the (C) component in the resin composition of this embodiment is not particularly limited, but is preferably 30 to 300 parts by mass, more preferably 50 to 250 parts by mass, even more preferably 70 to 200 parts by mass, particularly preferably 100 to 200 parts by mass, and most preferably 130 to 170 parts by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component. If the content of the (C) component is equal to or greater than the lower limit, the composition tends to have excellent low thermal expansion properties and high heat resistance. If the content of the (C) component is equal to or less than the upper limit, the composition tends to have the properties of the (A) component.
• the resin composition of the present embodiment further contains a silane coupling agent as component (D).
• the silane coupling agent is a compound having a substituted silyl group.
• the substituent of the substituted silyl group include a hydroxyl group; an alkyl group such as a methyl group; an alkoxy group such as a methoxy group or an ethoxy group; and a carboxyl group.
• the substituent of the substituted silyl group is bonded to a silicon atom, and the number of the substituents is 1 to 3, and may be 3.
• the compound having a substituted silyl group has three substituents, the compound can be called a compound having a tri-substituted silyl group.
• the (D) component preferably has a functional group that can react with the (A) component or the (B) component.
• the (D) component can be classified according to the type of functional group, and examples thereof include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, silicone oligomer coupling agents, (meth)acrylicsilane coupling agents, isocyanatesilane coupling agents, isocyanuratesilane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, carboxysilane coupling agents, alkylene glycol silane coupling agents, etc.
• Component (D) can be a commercially available product.
• commercially available products include the KBM series and KBE series manufactured by Shin-Etsu Chemical Co., Ltd., and silane coupling agents manufactured by Dow Toray Co., Ltd.
• the content of the (D) component in the resin composition of this embodiment is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, even more preferably 0.1 to 1.5 parts by mass, particularly preferably 0.1 to 1.0 parts by mass, and most preferably 0.1 to 0.7 parts by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component. If the content of the (D) component is equal to or greater than the lower limit, there is a tendency that the flame retardancy is easily improved while maintaining good adhesion strength with the copper foil and desmear resistance, even in a resin composition containing the (A) component, which is an easily combustible component. If the content of the (D) component is equal to or less than the upper limit, there is a tendency that the adhesion strength with the copper foil is easily maintained.
• the resin composition of the present embodiment may contain a curing accelerator (E) (hereinafter, may be referred to as "component (E)").
• the component (E) may be used alone or in combination of two or more kinds.
• the (E) curing accelerator is not particularly limited, but preferably contains one or more selected from the group consisting of an amine compound and an imidazole-based compound, and more preferably contains an imidazole-based compound.
• the amine compound include dicyandiamide, diaminodiphenylethane, and guanylurea.
• imidazole-based compound examples include 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, benzimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, etc.).
• the content thereof is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
• the resin composition of the present embodiment may contain, as necessary, a resin other than the component (B), an elastomer other than the component (A), a curing agent, a crosslinking agent, a flame retardant, a flame retardant assistant, conductive particles, a coupling agent, a flow control agent, an antioxidant, a heat stabilizer, an antistatic agent, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, etc.
• a resin other than the component (B) an elastomer other than the component (A)
• a curing agent elastomer other than the component (A)
• a crosslinking agent e.g., ethylene glycol dimethacrylate
• a flame retardant elastomer other than the component (A)
• a curing agent elastomer other than the component (A)
• a crosslinking agent e.g., ethylene glycol dimethacrylate
• the resin composition of the present embodiment may be in a state of being dissolved or dispersed in an organic solvent, that is, in a state of a so-called “resin varnish.”
• a resin composition containing an organic solvent may be referred to as a resin varnish.
• organic solvent examples include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon-based solvents such as toluene and xylene; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; amide-based solvents such as N-methylpyrrolidone, formamide, N-methylformamide, and N,N-dimethylacetamide; and alcohol-based solvents such as methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glyco
• the prepreg of the present embodiment includes a substrate and the resin composition of the present embodiment or a semi-cured product of the resin composition.
• the expression "including a substrate and a semi-cured product of the resin composition of the present embodiment” means that the substrate is impregnated with the resin composition and semi-cured (B-staged).
• B-staged refers to bringing the substrate into the B-stage state defined in JIS K6900 (1994).
• the prepreg can be produced, for example, by impregnating or coating a substrate with the resin composition of the present embodiment in a varnish form, and then heating and drying the resin composition to semi-cure (B-stage).
• the resin composition can be impregnated or coated on a substrate by the following hot melt method or solvent method.
• the hot melt method is a method in which the resin composition does not contain an organic solvent, and (1) the resin composition is first coated onto a coated paper having good peelability from the paper, and then the coated paper is laminated onto a substrate, or (2) the resin composition is directly coated onto a substrate using a die coater.
• the solvent method is a method in which an organic solvent is added to a resin composition, a substrate is immersed in the obtained resin composition to impregnate the substrate with the resin composition, and then the substrate is dried.
• a fiber substrate such as a woven fabric or a nonwoven fabric is usually used, and a woven fabric is preferable.
• the substrate is preferably a sheet-like fiber substrate.
• the material of the fiber substrate include inorganic fibers such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, Tyranno, silicon carbide, silicon nitride, and zirconia; organic fibers such as aramid, polyether ether ketone, polyether imide, polyether sulfone, carbon, and cellulose; and mixtures thereof.
• inorganic fibers are preferred, and glass fibers are more preferred.
• the substrate is preferably a woven fabric of glass fibers, that is, a glass cloth.
• the thickness of the substrate is preferably 5 to 200 ⁇ m, may be 10 to 100 ⁇ m, or may be 20 to 50 ⁇ m. By making the thickness of the substrate equal to or less than the upper limit value, dimensional changes due to temperature changes, moisture absorption, etc. during the manufacturing process can be reduced.
• the conditions for producing the prepreg are not particularly limited, but in the case of a solvent method, it is preferable that 80 mass % or more of the organic solvent used in the resin varnish has been evaporated in the obtained prepreg.
• the drying temperature after impregnating or coating the resin composition on the substrate is preferably 80 to 180°C, more preferably 100 to 140°C, and the drying time is appropriately set taking into account the gelation time of the resin composition.
• the solid content derived from the resin composition in the prepreg of this embodiment is not particularly limited, but is preferably 30 to 90 mass%, more preferably 35 to 80 mass%, even more preferably 40 to 70 mass%, and particularly preferably 45 to 60 mass%. If the solid content derived from the resin composition in the prepreg is within the above range, good moldability tends to be obtained when it is made into a laminate.
• the thickness of the prepreg in this embodiment is not particularly limited, and may be 10 to 200 ⁇ m, 10 to 150 ⁇ m, or 10 to 100 ⁇ m.
• the laminate of the present embodiment is a laminate containing a cured product of the resin composition of the present embodiment.
• the laminate of the present embodiment may also be a laminate containing a cured product of the prepreg of the present embodiment.
• the metal-clad laminate of the present embodiment is a metal-clad laminate including a metal foil and a cured product of the resin composition of the present embodiment.
• the metal-clad laminate of the present embodiment may also be a metal-clad laminate including a cured product of the prepreg of the present embodiment.
• the metal-clad laminate can be produced, for example, by stacking both adhesive surfaces of one prepreg of the present embodiment or two or more (preferably 2 to 20) prepregs of the present embodiment together with metal foil, and then heating and press-molding the laminate in a vacuum press at preferably 130 to 260° C., more preferably 180 to 250° C., and even more preferably 210 to 250° C., and at a pressure of 0.5 to 10 MPa, preferably 1 to 5 MPa.
• metal foils used in metal-clad laminates include copper foil, aluminum foil, tin foil, tin-lead alloy (solder) foil, nickel foil, etc.
• a three-layer composite foil having an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc., and a copper layer of 0.5 to 15 ⁇ m and a copper layer of 10 to 300 ⁇ m on both sides of the intermediate layer, and a two-layer composite foil having aluminum and copper foils can be used.
• copper foil and aluminum foil are preferred, and copper foil is more preferred.
• the thickness of the metal foil can be a thickness generally used for laminates, for example, 1 to 200 ⁇ m.
• the prepreg (more specifically, the resin composition in the prepreg) is C-staged and cured.
• the laminate of this embodiment contains a C-staged prepreg
• the metal-clad laminate of this embodiment contains a C-staged prepreg and a metal foil.
• C-staging refers to bringing the material into the C-stage state defined in JIS K6900 (1994).
• the printed wiring board of this embodiment is a printed wiring board containing a cured product of the resin composition of this embodiment.
• the printed wiring board of this embodiment may also contain one or more selected from the group consisting of the cured product of the prepreg of this embodiment, the laminate of this embodiment, and the metal-clad laminate.
• the printed wiring board of this embodiment does not necessarily have to contain the laminate or the metal-clad laminate as it is, and may also contain, for example, a laminate or a metal-clad laminate in a state in which a circuit formation process such as a hole drilling process, a metal plating process, or an etching process of a metal foil is performed.
• the printed wiring board of this embodiment can be manufactured by using the laminate or metal-clad laminate of this embodiment and performing circuit formation processing by known methods such as drilling, metal plating, and etching of metal foil, and further performing multi-layer processing as necessary.
• the semiconductor package of this embodiment includes the printed wiring board of this embodiment and a semiconductor element, that is, the semiconductor package of this embodiment is configured by mounting a semiconductor element on the printed wiring board of this embodiment.
• the semiconductor package of this embodiment can be manufactured, for example, by mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on the printed wiring board of this embodiment by a known method, and sealing the semiconductor elements with sealing resin or the like.
• the weight average molecular weight (Mw) was measured by the following method.
• the values were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
• the calibration curve was approximated by a third-order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name].
• TSKstandard POLYSTYRENE Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 [manufactured by Tosoh Corporation, product name].
• the measurement conditions for GPC are shown below.
• Test method (1) Flame retardancy In accordance with UL-94, five test pieces were used to investigate the flaming combustion time (seconds) and calculate the average value of the five.
• the test pieces were prepared by immersing a double-sided copper-clad laminate in a copper etching solution to remove the copper foil, and then cutting the laminate into a size of 125 mm x 13 mm.
• Adhesive strength with copper foil was evaluated by measuring the load when the copper foil line was peeled off at a speed of 50 mm/min in a 90° direction to the adhesive surface, using the copper foil of the double-sided copper-clad laminate obtained in each example as a test piece by partially etching the copper foil to form a copper foil line with a width of 3 mm. If the load when peeling was 0.3 kN/m or more, it was determined that the adhesion with the copper foil was sufficient.
• the double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to remove the copper foil, thereby preparing a test piece of 40 mm x 40 mm.
• the test piece was treated with a swelling treatment liquid "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) at 70°C for 5 minutes. Then, it was washed with water at room temperature for 2 minutes, and then roughened by treating with a roughening liquid "Concentrate Compact CP" (manufactured by Atotech Japan Co., Ltd.) at 80°C for 10 or 15 minutes.
• the desmear weight loss was calculated from the difference between the dry weight before the desmear treatment and the dry weight after the desmear treatment (dry weight before the desmear treatment ⁇ dry weight after the desmear treatment).
• Example 1 a percentage based on the desmear weight reduction amount in Comparative Example 1 [100 ⁇ (desmear weight reduction amount in Example 1 or Example 2)/(desmear weight reduction amount in Comparative Example 1)] was determined, and in Examples 3 and 4, a percentage based on the desmear weight reduction amount in Comparative Example 2 [100 ⁇ (desmear weight reduction amount in Example 3 or Example 4)/(desmear weight reduction amount in Comparative Example 2)] was determined.
• thermomechanical analyzer manufactured by TA Instruments Japan, product name: Q400
• IPC The Institute for Interconnecting and Packaging Electronic Circuits
• Epoxy resin "EPICLON HP-9500", a naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, product name)
• Maleimide compound siloxane-modified maleimide compound prepared in Production Example 1
• Inorganic filler 1 Fused spherical silica surface-treated with a phenylsilane coupling agent, average particle size 0.5 ⁇ m
• Vinylsilane coupling agent 1 "KBM-1083" (manufactured by Shin-Etsu Chemical Co., Ltd.)
• Epoxy silane coupling agent 1 "KBM-4803" (Shin-Etsu Chemical Co., Ltd.)
• Aminosilane coupling agent 1 "KBM-6803" (manufactured by Shin-Etsu Chemical Co., Ltd.)
• Aminosilane coupling agent 2 “KBM-603" (manufactured by Shin-Etsu Chemical Co., Ltd.)
• Curing accelerator 1 Isocyanate masked imidazole "G-8009L" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name)
• the double-sided copper-clad laminates of the examples using the resin composition of this embodiment were excellent in flame retardancy while maintaining good adhesive strength to the copper foil and desmear resistance, even though the resin composition contained the relatively easily combustible component (A).
• the double-sided copper-clad laminates of the examples also had good low thermal expansion properties.
• the double-sided copper-clad laminate of the comparative example, which used a resin composition not containing component (D) had lower flame retardancy than the examples.

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