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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
  • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
  • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
  • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/527—Cyclic esters
• • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen
• • 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
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • 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
• • 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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

• the present disclosure relates to resin compositions, prepregs, laminates, metal-clad laminates, printed wiring boards, and semiconductor packages.
• Warpage is considered to be one of the causes of poor connection between a semiconductor element and a printed wiring board, and there is a demand for a reduction in warpage.
• One of the causes of warping of a semiconductor package is the difference in coefficient of thermal expansion between the semiconductor element and the printed wiring board.
• the coefficient of thermal expansion of the printed wiring board is higher than that of the semiconductor element, so stress is generated due to the thermal history and the like applied when the semiconductor element is mounted, and warping occurs. Therefore, in order to suppress the warp of the semiconductor package, it is necessary to reduce the thermal expansion coefficient of the printed wiring board so as to reduce the difference from the thermal expansion coefficient of the semiconductor element.
• the coefficient of thermal expansion of a prepreg obtained by impregnating a glass cloth with a resin composition follows the Scapery formula shown by the following formula.
• A is the thermal expansion coefficient of the prepreg
• Ar is the thermal expansion coefficient of the resin composition
• Er is the elastic modulus of the resin composition
• Fr is the volume fraction of the resin composition
• Ag is the thermal expansion coefficient of the glass cloth.
• Eg is the elastic modulus of the glass cloth
• Fg is the volume fraction of the glass cloth.
• resin compositions that provide low thermal expansion include resin compositions containing a "siloxane-modified maleimide compound" obtained by modifying a polybismaleimide compound with a siloxane compound (see, for example, Patent Document 1). Moreover, as a resin composition from which a low elastic modulus can be obtained, there is a resin composition containing an acrylic polymer (see, for example, Patent Document 2).
• the present disclosure aims to provide a resin composition that has low thermal expansion and exhibits high adhesive strength with metal foil and high solder heat resistance.
• a further object of the present invention is 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 [1] to [12].
• C1 A resin composition containing (A) an acrylic polymer and (B) a thermosetting resin, A resin composition further comprising at least one selected from the group consisting of (C) (C1) a phosphate ester compound, (C2) a phosphazene compound and (C3) a phosphaphenanthrene compound.
• RA1 represents a hydrogen atom or a methyl group
• RA2 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• Component (B) is epoxy resin, polyimide resin, maleimide compound, phenol resin, polyphenylene ether resin, bismaleimide triazine resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester
• a metal-clad laminate comprising a metal foil and the cured prepreg of [8] above.
• a printed wiring board comprising the laminate according to [9] or the metal-clad laminate according to [10].
• a semiconductor package including the printed wiring board according to [11] above and a semiconductor element.
• a resin composition that has low thermal expansion and exhibits high adhesive strength with metal foil and high heat resistance.
• a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a semiconductor package can be provided using the resin composition.
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• the lower and upper limits of a numerical range can be arbitrarily combined with the lower and upper limits of other numerical ranges, respectively.
• both numerical values AA and BB are included in the numerical range as lower and upper limits, respectively.
• the description of "10 or more” means 10 and a numerical value exceeding 10, and this also applies when the numerical values are different.
• the description "10 or less” means 10 and less than 10, and the same applies when the numerical values are different.
• each component and material exemplified in this specification may be used alone or in combination of two or more unless otherwise specified.
• the content of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means
• solid content refers to components in the resin composition other than volatile substances such as water and organic solvents. That is, the solid content includes those that are liquid at around 25°C, starch syrup, or wax, and does not necessarily mean that they are solid. Aspects in which the items described in this specification are arbitrarily combined are also included in the present disclosure and the embodiments.
• One of the present embodiments includes (A) an acrylic polymer (hereinafter sometimes referred to as "(A) component”) and (B) a thermosetting resin (hereinafter sometimes referred to as “(B) component”) (C) (C1) a phosphate ester compound, (C2) a phosphazene compound, and (C3) a phosphaphenanthrene compound. It is a resin composition comprising: Here, in the present embodiment, "at least one selected from the group consisting of (C1) a phosphate ester compound, (C2) a phosphazene compound and (C3) a phosphaphenanthrene compound” is used as the component (C).
• Each component contained in the resin composition of the present embodiment will be described in detail below.
• the component (A) is an acrylic polymer, more specifically, a polymer containing a (meth)acrylic acid ester as a monomer.
• “(meth)acrylic acid” indicates both "acrylic acid” and "methacrylic acid”.
• (A) component may be used individually by 1 type, and may use 2 or more types together.
• Component (A) can also be said to be an acrylic polymer containing a structural unit derived from a (meth)acrylic acid ester, and includes a structural unit derived from a (meth)acrylic acid ester represented by the following general formula (A1). Acrylic polymers are preferred.
• RA1 represents a hydrogen atom or a methyl group
• RA2 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
• the number of carbon atoms in the alkyl group represented by R A2 is preferably 1-20, more preferably 1-15, even more preferably 2-10.
• Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group and the like.
• the alkyl group may have a substituent.
• substituents for the alkyl group include cycloalkyl groups, hydroxyl groups, halogens, oxygen-containing hydrocarbon groups, nitrogen-containing cyclic groups, and the like.
• the total carbon number of the cycloalkyl-substituted alkyl group is preferably 6-13, more preferably 7-10.
• Cycloalkyl-substituted alkyl groups include a norbornylmethyl group, a tricyclodecylethyl group, and the like.
• the number of carbon atoms in the cycloalkyl group represented by R A2 is preferably 6-13, more preferably 7-10.
• Cycloalkyl groups include cyclohexyl, norbornyl, tricyclodecanyl, isobornyl, and adamantyl groups. Among these, as the cycloalkyl group, a norbornyl group, a tricyclodecanyl group, and an isobornyl group are preferable.
• the number of carbon atoms in the aryl group represented by R A2 is preferably 6-13, more preferably 6-10.
• the aryl group includes a phenyl group, a nonylphenyl group, and the like.
• the number of carbon atoms in the aralkyl group represented by R A2 is preferably 7-15, more preferably 7-11.
• the aralkyl group includes benzyl group, 4-methylbenzyl group and the like.
• acrylic polymers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylic 2-ethylhexyl acid, 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, (meth)acrylic Lauryl acid, allyl (meth)acrylate, norbornylmethyl (meth)acrylate, tricyclodecylethyl
• Component (A) is not particularly limited, but is preferably an acrylic polymer having a crosslinkable functional group.
• the acrylic polymer having a crosslinkable functional group a (meth)acrylic acid ester and a copolymerizable monomer having a crosslinkable functional group (hereinafter sometimes simply referred to as "crosslinkable copolymerizable monomer").
• the crosslinkable copolymer monomer preferably has a crosslinkable functional group such as a carboxy group, a hydroxyl group, an amino group, a vinyl group, a glycidyl group, or an epoxy group.
• an epoxy group is preferable as the crosslinkable functional group from the viewpoint of low hygroscopicity and soldering heat resistance.
• the crosslinkable copolymerizable monomer is preferably a compound having a double bond.
• crosslinkable copolymerizable monomer examples 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; hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxy methacrylate; monomers having a hydroxyl group such as ethyl 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 a monomer having a nitrile group such as acrylonitrile; These may be used individually by 1 type, and may use 2 or more types together.
• a monomer having a carboxy group a monomer having an epoxy group, a monomer having a hydroxyl group, and a monomer having an amino group are preferable. is more preferred, and glycidyl acrylate and glycidyl methacrylate are even more preferred.
• the acrylic polymer includes N-vinylpyrrolidone acrylate, N-vinylpyrrolidone methacrylate, N-acryloylmorpholine, N-methacryloylmorpholine, an aromatic vinyl compound, an N-substituted maleimide compound, and general formula (A1) above. It may be a copolymer of a (meth)acrylic ester and a polymerizable monomer selected from the group consisting of (meth)acrylic esters other than those represented by.
• the amount of the (meth)acrylic acid ester used is It 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, based on 100 parts by mass as the total amount with the 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, with respect to 100 parts by mass of the total amount of the (meth)acrylic acid ester and the crosslinkable copolymer monomer. Preferably, 3 to 20 parts by mass is more preferable.
• the total content of the (meth)acrylic acid ester and the crosslinkable copolymer monomer in all raw material monomers of the acrylic polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. More preferably, it may be 100% by mass.
• component (A) has an epoxy group
• its epoxy equivalent is preferably 1,000 to 18,000 g/eq, more preferably 2,000 to 15,000 g/eq, and 3,000 to 10,000 g/eq. is more preferred, and 3,500 to 7,000 g/eq is particularly preferred.
• the epoxy equivalent is at least the lower limit, the dimensional stability of the substrate tends to be maintained. tend to be better.
• the epoxy equivalent of component (A) can be adjusted by appropriately adjusting the copolymerization ratio when glycidyl (meth)acrylate and other monomers copolymerizable therewith are copolymerized.
• acrylic polymer (A) having an epoxy group examples include “HTR-860” (manufactured by Nagase ChemteX Corporation, trade name, epoxy equivalent: 2,900 g/eq), "Teisan Resin (registered trademark) SG -P3” (manufactured by Nagase ChemteX Corporation, trade name, epoxy equivalent 4,761 to 14,285 g / eq, weight average molecular weight 350,000 to 850,000), “KH-CT-865” (Showa Denko Materials Co., Ltd. product, trade name, epoxy equivalent of 3,300 g/eq), and the like.
• the weight average molecular weight (Mw) of component (A) is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,300,000 from the viewpoint of improving low elasticity and elongation. ,000 to 1,100,000, 100,000 to 950,000, or 300,000 to 1,100,000, or 500,000 ⁇ 1,000,000, or 700,000 to 1,000,000. If the weight-average molecular weight of component (A) is at least the lower limit, the components (A) and (B) are not completely compatible with each other and tend to form a phase-separated structure. If so, it tends to be easily dissolved in a solvent and to be excellent in handleability and dispersibility. In addition, (A) component may combine 2 or more types from which a weight average molecular weight differs.
• the weight average molecular weight is a value measured by gel permeation chromatography (GPC) analysis, and means a standard polystyrene conversion value.
• GPC analysis can be performed using tetrahydrofuran (THF) as a solvent.
• THF tetrahydrofuran
• the component (A) may be powdery at 25°C or liquid at 25°C. It is preferably liquid at 25°C from the viewpoint of being excellent in
• the content of component (A) in the resin composition of the present embodiment is not particularly limited, but is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C). 45 parts by mass is more preferred, 15 to 40 parts by mass is even more preferred, and 15 to 35 parts by mass is particularly preferred.
• the content of component (A) is at least the above lower limit, there is a tendency to sufficiently obtain low elasticity and flexibility, which are excellent features of component (A). Sufficient adhesive strength with metal foil and high solder heat resistance tend to be obtained.
• Component (B) includes epoxy resins, polyimide resins, maleimide compounds, phenol resins, polyphenylene ether resins, bismaleimide triazine resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, and allyl. resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, and the like. Among these, epoxy resins and maleimide compounds are preferred as component (B).
• (B) As a component you may use individually by 1 type, and may use 2 or more types together.
• 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, and the like. 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 in each of the above types of epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.
• Epoxy resins alicyclic epoxy resins such as dicyclopentadiene type epoxy resins; aliphatic linear epoxy resins; Novolac type epoxy resins such as phenol aralkyl novolac type epoxy resins and biphenyl aralkyl novolac type epoxy resins; stilbene type epoxy resins; naphthol novolak type epoxy resins and naphthol aralkyl type epoxy resins such as naphthalene skeleton-containing epoxy resins; biphenyl type epoxy resins; It is classified into xylylene type epoxy resin, dihydroanthracene type epoxy resin, etc.
• the epoxy resin is preferably a naphthalene skeleton-containing type epoxy resin, more preferably a naphthol aralkyl type epoxy resin, from the viewpoint of solder heat resistance and low thermal expansion.
• the weight average molecular weight of the epoxy resin may be 200-1,000, or 300-900.
• the weight-average molecular weight of the epoxy resin is at least the lower limit, the soldering heat resistance tends to be excellent, and when it is at most the upper limit, low elasticity and flexibility tend to be exhibited.
• 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.
• maleimide compound examples include a maleimide compound (b1) having two or more N-substituted maleimide groups [hereinafter sometimes simply referred to as “maleimide compound (b1)” or “component (b1)”. ] and derivatives thereof.
• the component (B) preferably contains 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 thereof” include an addition reaction product of a maleimide compound (b1) having two or more N-substituted maleimide groups and an amine compound such as a diamine compound described later.
• the maleimide compound (b1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups.
• Specific examples of the maleimide compound (b1) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3′- Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy) aromatic maleimide compounds such as phenyl]propane; aliphatic maleimide compounds such as 1,6-bismaleimide-(2,2,4-trimethyl)hexane and pyrrolonic acid binder type long-chain alkylbismaleimide.
• the maleimide compound (b1) is preferably an aromatic maleimide compound, more preferably an aromatic bismaleimide compound, and 2,2-bis[4-( More preferred are 4-maleimidophenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide.
• maleimide compound (b1) a compound represented by the following general formula (B1-1) is preferable.
• X b1 represents a divalent organic group.
• the divalent organic group represented by X b1 in the general formula (B1-1) is represented by the following general formula (B1-2), (B1-3), (B1-4) or (B1-5). and the group to be carried out.
• 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 aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R b1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl. and the like.
• the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group.
• nb1 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0, from the viewpoint of availability. When n b1 is an integer of 2 or more, a plurality of 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 is an alkylene group having 1 to 5 carbon atoms;
• n b2 and n b3 are an alkylidene group, 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). , each independently represents an integer of 0 to 4. * represents a bonding position.
• the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b2 and R b3 refers to the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in general formula (B1-2) above. Same as description.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. is mentioned.
• the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
• the alkylidene group is preferably an isopropylidene group.
• nb2 and nb3 are integers of 0 to 4, preferably integers of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. When n b2 is an integer of 2 or more, the plurality of R b2 may be the same or different. When n b3 is an integer of 2 or more, the plurality of R b3 may be the same or different.
• the divalent group represented by the general formula (B1-3-1) 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 is an alkylene group having 1 to 5 carbon atoms
• nb4 and nb5 each independently represents an integer of 0 to 4. * represents a bonding position. .
• the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b4 and R b5 refers to the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in general formula (B1-2) above. Same as description.
• 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 alkylene group having 1 to 5 carbon atoms and 2 carbon atoms represented by X b2 in the general formula (B1-3). The same as the alkylidene group of 1 to 5 can be mentioned.
• nb4 and nb5 are integers of 0 to 4, preferably integers of 0 to 2, more preferably 0, from the viewpoint of availability.
• n b4 is an integer of 2 or more
• the plurality of R b4 may be the same or different.
• n b5 is an integer of 2 or more, the plurality of R b5 may be the same or different.
• n b6 represents an integer of 1 to 10. * represents a binding position.
• nb6 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, from the viewpoint of availability.
• 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. .
• nb7 represents an integer of 1 to 8, preferably an integer of 1 to 3, more preferably 1.
• n b7 is an integer of 2 or more, the plurality of R b6 may be the same or different, and the plurality of R b7 may be the same or different.
• the maleimide compound is preferably a derivative of the maleimide compound (b1) from the viewpoints of solubility in organic solvents, compatibility, adhesion to metal foil, and dielectric properties.
• Derivatives of the maleimide compound (b1) include structural units derived from the maleimide compound (b1) and an amine compound (b2) having a primary amino group [hereinafter referred to as “amine compound (b2)" or “(b2) component”]. may be abbreviated. ] and a modified maleimide compound (Z) [hereinafter sometimes abbreviated as “modified maleimide compound (Z)” or “(Z) component”. ] is preferable.
• the resin composition of the present embodiment contains the maleimide compound as the component (B), and the maleimide compound has at least two N-substituted maleimide groups and is derived from a structural unit derived from the maleimide compound (b1). and a structural unit derived from the 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 consist of one type, or a combination of two or more types. It can be anything.
• the modified maleimide compound (Z) includes a structure represented by the following formula (B-1) obtained by an addition reaction between the maleimide group of the component (b1) and the primary amino group of the component (b2). A compound is preferred. (* indicates the binding position to other structures.)
• the structural unit derived from the component (b1) is, for example, one or more selected from the group consisting of a group represented by the following general formula (B1-6) and a group represented by the following general formula (B1-7). are mentioned.
• X b1 is the same as X b1 in the general formula (B1-1) above, and * indicates the bonding position to another structure.
• the content of the structural unit derived from the component (b1) in the modified maleimide compound (Z) is not particularly limited, but is preferably 50 to 95% by mass, more preferably 70 to 92% by mass, and further preferably 75 to 90% by mass. preferable. If the content of the structural unit derived from the component (b1) 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, 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, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3
• the modified maleimide compound (Z) is preferably a siloxane-modified maleimide compound (Z).
• 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.
• Component (b2) is an aromatic diamine compound in which X b4 in general formula (B2-1) above is a divalent group represented by general formula (B2-2) below [hereinafter referred to as "aromatic diamine compound (B2-2)” may be abbreviated. ] is preferably contained.
• 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 1 carbon atom; ⁇ 5 alkylene group, 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 the following general formula (B2-2-1) or ( B2-2-2) represents a divalent group, n b8 and n b9 each independently 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 b11 and R b12 in the general formula (B2-2) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl. group, isobutyl group, t-butyl group, n-pentyl group and the like.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b5 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. is mentioned.
• alkylidene group having 2 to 5 carbon atoms represented by X b5 examples include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
• n b8 and n b9 each represent an integer of 0 to 4, preferably 0 or 1 from the viewpoint of availability. When nb8 or nb9 is an integer of 2 or more, a plurality of Rb11 's or a plurality of Rb12 's may be the same or different.
• the divalent group represented by general formula (B2-2-1) represented by X b5 in general formula (B2-2) is as follows.
• R b13 and R b14 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom
• X b6 is an alkylene group having 1 to 5 carbon atoms
• nb10 and nb11 each independently , indicates an integer from 0 to 4. * indicates a binding position.
• the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R b13 and R b14 in general formula (B2-2-1) are described in terms of R b11 and R b12 in general formula (B2-2). is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms shown by .
• the description of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b6 refers to the alkylene group having 1 to 5 carbon atoms represented by X b5 in the above general formula (B2-2), carbon The description is the same as for the alkylidene groups of numbers 2 to 5.
• n b10 and n b11 each represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0, from the viewpoint of availability.
• n b10 is an integer of 2 or more
• the plurality of R b13 may be the same or different.
• n b11 is an integer of 2 or more
• the plurality of R b14 may be the same or different.
• the divalent group represented by general formula (B2-2-2) represented by X b5 in 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; represents an alkylidene group, 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 the bonding position.
• the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b15 in the general formula (B2-2-2) includes the carbon atoms represented by R b11 and R b12 in the general formula (B2-2). It is the same as the explanation for the aliphatic hydrocarbon groups of numbers 1 to 5.
• 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 alkylene group having 1 to 5 carbon atoms represented by X b5 in the general formula (B2-2), The same as the alkylidene group having 2 to 5 carbon atoms are exemplified.
• X b7 and X b8 are preferably alkylidene groups having 2 to 5 carbon atoms, and more preferably iropropylidene groups.
• nb12 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0, from the viewpoint of availability.
• n b12 is an integer of 2 or more, a plurality of R b15 may be the same or different.
• the component (b2) is 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). "is preferably contained.
• Component (b2) contains a "terminal amine-modified siloxane compound” in which X b4 in general formula (B2-1) above contains a structural unit represented by general formula (B2-4) below. more preferred.
• 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 a bonding position.
• R b16 and R b17 are the same as in the general formula (B2-3) above, R b18 and R b19 are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group, or represents a substituted phenyl group, X b9 and X b10 each independently represents a divalent organic group, n b13 represents an integer of 2 to 100, * represents a bonding position.
• alkyl groups having 1 to 5 carbon atoms represented by R b16 to R b19 in general formulas (B2-3) and (B2-4) above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like.
• the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
• Examples of substituents possessed by 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, an alkynyl group having 2 to 5 carbon atoms, and the like. mentioned.
• Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group.
• Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl group and allyl group.
• Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group and 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—, and a divalent linking group in which these are combined.
• Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group.
• Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms.
• the alkynylene group includes, for example, an alkynylene group having 2 to 10 carbon atoms.
• arylene group examples include arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group.
• Xb9 and Xb10 are preferably an alkylene group or an arylene group, more preferably an alkylene group.
• nb13 represents an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 30.
• the plurality of R b16 or the plurality of R b17 may be the same or different.
• the structural unit derived from the component (b2) is, for example, one or more selected from the group consisting of a group represented by the following general formula (B2-5) and a group represented by the following general formula (B2-6). is mentioned. (Wherein, X b4 is the same as X b4 in the general formula (B2-1) above, and * indicates the bonding position.)
• the content of the structural unit derived from the component (b2) in the modified maleimide compound (Z) is not particularly limited, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass, and further preferably 10 to 25% by mass. preferable. If the content of the structural unit derived from the component (b2) is within the above range, there is a tendency to obtain 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 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 is preferably 80% by mass or more, more preferably 90% by mass or more. It is preferably 95% by mass or more, more preferably 100% by mass (that is, composed only of structural units derived from component (b1) and structural units derived from component (b2)).
• 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 group derived from the —NH 2 group of the component (b2) ( —NH 2 ) to the total equivalent (Ta2) of the maleimide group-derived group (including the maleimide group) derived from the component (b1), the equivalent ratio (Ta1/Ta2) of the total equivalent (Ta1) is preferably The content ratio is 0.05 to 10, more preferably 2 to 8. If the equivalent ratio (Ta1/Ta2) is within the above range, there is a tendency to obtain excellent low thermal expansion properties and dielectric properties, as well as good solder heat resistance, flame retardancy and glass transition temperature.
• the maleimide compound may contain a compound represented by the following general formula (B-2) from the viewpoint of dielectric properties, insulation reliability, solubility in organic solvents, adhesion to metal foil, moldability, etc. preferable.
• the (Z) component can be produced, for example, by reacting the (b1) component and the (b2) component in an organic solvent. Specifically, the components (b1), (b2), and, if necessary, other components are charged in predetermined amounts into a reactor, and the components (b1) and (b2) undergo a Michael addition reaction [hereinafter referred to as a "pre-reaction”. sometimes referred to as ] to obtain a modified maleimide compound (Z).
• 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 is preferably 1 to 10 hours, more preferably 1 to 5 hours.
• a reaction catalyst may be used in the pre-reaction as necessary.
• the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. . These may be used individually by 1 type, and may use 2 or more types together.
• the amount of the reaction catalyst to be added is not particularly limited, but is, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of components (b1) and (b2).
• an organic solvent may be added or concentrated as necessary to adjust the solid content concentration of the reaction raw materials and the viscosity of the reaction liquid.
• the solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. If the solid content concentration of the reaction raw material is at least the above lower limit, a sufficient reaction rate can be obtained, which tends to be advantageous in terms of production cost, and if it is below the above upper limit, good solubility can be obtained. , the stirring efficiency is improved, and gelation tends to be difficult.
• 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, further preferably 1,500 to 4,000, 2,000 to 3,000 are particularly preferred.
• the content of component (B) is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and more preferably 60 to 85 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C). More preferably, 65 to 85 parts by mass is particularly preferable. If the content of component (B) is at least the above lower limit, there is a tendency to obtain sufficient adhesive strength with the metal foil and high solder heat resistance. tend to be of good quality.
• Component (C) is at least one selected from the group consisting of (C1) phosphate ester compounds, (C2) phosphazene compounds and (C3) phosphaphenanthrene compounds.
• Component (C) is selected from the group consisting of (C1) a phosphate ester compound and (C2) a phosphazene compound from the viewpoint of improving the adhesive strength with a metal foil and soldering heat resistance while maintaining good low thermal expansion properties. At least one selected is preferred.
• the resin composition further contains the (C) component, so that the resin composition has excellent low thermal expansion, and furthermore, excellent adhesive strength with the metal foil and solder heat resistance. It becomes a thing.
• the specific component (C) has excellent compatibility or solubility in the resin composition or resin varnish containing the components (A) and (B). It is inferred that the fact that the The components (C1) to (C3) are described in detail below.
• the phosphate ester compounds may be used singly or in combination of two or more.
• a commercial item can be used for the phosphate ester compound.
• an aromatic phosphate (hereinafter referred to as aromatic phosphate (C1-1). ] is preferable.
• the aromatic phosphate ester is a phosphate ester having an aromatic hydrocarbon group.
• the aromatic hydrocarbon group possessed by the aromatic phosphate (C1-1) may be a monovalent group or a divalent or higher valent group.
• the aromatic ring contained in the aromatic hydrocarbon group may be a non-condensed ring or a condensed ring.
• the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and pyrene ring.
• a benzene ring is preferable from the viewpoint of improving adhesive strength with a metal foil and soldering heat resistance while maintaining good low thermal expansion properties.
• Aromatic rings may or may not be substituted by substituents.
• substituents examples include aliphatic hydrocarbon groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group.
• aromatic hydrocarbon group a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenylene group, or a group, and more preferably an unsubstituted phenyl group or an unsubstituted phenylene group.
• aromatic phosphate (C1-1) has a plurality of aromatic hydrocarbon groups, they may be the same or different.
• the aromatic hydrocarbon group may have a linking group having 5 or less carbon atoms.
• the linking group having 5 or less carbon atoms includes a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent heteroatom-containing group having 5 or less carbon atoms, and a hydrocarbon group and a heteroatom-containing group linked together. Examples thereof include divalent groups having 1 to 5 carbon atoms.
• Examples of the divalent hydrocarbon group having 1 to 5 carbon atoms include carbon atoms such as methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. alkylene groups of number 1 to 5; alkylidene groups having 2 to 5 carbon atoms such as ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group and isopentylidene group.
• Examples of divalent heteroatom-containing groups having 5 or less carbon atoms include ether groups, sulfide groups, sulfonyl groups, carbonyloxy groups and keto groups.
• the aromatic hydrocarbon group is a divalent group
• the aromatic hydrocarbon group maintains good low thermal expansion properties, and from the viewpoint of improving adhesive strength with metal foil and solder heat resistance, A divalent group represented by the following general formula (C-1-1) is preferred.
• R c5 and R c6 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
• X c2 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond of n c6 and n c7 each independently represent an integer of 0 to 4.
• n c8 represents 1 to indicates an integer of 3.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X c2 in the general formula (C-1-1) include methylene group, 1,2-dimethylene group, 1,3-trimethylene group and 1,4-tetramethylene group, 1,5-pentamethylene group, and the like.
• the alkylidene group having 2 to 5 carbon atoms represented by X c2 includes ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
• a methylene group, an isopropylidene group, and a single bond are preferable from the viewpoint of improving adhesive strength with a metal foil and soldering heat resistance while maintaining good low thermal expansion properties.
• An isopropylidene group is more preferred.
• Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R c5 and R c6 in general formula (C-1-1) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl. group, isobutyl group, t-butyl group, n-pentyl group and the like.
• n c6 and n c7 in the general formula (C-1-1) are 0 to 3 from the viewpoint of improving the adhesive strength with the metal foil and the solder heat resistance while maintaining good low thermal expansion properties.
• An integer is preferred, 0 or 1 is more preferred, and 0 is even more preferred.
• n c6 is an integer of 2 or more
• the plurality of R c5 may be the same or different.
• n c7 is an integer of 2 or more, the plurality of R c6 may be the same or different.
• n c8 in the general formula (C-1-1) is preferably 1 or 2, more preferably 1.
• n c8 is an integer of 2 or more
• multiple X c2 may be the same or different
• multiple n c7 may be the same or different.
• the number of phosphorus atoms in one molecule of the aromatic phosphate (C1-1) is not particularly limited, but it improves the adhesive strength with the metal foil and solder heat resistance while maintaining good low thermal expansion. From this point of view, the number is preferably 1 to 10, more preferably 2 to 5, even more preferably 2 or 3, and particularly preferably 2.
• the aromatic phosphate (C1-1) has two or more phosphorus atoms, the phosphate ester bond formed by a specific phosphorus atom and the phosphate ester bond formed by another phosphorus atom are Preferred are condensed phosphate esters linked by a divalent aromatic hydrocarbon group.
• the phosphate group of the aromatic phosphate (C1-1) may be an alkyl ester, an aryl ester, an aralkyl ester, or the like.
• An aryl ester is preferable from the viewpoint of improving the adhesive strength and soldering heat resistance of .
• the aryl group constituting the aryl ester is the same as the monovalent aromatic hydrocarbon group, and examples thereof include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and the like.
• Substituents for the aryl group include hydrocarbons having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group. group; halogen atom and the like.
• the aryl group is preferably an unsubstituted phenyl group or a 2,5-dimethylphenyl group.
• the aromatic phosphate ester (C1-1) is represented by the following general formula (C-1) from the viewpoint of improving the adhesive strength with the metal foil and solder heat resistance while maintaining good low thermal expansion properties.
• R c1 to R c4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X c1 is represented by the following general formula (C-1-1). represents a divalent group or a divalent condensed polycyclic aromatic hydrocarbon group, n c1 to n c4 each independently represent an integer of 0 to 5, and n c5 represents an integer of 0 to 5; .
• R c5 and R c6 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
• X c2 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond of n c6 and n c7 each independently represent an integer of 0 to 4.
• n c8 represents 1 to indicates an integer of 3.
• Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R c1 to R c4 in general formula (C-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like.
• the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
• n c1 to n c4 represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 2, further preferably 2.
• n c1 to n c4 are integers of 2 or more, a plurality of R c1s , R c2s , R c3s , or R c4s may be the same or different.
• n c5 represents an integer of 0 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, further preferably 1.
• multiple X c1 and multiple n c4 may be the same or different.
• the divalent condensed polycyclic aromatic hydrocarbon group represented by X c1 in the general formula (C-1) includes two hydrogen atoms from condensed polycyclic aromatic hydrocarbons such as naphthalene, anthracene and pyrene.
• a divalent group excluding is exemplified.
• the condensed polycyclic aromatic hydrocarbon group may or may not be substituted with a substituent.
• Substituents for the condensed polycyclic aromatic hydrocarbon group include carbon numbers such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group. 1 to 5 aliphatic hydrocarbon groups; and halogen atoms such as fluorine, chlorine, bromine and iodine atoms.
• phosphate compounds include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, 1,3-phenylene-bis(di- 2,6-dimethylphenyl phosphate), 1,3-phenylene-bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,4-phenylene-bis(di-2,6-dimethylphenyl phosphate), 4, 4′-biphenylene-bis(di-2,6-dimethylphenyl phosphate), bisphenol A-polyphenyl phosphate, 4,4′-biphenol-polycresyl phosphate, bisphenol A-polycresyl phosphate, 4,4′- biphenol-poly(2,6-xylenyl phosphate), bisphenol A-poly(2,6-xyl
• the “poly” in the specific examples of the phosphate ester compound is a repeating unit composed of a structure derived from a divalent phenol compound and a structure derived from phosphoric acid constituting the phosphate ester compound (for example, the general formula (C -1) means the structural unit in square brackets) means a compound whose number is 2 or more, and the average value of the repeating units exceeds 1 by containing the compound Sometimes it means
• a phosphazene compound may be used individually by 1 type, and may use 2 or more types together. Commercially available phosphazene compounds can be used.
• the phosphazene compound preferably has a structural unit represented by general formula (C-2) below.
• R c8 and R c9 each independently represent an organic group having 1 to 20 carbon atoms.
• the organic group having 1 to 20 carbon atoms represented by R c8 and R c9 in the general formula (C-2) includes an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. and the like.
• Aliphatic hydrocarbon groups having 1 to 20 carbon atoms which are exemplified as organic groups having 1 to 20 carbon atoms represented by R c8 and R c9 include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, Examples thereof include alkynyl groups having 2 to 20 carbon atoms.
• the above aliphatic hydrocarbon group may be linear, branched or cyclic.
• alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-ethylhexyl group and cyclohexyl group. etc.
• alkenyl group having 2 to 20 carbon atoms include vinyl group, propenyl group and butenyl group.
• the alkynyl group having 2 to 20 carbon atoms includes 2-propynyl group, 3-butynyl group and the like.
• the aliphatic hydrocarbon group having 1 to 20 carbon atoms may or may not have a substituent.
• substituents examples include a hydroxyl group, a carboxyl group, a halogen atom, an aromatic hydrocarbon group, an acyl group, an alkoxy group, and groups in which these substituents are linked.
• the carbon number of the substituent is also included in the number of carbon atoms.
• the number of carbon atoms in the aromatic hydrocarbon group with 6 to 20 carbon atoms exemplified as the organic group with 1 to 20 carbon atoms represented by R c8 and R c9 is preferably 6 to 15, more preferably 6 to 10.
• aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group and anthranyl group.
• the aromatic hydrocarbon group having 6 to 20 carbon atoms may or may not have a substituent.
• substituents examples include a hydroxyl group, a carboxyl group, a halogen atom, an aliphatic hydrocarbon group, an acyl group, an alkoxy group, a cyano group, a group in which these substituents are linked, and the like.
• a cyano group is preferable as the substituent.
• the carbon number of a substituent is also included in the said carbon number.
• the organic group having 1 to 20 carbon atoms represented by R c8 and R c9 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms from the viewpoint of flame retardancy, and an unsubstituted phenyl group, a substituent is more preferred, and unsubstituted phenyl and cyanophenyl groups are even more preferred.
• the phosphazene compound may be a chain phosphazene compound or a cyclic phosphazene compound, preferably a cyclic phosphazene compound.
• a phosphazene compound represented by the following general formula (C-3-1) is preferable, and a phosphazene compound represented by the following general formula (C-3-2) is more preferable.
• Ar c1 and Ar c2 each independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• n c8 represents an integer of 3 to 20.
• Arc3 to Arc8 each independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• the description of the aromatic hydrocarbon group having 6 to 20 carbon atoms is the same as the description of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R c8 and R c9 in the general formula (C-2).
• n c8 in general formula (C-3-1) above represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 5, and still more preferably 3.
• the phosphaphenanthrene compounds may be used singly or in combination of two or more. Commercially available phosphaphenanthrene can be used. Examples of phosphaphenanthrene include compounds represented by the following formula (C-4). (wherein R C10 and R C11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; b and c are each independently an integer of 0 to 4; A is a hydrogen atom or a group represented by any of the following formulas (C-5) to (C-7).) (* indicates the binding position.) (* indicates the binding position.) (* indicates the binding position.) (* indicates the binding position.)
• Phosphaphenanthrenes include 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 9,10-dihydro-10-(2,5-dihydroxyphenyl)-9-oxa-10-phospha phenanthrene 10-oxide and the like.
• the content of component (C) in the resin composition of the present embodiment is not particularly limited, but is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C). It is more preferably up to 30 parts by mass, even more preferably 5 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass. If the content of component (C) is at least the above lower limit, the adhesive strength with the metal foil and solder heat resistance tend to improve while maintaining low thermal expansion. , tends to provide excellent low thermal expansion properties.
• the resin composition of the present embodiment may further contain (D) a filler (hereinafter sometimes referred to as "(D) component").
• the filler is not particularly limited, but an inorganic filler is preferable from the viewpoint of ensuring low thermal expansion and flame retardancy.
• Inorganic fillers include silica, alumina, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whiskers, boron nitride, silicon carbide, and the like. mentioned.
• the filler may be used singly or in combination of two or more.
• silica is preferable because of its low dielectric constant and low coefficient of linear expansion.
• examples of silica include synthetic silica synthesized by a wet method or a dry method, crushed silica, fused silica, and the like.
• the filler may be a filler subjected to coupling treatment.
• a silane coupling agent is preferable as the coupling agent used in the coupling treatment.
• Silane coupling agents include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and silicone oligomers. system coupling agents, and the like. These may be used individually by 1 type, and may use 2 or more types together.
• the average particle size of component (D) is preferably 0.1 to 2.5 ⁇ m, more preferably 0.2 to 1.5 ⁇ m, even more preferably 0.3 to 0.8 ⁇ m. If the average particle diameter of component (D) is at least the lower limit, the filler tends to disperse easily in the resin varnish, and aggregation tends to occur with difficulty. D) Sedimentation of components tends not to occur easily.
• the average particle size in the present embodiment is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 100%, and laser diffraction It can be measured with a particle size distribution analyzer using a scattering method.
• the content of component (D) is not particularly limited, but 30 to 300 parts per 100 parts by mass of the total amount of the component (A) and the component (B). Parts by weight are preferred, 50 to 250 parts by weight are more preferred, 70 to 200 parts by weight are even more preferred, 100 to 200 parts by weight are particularly preferred, and 130 to 170 parts by weight are most preferred.
• the content of the (D) filler is at least the above lower limit, there is a tendency that the low thermal expansion property becomes high and sufficient solder heat resistance is obtained.
• the content of the filler (D) is equal to or less than the above upper limit, there is a tendency that the low elasticity and flexibility of the (A) acrylic polymer can be sufficiently obtained.
• the resin composition of the present embodiment may contain (E) a curing agent (hereinafter sometimes referred to as “(E) component”).
• the component (E) tends to increase the adhesive strength with the metal foil.
• Curing agents include phenolic resins such as phenolic novolac resin, cresol novolac resin, bisphenol A novolak resin, biphenyl novolac type phenolic resin, aminotriazine novolac type phenolic resin; Curing agents; acid anhydrides such as pyromellitic anhydride, trimellitic anhydride and benzophenonetetracarboxylic acid; and active ester curing agents.
• (E) component may be used individually by 1 type, and may use 2 or more types together.
• the content of component (E) is not particularly limited, but the total amount of active groups derived from the (E) curing agent with respect to the functional groups of the component (B) is 0. It is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.3 equivalents, even more preferably 0.7 to 1.2 equivalents.
• the content of the curing agent is within the above range, the adhesiveness to the metal foil, the glass transition temperature, and the insulating properties tend to be excellent.
• the resin composition of the present embodiment may contain (F) a curing accelerator (hereinafter sometimes referred to as "component (F)").
• component (F) component may be used individually by 1 type, and may use 2 or more types together.
• the (F) curing accelerator is not particularly limited, but is selected from the group consisting of amine compounds and imidazole compounds. It is preferable to contain one or more of these, and it is more preferable to contain an imidazole compound.
• the amine compound include dicyandiamide, diaminodiphenylethane, guanylurea, and the like.
• imidazole compounds examples include 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium tri Melitate, benzimidazole, isocyanate mask imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole) and the like.
• composition of the present embodiment contains (F) a curing accelerator
• its content is not particularly limited, but the total amount of the component (A) and the component (B) is 100 parts by mass. 0.01 to 10 parts by weight is preferred, 0.03 to 2 parts by weight is more preferred, and 0.1 to 1 part by weight is even more preferred.
• the resin composition of the present embodiment may optionally contain a cross-linking agent such as a melamine resin, a flame retardant, a flame retardant aid, a rubber-based elastomer, conductive particles, a coupling agent, a flow control agent, an antioxidant, a heat Stabilizers, antistatic agents, pigments, leveling agents, antifoaming agents, ion trapping agents and the like may be contained.
• a cross-linking agent such as a melamine resin, a flame retardant, a flame retardant aid, a rubber-based elastomer, conductive particles, a coupling agent, a flow control agent, an antioxidant, a heat Stabilizers, antistatic agents, pigments, leveling agents, antifoaming agents, ion trapping agents and the like may be contained.
• a cross-linking agent such as a melamine resin, a flame retardant, a flame retardant aid, a rubber-based elastomer, conductive particles
• 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 so-called "resin varnish” state.
• a resin composition containing an organic solvent may be referred to as a resin varnish.
• the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate.
• Solvent such as N-methylpyrrolidone, formamide, N-methylformamide, N,N-dimethylacetamide; methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol Alcohol solvents such as monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, and the like are included.
• An organic solvent may be used individually by 1 type, and may use 2 or more types together.
• the solid content concentration in the varnish is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, even more preferably 35 to 60% by mass.
• the prepreg of the present embodiment includes a base material and a semi-cured product of the resin composition of the present embodiment.
• the expression “comprising a base material and a semi-cured product of the resin composition of the present embodiment” means that the resin composition is semi-cured (B-staged) in a state in which the base material is impregnated. means to contain things.
• B-staging refers to making the state of B-stage 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 the form of varnish, followed by heating and drying to semi-harden (B-stage) the resin composition. can be done.
• the following hot-melt method or solvent method can be employed as a method for impregnating or coating the substrate with the resin composition.
• the hot-melt method does not contain an organic solvent in the resin composition, and (1) a method in which a coated paper having good releasability from the resin composition is once coated and then laminated to a substrate, or (2) ) A method of directly coating the substrate with a die coater.
• the solvent method is a method in which a substrate is impregnated with the resin composition by adding an organic solvent to the resin composition and immersing the substrate in the resulting resin composition, followed by drying.
• the substrate a fiber substrate such as a woven fabric or a nonwoven fabric is usually used, and the woven fabric is preferred.
• the base material is a sheet-like fiber base material.
• Inorganic fibers such as glass, alumina, asbestos, boron, silica-alumina glass, silica glass, tyranno, silicon carbide, silicon nitride, zirconia; aramid, polyetheretherketone, polyetherimide, polyether organic fibers such as sulfone, carbon and cellulose; Among these, inorganic fibers are preferred, and glass fibers are more preferred. That is, the base material is preferably a woven fabric of glass fibers, that is, a glass cloth.
• the thickness of the substrate is preferably 5-200 ⁇ m, may be 10-100 ⁇ m, or may be 20-50 ⁇ m.
• the prepreg production conditions are not particularly limited, but in the case of the solvent method, it is preferable that 80% by mass or more of the organic solvent used for the resin varnish volatilize in the prepreg to be obtained.
• the drying temperature after impregnating or applying the resin composition to the substrate is preferably 80 to 180° C., more preferably 100 to 140° C., and the drying time is in consideration of the gelation time of the resin composition. Appropriately set.
• the solid content derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, further preferably 40 to 70% by mass, and 45% by mass. ⁇ 60% by weight is particularly preferred. If the content of solids derived from the resin composition in the prepreg is within the above range, there is a tendency that good moldability can be obtained when the prepreg is formed into a laminate.
• the thickness of the prepreg of the present embodiment is not particularly limited, and may be 10-200 ⁇ m, 10-150 ⁇ m, or 10-100 ⁇ m.
• the laminate of the present embodiment is a laminate containing the cured prepreg of the present embodiment.
• the metal-clad laminate of the present embodiment is a metal-clad laminate containing a metal foil and a cured product of the prepreg of the present embodiment.
• the metal-clad laminate overlaps the adhesive surfaces on both sides of one prepreg of the present embodiment or a laminate obtained by laminating two or more (preferably 2 to 20) prepregs and a metal foil, Manufactured by heating and pressure molding in a vacuum press at a temperature of preferably 130 to 260° C., more preferably 180 to 250° C., still more preferably 210 to 250° C., and a pressure of 0.5 to 10 MPa, preferably 1 to 5 MPa. can do.
• Metal foils used for metal-clad laminates include copper foil, aluminum foil, tin foil, tin-lead alloy (solder) foil, nickel foil and the like.
• nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a copper layer of 0.5 to 15 ⁇ m and a copper layer of 10 to 300 ⁇ m are formed on both sides of the intermediate layer. can be used.
• the metal foil copper foil and aluminum foil are preferable, and copper foil is more preferable.
• the thickness of the metal foil can be the thickness commonly used for laminates, for example, 1 to 200 ⁇ m.
• the prepreg (specifically, the resin composition in the prepreg) is C-staged to be a cured product.
• the laminate of this embodiment includes C-staged prepreg
• the metal-clad laminate of this embodiment includes C-staged prepreg and metal foil.
• the printed wiring board of this embodiment includes the laminate or metal-clad laminate of this embodiment.
• the printed wiring board of the present embodiment does not necessarily include the laminate or the metal-clad laminate as it is. It also includes the case where it is included in a state in which formation processing or the like has been performed.
• the printed wiring board of the present embodiment uses the laminate or metal-clad laminate of the present embodiment, and performs circuit formation processing such as hole drilling, metal plating, and etching of metal foil by a known method. It can be manufactured by performing a multi-layering process as needed.
• the semiconductor package of this embodiment includes the printed wiring board of this embodiment and a semiconductor element.
• the semiconductor package of this embodiment is formed by mounting a semiconductor element on the printed wiring board of this embodiment.
• the semiconductor package of the present embodiment is obtained by, for example, mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board of the present embodiment by a known method, and sealing the semiconductor element with a sealing resin or the like. can be manufactured by
• the weight average molecular weight (Mw) was measured by the following method. Conversion was performed from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Calibration curve, standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name] and approximated by a cubic equation. GPC measurement conditions are shown below.
• Electrodeposited copper foil "3EC-M3-VLP-12" (manufactured by Mitsui Mining & Smelting Co., Ltd., trade name) with a thickness of 12 ⁇ m is superimposed on both sides of the four prepregs so that the adhesive surfaces are aligned with the prepregs, and then heated at 240 ° C.
• a double-sided copper-clad laminate was produced by heating and pressing under vacuum press conditions of 3 MPa for 80 minutes.
• Thermal expansion coefficient A 5 mm square evaluation board was prepared by removing the copper foil by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution, and using a thermomechanical measurement device (TMA) ⁇ Thermomechanical analysis was performed by a compression method using Q400 (model number) manufactured by Instruments Japan Co., Ltd.). After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. The average coefficient of thermal expansion (average of linear thermal expansion coefficients in the surface direction) from 30° C. to 100° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion (linear thermal expansion coefficient). The reason for using the second measurement result is to improve the measurement accuracy.
• TMA thermomechanical measurement device
• Adhesive strength with copper foil was evaluated by partially etching the copper foil of the double-sided copper-clad laminate obtained in each example to form a copper foil line with a width of 3 mm. , the load was measured and evaluated when the copper foil line was peeled off at a rate of 50 mm/min in the direction of 90° with respect to the adhesive surface. If the load at the time of peeling was 0.3 kN/m or more, it was judged that the adhesiveness with the copper foil was sufficient.
• solder heat resistance For solder heat resistance, a test piece obtained by cutting the double-sided copper-clad laminate obtained in each example into a 50 mm square was floated in a solder bath at 288 ° C. and allowed to stand for 30 minutes. bottom. The surface of the test piece was visually observed and evaluated according to the following evaluation criteria. A: No swelling was observed on the surface of the test piece. C: Blistering was observed on the surface of the test piece.
• Epoxy resin "EPICLON (registered trademark) HP-9500", naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, trade name)
• Maleimide compound the siloxane-modified maleimide compound prepared in Production Example 1
• [(C) Component] - Phosphate ester compound 1 a phosphate ester compound having the following structure. (n c5 represents an integer from 0 to 5.)
• - Phosphate ester compound 2 a phosphate ester compound having the following structure.
• phosphazene compound 1 A phosphazene compound having the following structure.
• - Phosphazene compound 2 A phosphazene compound having the following structure. (n c9 is each independently 0 or 1.)
• Curing accelerator 1 isocyanate mask imidazole “G-8009L” (Daiichi Kogyo Seiyaku Co., Ltd., trade name)
• the copper-clad laminates of Examples using the resin composition of the present embodiment are excellent in low thermal expansion, and have high adhesive strength with metal foil and high soldering heat resistance.
• the copper-clad laminate of Comparative Example 1 in which aluminum phosphate was used instead of component (C), had increased thermal expansibility and insufficient adhesive strength to the metal foil.
• Comparative Example 2 in which (A) the acrylic polymer was not used and the amount of the siloxane-modified maleimide compound was increased accordingly, the low thermal expansion property was good, but the adhesive strength with the metal foil and the Solder heat resistance became insufficient.

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• 2022
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