Classifications

• • 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
  • 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
  • B32B15/092—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 comprising epoxy resins
• • 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
• • 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
  • C08G59/20—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 epoxy compounds used
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/226—Mixtures of di-epoxy compounds
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
  • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4028—Isocyanates; Thioisocyanates
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4042—Imines; Imides
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
  • C08K5/1539—Cyclic anhydrides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C08L61/14—Modified phenol-aldehyde condensates
• • 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
• • 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
• • 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
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

• the present invention relates to curable compositions, prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards.
• Patent Document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group is excellent in heat resistance and low thermal expansion. , metal foil-clad laminates and multilayer printed wiring boards.
• Patent Document 2 polymaleimide, a diglycidylpolysiloxane represented by the following formula (I), and an addition polymer of a diallyl bisphenol represented by the following formula (II), and the following formula (III)
• a manufacturing method is disclosed in which a resin for encapsulating a semiconductor is obtained by reacting an allylated phenol resin represented by the formula in a predetermined ratio and under predetermined conditions.
• the resin for semiconductor encapsulation obtained by the above production method has good compatibility with polymaleimide and the addition polymer described above, and furthermore, the composition using the resin for semiconductor encapsulation has good compatibility.
• component b in the following formula (III) is an important component that reacts with maleimide groups in a resin formation reaction with polymaleimide and improves the compatibility between polymaleimide and polysiloxane. ing.
• R 1 represents an alkylene group or a phenylene group
• each R 2 independently represents an alkyl group or a phenyl group
• n represents an integer of 1 to 100.
• R4 represents an ether bond, a methylene group, a propylidene group or a direct bond (single bond).
• a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound is excellent in low thermal expansion.
• the resin composition has a problem in moldability due to insufficient compatibility between the silicone compound and the thermosetting resin.
• the present inventors have found that the above resin composition does not have sufficient metal foil peel strength (for example, copper foil peel strength) when used as a metal foil clad laminate.
• Patent Document 2 the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and low thermal expansion and copper foil peel strength required as characteristics of printed wiring boards have not been studied.
• the present invention has been made in view of the above problems, and provides a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board having excellent low thermal expansion and copper foil peel strength. for the purpose.
• a curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D.
• the average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3
• the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3
• the epoxy compound C has an average number of The curable composition according to [1] above, which has an average number of epoxy groups of 1 or more and less than 3.
• each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group; each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group; n is , represents an integer from 0 to 100.
• each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
• the content of the epoxy compound C is 20 to 50% by mass with respect to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C, according to any one of [1] to [6] above.
• the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [1] to [7].
• a curable composition according to [9] above, wherein the polymer E has a weight average molecular weight of 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 .
• the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass with respect to the total mass of the polymer E. curable composition.
• each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group; each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group; n is , represents an integer from 0 to 100.
• each R a independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
• the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. , the curable composition according to any one of the above [9] to [18].
• each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.
• each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.
• any one of the above [1] to [20] further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadimide compounds.
• the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,
• the curable composition according to [21] above which contains at least one selected from the group consisting of a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3′).
• each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.
• each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
• the cyanate ester compound contains a compound represented by the following formula (5) excluding the compound represented by the following formula (4) and / or the compound represented by the following formula (4) [21] or The curable composition according to [22].
• each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more.
• R ya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom
• each R yb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
• Each R yc independently represents an aromatic ring having 4 to 12 carbon atoms
• R yc may form a condensed structure with a benzene ring
• a 1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, represents a sulfur atom or a single bond
• one benzene ring may have two or more R ya and/or R ya and/or R ya and/
• each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.
• a prepreg comprising a substrate and the curable composition according to any one of [1] to [27] impregnated or applied to the substrate.
• a resin sheet comprising a support and the curable composition according to any one of [1] to [27] disposed on the surface of the support.
• a metal foil clad laminate comprising: [31] an insulating layer formed of one or more selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above; a conductor layer formed on the surface of the insulating layer; A printed wiring board.
• curable compositions, prepregs, resin sheets, metal foil-clad laminates and printed wiring boards having excellent low thermal expansion and copper foil peel strength.
• this embodiment a mode for carrying out the present invention (hereinafter referred to as “this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. It is possible.
• resin solid content refers to the components excluding the solvent and filler in the curable composition of the present embodiment, unless otherwise specified. It means that the total amount of components excluding the solvent and filler in the curable composition is 100 parts by mass. Moreover, 100 mass % of resin solid content means that the sum total of the component except a solvent and a filler in a curable composition is 100 mass %.
• excellent compatibility means a mixture containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D ( For example, it means that liquid phase separation does not occur in the state of varnish.
• excellent compatibility means that liquid phase separation does not occur in a state of a mixture (for example, varnish) containing the polymer E and other components.
• the curable composition of the first embodiment comprises alkenylphenol A, epoxy-modified silicone B, epoxy compound C excluding epoxy-modified silicone B (hereinafter also simply referred to as “epoxy compound C”), and acid anhydride D and A curable composition containing these components tends to be more compatible with thermosetting resins (hereinafter also simply referred to as “thermosetting resins”) that are not sufficiently compatible with epoxy-modified silicone B. Due to this, the curable composition of the first embodiment can exhibit more excellent compatibility, and is excellent in low thermal expansion and copper foil peel strength. In addition, when the curable composition is used by partially reacting (polymerizing) each of these components, it is possible to exhibit even better compatibility, and it is possible to exhibit better low thermal expansion and copper foil peel strength. (the curable composition of the second embodiment).
• Alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. By containing alkenylphenol A, the curable composition of the present embodiment can exhibit excellent compatibility.
• the alkenyl group is not particularly limited, but examples thereof include alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, more preferably an allyl group, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.
• the number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-4.
• the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, more preferably 1, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.
• the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, but the ortho positions (2,6 positions) are preferable.
• a phenolic aromatic ring is one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and includes phenol rings and naphthol rings.
• the number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, preferably 1.
• the phenolic aromatic ring may have substituents other than alkenyl groups.
• substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkyl groups having 1 to 10 carbon atoms, A chain alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom.
• the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2.
• the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.
• Alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and has two is preferred.
• Alkenylphenol A may be, for example, a compound represented by formula (1A) or formula (1B) below.
• Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms
• Rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
• Rxc each independently represents represents an aromatic ring having 4 to 12 carbon atoms
• Rxc may form a condensed structure with a benzene ring
• Rxc may or may not be present
• A is an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom or a direct bond (single bond); If it does not exist, one benzene ring may have two or more Rxa and/or Rxb groups.
• Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms
• Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom
• Rxf may form a fused structure with a benzene ring, Rxf may or may not be present, and when Rxf is absent, one
• the benzene ring may have two or more Rxd and/or Rxe groups.
• alkenyl groups having 2 to 8 carbon atoms represented by Rxa and Rxd are not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group and hexenyl group. etc.
• the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group and pentyl group. , straight-chain alkyl groups such as hexyl group, branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group.
• the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene group, ethylene group, trimethylene group and propylene group.
• the aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, but is, for example, represented by the formulas: -CH 2 -Ar-CH 2 -, -CH 2 -CH 2 -Ar-CH 2 -CH 2 - , or a group represented by the formula: —CH 2 —Ar—CH 2 —CH 2 — (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group).
• the arylene group having 6 to 10 carbon atoms is not particularly limited and includes, for example, a phenylene ring.
• Rxf is preferably a benzene ring (compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.
• alkenylphenol A is preferably alkenylbisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols.
• alkenyl bisphenol is diallyl bisphenol in which two phenolic aromatic rings of the bisphenol are respectively bound to one allyl group, and/or two phenolic aromatic rings of the bisphenol are respectively bound to one propenyl group. preferably dipropenyl bisphenol.
• the diallyl bisphenol is not particularly limited, but for example, o,o'-diallyl bisphenol A ("DABPA", a product of Daiwa Kasei Kogyo Co., Ltd.), o, o'-diallyl bisphenol F, o, o'-diallyl bisphenol S , o,o'-diallylbisphenol fluorene.
• DABPA o,o'-diallyl bisphenol A
• F o, o'-diallyl bisphenol F
• S o,o'-diallylbisphenol fluorene
• the dipropenyl bisphenol is not particularly limited, and examples thereof include o,o'-dipropenylbisphenol A ("PBA01" from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o,o'- Dipropenyl bisphenol S, o,o'-dipropenyl bisphenol fluorene.
• the average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, and preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. more preferred.
• the average number of phenol groups is calculated by the following formula.
• A represents the number of phenol groups in alkenylphenol having i phenol groups in the molecule
• Xi represents the ratio of alkenylphenol having i phenol groups in the molecule to all alkenylphenols
• X 1 + X 2 + . . . X n 1.
• Epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. By containing the epoxy-modified silicone B, the curable composition of the present embodiment can exhibit excellent low thermal expansion and copper foil peel strength.
• the silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are repeatedly formed.
• the polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.
• the epoxy group-containing group is not particularly limited, but includes, for example, a group represented by the following formula (a1).
• R 0 represents an alkylene group (e.g., a methylene group, an ethylene group, an alkylene group having 1 to 5 carbon atoms such as a propylene group), and X is a monovalent represented by the following formula (a2) group or a monovalent group represented by the following formula (a3).)
• Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol.
• epoxy-modified silicone B has excellent compatibility with thermosetting resins, and tends to further improve low thermal expansion and copper foil peel strength in a well-balanced manner. It is in. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, still more preferably 150 to 240 g/mol.
• Epoxy-modified silicone B preferably contains two or more types of epoxy-modified silicones from the viewpoint of further improving compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner.
• the two or more epoxy-modified silicones preferably have different epoxy equivalents, and an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low equivalent epoxy-modified silicone B1"). and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (hereinafter also referred to as "high equivalent epoxy-modified silicone B2”), and an epoxy having an epoxy equivalent of 140 to 250 g/mol. More preferably, it contains a modified silicone (low-equivalent epoxy-modified silicone B1′) and an epoxy-modified silicone having an epoxy equivalent of 450 to 3000 g/mol (high-equivalent epoxy-modified silicone B2′).
• the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol. More preferably 300 to 1000 g/mol.
• the average epoxy equivalent is calculated by the following formula.
• Ei represents the epoxy equivalent of one epoxy-modified silicone among two or more epoxy-modified silicones
• Wi represents the ratio of the epoxy-modified silicone in epoxy-modified silicone B
• W 1 +W 2 + . . . W n 1.
• Epoxy-modified silicone B should contain an epoxy-modified silicone represented by the following formula (1) from the viewpoint of having excellent compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner. is preferred.
• each R 1 independently represents a single bond, an alkylene group, an arylene group or an aralkylene group; each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group; n represents an integer from 0 to 100;
• the alkylene group represented by R 1 may be linear, branched or cyclic.
• the number of carbon atoms in the alkylene group is preferably 1-12, more preferably 1-4.
• Alkylene groups include, for example, a methylene group, an ethylene group, or a propylene group. Among these, R 1 is preferably a propylene group.
• the arylene group represented by R 1 may have a substituent.
• the number of carbon atoms in the arylene group is preferably 6-40, more preferably 6-20.
• the arylene group includes, for example, a phenylene group, a cyclohexylphenylene group, a hydroxyphenylene group, a cyanophenylene group, a nitrophenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a pyrenylene group, a fluorenylene group and the like. These groups may contain an ether bond, a ketone bond, or an ester bond.
• the aralkylene group represented by R 1 preferably has 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms.
• Examples of the aralkylene group include groups represented by the following formula (XI). (In formula (XI), * represents a bond.)
• the group represented by R 1 may further have a substituent.
• substituents include linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups, cyclic alkyl groups having 3 to 10 carbon atoms, linear alkoxy groups having 1 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms, and cyclic alkoxy groups having 3 to 10 carbon atoms. be done.
• R 1 is particularly preferably a propylene group.
• each R 2 independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group.
• the above alkyl group and phenyl group may have a substituent.
• the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
• Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups.
• R 2 is preferably a methyl group or a phenyl group.
• n represents an integer of 0 or more, for example, 0 to 100. n is preferably 50 or less, more preferably 30 or less, and even more preferably 20, from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is below.
• Epoxy-modified silicone B is more excellent in compatibility with the thermosetting resin, and from the viewpoint of further improving low thermal expansion and copper foil peel strength in a well-balanced manner, two or more types of epoxy-modified silicones represented by formula (1) are used. It is preferable to contain. In this case, two or more types of epoxy-modified silicones preferably have different values of n. It is more preferable to contain a certain epoxy-modified silicone.
• the average number of epoxy groups per molecule of epoxy-modified silicone B is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. is more preferred.
• the average number of epoxy groups is calculated by the following formula.
• the content of the epoxy-modified silicone B is 5 to 95% by mass with respect to the total 100% by mass of the epoxy-modified silicone B and the epoxy compound C, from the viewpoint of expressing even better low thermal expansion and chemical resistance. , more preferably 10 to 90% by mass, even more preferably 40 to 85% by mass, even more preferably 50 to 80% by mass.
• epoxy-modified silicone B a commercially available product may be used, or a product manufactured by a known method may be used. Examples of commercially available products include “X-22-163" and “KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.
• Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, more specifically, an epoxy compound that does not have a polysiloxane skeleton. By containing the epoxy compound C, the curable composition of the present embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
• the epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B.
• the epoxy compound C in the curable composition of the present embodiment is typically a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule. can be used.
• Epoxy compound C preferably contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of being able to exhibit better compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability.
• the epoxy compound C in the curable composition of the present embodiment is not particularly limited, but a compound represented by the following formula (3a) can be used.
• Ar 3 each independently represents a benzene ring or naphthalene ring
• Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
• R 3a each independently represents a hydrogen atom.
• the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituent may be a glycidyloxy group (not shown), or other substituents such as It may be an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.
• the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, which may be a glycidyloxy group, other substituents such as carbon number It may be an alkyl group of 1 to 5, a phenyl group, or the like.
• examples of bifunctional epoxy compounds include compounds represented by the following formula (b1).
• each Ar 3 independently represents a benzene ring or naphthalene ring
• each Ar 4 represents a benzene ring, naphthalene ring or biphenyl ring
• each R 3a independently represents a hydrogen atom or represents a methyl group
• the benzene ring or naphthalene ring in Ar 3 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group.
• the benzene ring, naphthalene ring or biphenyl ring in Ar 4 may further have one or more substituents, and the substituents are, for example, a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. It may be a substituent other than )
• the compound represented by formula (3a) is preferably a phenolic novolac type epoxy resin in which Ar 4 in formula (3a) is at least substituted with a glycidyloxy group.
• the phenolic novolak-type epoxy resin is not particularly limited. Epoxy resins may be mentioned.
• each Ar 31 independently represents a benzene ring or a naphthalene ring
• each Ar 41 independently represents a benzene ring, a naphthalene ring or a biphenyl ring
• each R 31a independently represents represents represents a hydrogen atom or a methyl group
• p represents 1
• kz represents an integer of 1 to 50
• each ring represents a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, a to 5 alkoxy groups or phenyl groups)
• at least one of Ar 31 and Ar 41 represents a naphthalene ring.
• Compounds having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2). (Wherein, R represents a methyl group, and kz is synonymous with kz in the above formula (3-1).)
• the naphthalene cresol novolak type epoxy resin is not particularly limited, but for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable.
• the compound represented by the following formula (NE) is a random copolymer of a cresol novolak epoxy structural unit and a naphthol novolak epoxy structural unit, and both cresol epoxy and naphthol epoxy can be terminals.
• n and n in the formula (NE) each represent an integer of 1 or more.
• naphthalene cresol novolac type epoxy resin a commercially available product or a product manufactured by a known method may be used.
• commercially available products include "NC-7000", “NC-7300” and “NC-7300L” manufactured by Nippon Kayaku Co., Ltd., and "HP-9540” and “HP-9500” manufactured by DIC Corporation. and "HP-9540" is particularly preferred.
• the compound represented by formula (3a) may be a compound (hereinafter also referred to as "aralkyl epoxy resin") that does not correspond to the phenolic novolac epoxy resins described above.
• Aralkyl-type epoxy resins include compounds in which Ar 3 is a naphthalene ring and Ar 4 is a benzene ring in the formula (3a) (also referred to as a "naphthol aralkyl- type epoxy resin”); It is preferably a compound in which it is a benzene ring and Ar 4 is a biphenyl ring (also referred to as a "biphenylaralkyl-type epoxy resin”), and more preferably a biphenylaralkyl-type epoxy resin.
• naphthol aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
• Examples of commercially available products include “HP-5000” and “HP-9900” manufactured by DIC Corporation, “ESN-375” and “ESN-475" manufactured by Nippon Steel Chemical Co., Ltd., and the like.
• the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b). (Wherein, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6.)
• bifunctional epoxy compounds include, for example, compounds in which ka is 1 in formula (3b).
• biphenyl aralkyl type epoxy resin a commercially available product or a product manufactured by a known method may be used.
• commercially available products include “NC-3000”, “NC-3000L”, and “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.
• the epoxy compound C in the curable composition of the present embodiment it is preferable to use a naphthalene-type epoxy resin (excluding those corresponding to the compounds represented by formula (3a)).
• the naphthalene-type epoxy resin is preferably a naphthylene ether-type epoxy resin from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.
• the naphthylene ether type epoxy resin is a bifunctional epoxy compound represented by the following formula (3-3) or the following formula (3 -4) is preferably a polyfunctional epoxy compound or a mixture thereof.
• each R 13 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (eg, vinyl group, allyl group or propenyl group).
• each R 14 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group or ethyl group), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl group, allyl group or propenyl group).)
• a commercially available product or a product manufactured by a known method may be used as the naphthylene ether type epoxy resin.
• Commercially available naphthylene ether type epoxy resins include, for example, DIC Corporation products "HP-6000", “EXA-7300”, “EXA-7310", “EXA-7311”, “EXA-7311L”, “ EXA7311-G3", “EXA7311-G4", “EXA-7311G4S”, “EXA-7311G5", etc., and HP-6000 is particularly preferred.
• each R 3b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group or ethyl group), an aralkyl group, a benzyl group, a naphthyl group, at least one glycidyl represents a naphthyl group containing an oxy group or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (eg, 0 to 2).)
• each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
• the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic.
• alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl groups.
• the biphenyl-type epoxy compound may be in the form of a mixture of compounds b2 having different numbers of Ra as alkyl groups. Specifically, it is preferably a mixture of biphenyl-type epoxy compounds having different numbers of Ra as alkyl groups. It is more preferred to be a mixture of compounds b2 which are
• a dicyclopentadiene type epoxy resin (excluding those corresponding to the epoxy compound C described above) can be used.
• the dicyclopentadiene-type epoxy resin is not particularly limited, but includes, for example, compounds represented by the following formula (3-5). (In the formula, each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.)
• each R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl group or ethyl group).)
• dicyclopentadiene type epoxy resin A commercially available product or a product manufactured by a known method may be used as the dicyclopentadiene type epoxy resin.
• Commercial products of dicyclopentadiene type epoxy resin include "EPICRON HP-7200L”, “EPICRON HP-7200”, “EPICRON HP-7200H” and "EPICRON HP-7000HH” manufactured by Dainippon Ink and Chemicals. mentioned.
• the epoxy compound C is an epoxy compound represented by the formula (3a), a naphthalene-type epoxy resin and a biphenyl, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil peel strength and insulation reliability.
• Epoxy compound C may contain other epoxy compounds that do not correspond to the epoxy compounds described above.
• other epoxy compounds include, but are not limited to, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, and fluorene-type epoxy resins.
• examples thereof include resins, epoxy resins composed of bisphenol A structural units and hydrocarbon structural units, and the like.
• bisphenol-type epoxy resins can be included.
• diallylbisphenol type epoxy resins for example, diallylbisphenol A type epoxy resin, diallylbisphenol E type epoxy resin, diallylbisphenol F type epoxy resin, diallylbisphenol S type epoxy resin, etc.
• diallylbisphenol type epoxy resins for example, diallylbisphenol A type epoxy resin, diallylbisphenol E type epoxy resin, diallylbisphenol F type epoxy resin, dially
• epoxy compound C one of the above-described epoxy compounds and epoxy resins may be used alone, or two or more thereof may be used in combination.
• the average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exhibiting the effects of the present embodiment. is more preferred.
• the content of the epoxy compound C is, from the viewpoint of being able to exhibit even better heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the total amount of the epoxy-modified silicone B and the epoxy compound C being 100% by mass, It is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
• the curable composition of the present embodiment contains acid anhydride D.
• Acid anhydride D reacts with terminal hydroxyl groups and epoxy groups generated by the reaction of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B to generate terminal carboxyl groups.
• a large number of carboxyl groups having high reactivity with the thermosetting resin are present, so compatibility and crosslink density are improved, and low thermal expansibility is improved.
• the acid anhydride D is not particularly limited, and is not particularly limited as long as it has a cyclic structure, and preferably has 4 to 20 carbon atoms because it tends to have better compatibility with thermosetting resins. More preferably an acid anhydride having 4 to 16 carbon atoms, more preferably an acid anhydride having 4 to 10 carbon atoms.
• Acid anhydride D is, for example, one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride.
• phthalic anhydride and succinic anhydride are more preferable from the viewpoint of better compatibility with thermosetting resins and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner.
• the content of acid anhydride D is 0.00% with respect to 100% by mass of resin solid content, from the viewpoint of better compatibility with the thermosetting resin and further improvement of low thermal expansion and copper foil peel strength in a well-balanced manner. It is preferably 8 to 15% by mass, more preferably 0.9 to 10% by mass, even more preferably 1 to 5% by mass.
• the curable composition of the present embodiment includes a maleimide compound, a cyanate ester compound, and a phenol compound A other than the alkenylphenol A. ' and at least one compound F selected from the group consisting of alkenyl-substituted nadimide compounds.
• compound F is not particularly limited, it is preferably bifunctional or higher, and may be trifunctional or higher polyfunctional.
• the content of compound F in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, relative to 100% by mass of the resin solid content. Preferably, it is more preferably 30 to 50% by mass.
• maleimide compound Compound F preferably contains a maleimide compound from the viewpoint of further improving low thermal expansion and copper foil peel strength.
• the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. -hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane
• n 1 is 1 or more, preferably 1-100, more preferably 1-10.
• each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 4 represents an integer of 1 or more and 10 or less.
• the maleimide compound is bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ At least one selected from the group consisting of propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide compound represented by formula (3), and a maleimide compound represented by formula (3′) is preferably included.
• maleimide compound a commercially available product or a product manufactured by a known method may be used.
• Commercially available maleimide compounds include "BMI-70", “BMI-80” and “BMI-1000P” manufactured by K.I. -4000”, “BMI-5100”, “BMI-7000”, “BMI-2300”, Nippon Kayaku Co., Ltd. product “MIR-3000-70MT” (R 13 in formula (3′) are all hydrogen atoms and n4 is a mixture of 1 to 10.) and the like.
• the content of the maleimide compound is preferably 1 to 50 parts by mass, and preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resin solid content, from the viewpoint of further improving low thermal expansion properties and copper foil peel strength. is more preferable, and 10 to 40 parts by mass is even more preferable.
• Compound F preferably contains a cyanate ester compound from the viewpoint of further improving low thermal expansion properties and copper foil peel strength.
• the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule.
• novolak-type cyanate ester compounds such as compounds represented by the following formula (5) excluding compounds represented by formula (4), biphenyl aralkyl-type cyanates, diallyl bisphenol-type cyanates compounds, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanato Naphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thio
• the cyanate ester compound is a polyfunctional cyanate ester such as a naphthol aralkyl-type cyanate ester compound and/or a novolac-type cyanate ester compound. It preferably contains a compound.
• each R 6 independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.
• each Rya independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom
• each Ryb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.
• Ryc each independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a fused structure with a benzene ring, Ryc may or may not be present
• a 1a each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, and a sulfur atom. or represents a direct bond (single bond), and when Ryc does not exist, one benzene ring may have two or more Rya and/or Ryb groups, n represents an integer of 1-20.
• the cyanate ester compound preferably contains a compound represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peel strength.
• n2 represents an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10.
• the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group.
• the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited. branched alkyl groups such as isopropyl group, isobutyl group and tert-butyl group;
• the alkylene group having 1 to 6 carbon atoms represented by A 1a is not particularly limited, but includes methylene group, ethylene group, trimethylene group and propylene group.
• the aralkylene group having 7 to 16 carbon atoms represented by A 1a is not particularly limited, and examples thereof include formulas: —CH 2 —Ar—CH 2 — and —CH 2 —CH 2 . -Ar-CH 2 -CH 2 -, or a group represented by the formula: -CH 2 -Ar-CH 2 -CH 2 - (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group) is mentioned.
• the arylene group having 6 to 10 carbon atoms represented by A 1a is not particularly limited, but includes, for example, a phenylene ring.
• n represents an integer of 1-20, preferably an integer of 1-15, more preferably an integer of 1-10.
• the compound represented by Formula (5) is preferably a compound represented by Formula (c1) below.
• each Rx independently represents a hydrogen atom or a methyl group
• each R independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or hydrogen represents an atom
• n represents an integer from 1 to 10.
• cyanate ester compounds may be produced according to known methods. Specific production methods include, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).
• the content of the cyanate ester compound as compound F is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion and copper foil peel strength. , more preferably 10 to 60 parts by mass, even more preferably 10 to 40 parts by mass.
• a phenol compound A' other than the alkenylphenol A can be contained from the viewpoint of being able to exhibit even better copper foil peel strength.
• the phenolic compound A′ is not particularly limited, but may be a bisphenol-type phenol resin (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resin (e.g., phenol novolak resin, naphthol novolac resin, cresol novolak resin, etc.), glycidyl ester type phenol resin, naphthalene type phenol resin, anthracene type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol Examples include resins, aralkyl-type phenol resins, phenol-modified aromatic hydrocarbon-formalde
• the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule from the viewpoint of being able to exhibit even better compatibility and copper foil peel strength.
• bifunctional phenol compound examples include, but are not limited to, bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), biphenols (e.g., p, p'- biphenol, etc.), dihydroxydiphenyl ether (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (e.g., 4,4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide) etc.), and dihydroxyarene (eg, hydroquinone, etc.).
• bisphenol biscresol
• bisphenols having a fluorene skeleton e.g., bisphenol having a fluorene skeleton, biscre
• bifunctional phenol compounds are used singly or in combination of two or more.
• the bifunctional phenol compound preferably contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton, from the viewpoint of being able to exhibit even better copper foil peel strength.
• bis-cresol fluorene is preferable as the bisphenols having a fluorene skeleton.
• aralkyl-type phenolic resins examples include compounds represented by the following formula (c2).
• Ar 1 each independently represents a benzene ring or naphthalene ring
• Ar 2 represents a benzene ring, naphthalene ring or biphenyl ring
• R 2a each independently represents a hydrogen atom or a methyl group
• m represents an integer of 1 to 50
• each ring may have a substituent other than a hydroxyl group (eg, an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.).
• the compound represented by formula (c2) is a compound in which Ar 1 is a naphthalene ring and Ar 2 is a benzene ring (hereinafter referred to as "naphthol aralkyl Also referred to as “biphenylaralkyl-type phenolic resin”), and in formula (c2), a compound in which Ar 1 is a benzene ring and Ar 2 is a biphenyl ring (hereinafter also referred to as "biphenylaralkyl-type phenolic resin").
• naphthol aralkyl also referred to as "biphenylaralkyl-type phenolic resin”
• the naphthol aralkyl-type phenolic resin is preferably a compound represented by the following formula (8).
• each R 7 independently represents a hydrogen atom or a methyl group, and n 3 represents an integer of 1 or more.
• n3 represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-6.
• the biphenylaralkyl-type phenolic resin is preferably a compound represented by the following formula (2c).
• each R 2b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group (preferably a hydrogen atom), m1 is an integer of 1 to 20 (preferably 1 to 6 integer).
• the phenolic compound A' preferably contains the compound represented by the above formula (8).
• a commercially available product or a product manufactured by a known method may be used as the aralkyl-type phenol resin.
• Commercially available aralkyl-type phenolic resins include Nippon Kayaku Co., Ltd.'s "KAYAHARD GPH-65”, “KAYAHARD GPH-78", “KAYAHARD GPH-103” (biphenylaralkyl-type phenolic resin), Nippon Steel Chemical Co., Ltd.
• the company's product "SN-495" (naphthol aralkyl type phenolic resin) can be mentioned.
• the content of alkenylphenol A as compound F is 1 part per 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenolic compound A', from the viewpoint of being able to exhibit even better compatibility.
• the amount is preferably to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass.
• the content of the epoxy-modified silicone B in the curable composition of the present embodiment is, from the viewpoint of achieving well-balanced expression of even better low thermal expansion and copper foil peel strength, alkenylphenol A, epoxy-modified silicone B, epoxy compound C and It is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass with respect to 100 parts by mass of the total amount of phenol compound A'.
• the content of the phenolic compound A' in the curable composition of the present embodiment is the total amount of the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C and the phenolic compound A' from the viewpoint of expressing even better copper foil peel strength. It is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, even more preferably 15 to 20 parts by mass, based on 100 parts by mass.
• the contents of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C are the same as those of alkenylphenol A, epoxy-modified silicone B, and epoxy compound C. It represents the content with respect to the total amount of 100 parts by mass.
• compound F preferably contains an alkenyl-substituted nadimide compound.
• the alkenyl-substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d).
• each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group or an ethyl group); represents an alkylene group, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or (7).
• R3 represents a methylene group, an isopropylidene group, CO, O, S or SO2 .
• each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
• alkenyl-substituted nadimide compound represented by formula (2d) a commercially available product or a product manufactured according to a known method may be used.
• Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.
• the content of the alkenyl-substituted nadimide compound as compound F is preferably 1 to 40 parts by mass, preferably 5 to 35 parts by mass, relative to 100 parts by mass of the resin solid content. More preferably, 10 to 30 parts by mass is even more preferable.
• the curable composition of the second embodiment includes a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, and an acid A constituent unit derived from the anhydride D, and a polymer E containing a Alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D are as described above.
• polymer E containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D
• the curable resin composition of the second embodiment containing is distinguished from the curable composition of the first embodiment described above, which relates to the aspect that does not have the polymer E.
• Polymer E can exhibit sufficient compatibility even when mixed with a thermosetting resin that has poor compatibility with silicone compounds. Thereby, the curable composition containing the polymer E and the thermosetting resin can give a uniform varnish or cured product.
• a cured product such as a prepreg obtained by using the curable composition has components uniformly dissolved therein, and variation in physical properties due to non-uniformity of the components is suppressed.
• the curable composition of the second embodiment contains one or more selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and acid anhydride D. good too.
• the alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D contained in the curable composition of the second embodiment may be unreacted components remaining after the polymerization of the polymer E. However, it may be a component added again to the synthesized polymer E.
• the curable composition of the second embodiment may optionally contain the above-described maleimide compound, cyanate ester compound, phenol compound A' other than the alkenylphenol A, and alkenyl-substituted nadimide. It may further contain compound F, which is at least one selected from the group consisting of compounds. The compound F may be an unreacted component remaining after polymerization of the polymer E, or may be a component newly added to the polymer E synthesized.
• Polymer E contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D, If necessary, it further contains a structural unit derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A′ other than the alkenylphenol A, and an alkenyl-substituted nadimide compound.
• the compound F is preferably a bifunctional compound.
• structural units derived from alkenylphenol A "structural units derived from epoxy-modified silicone B”, “structural units derived from epoxy compound C”, and “structural units derived from acid anhydride D”
• structural units derived from compound F are structural units obtained by polymerizing each component of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D and compound F in polymer E.
• structural units formed by reactions or the like that can give similar structural units are also included.
• each structural unit is also referred to as structural unit A, B, C, D, and F, respectively.
• the weight-average molecular weight of the polymer E is preferably 3.0 ⁇ 10 3 to 5.0 ⁇ 10 4 and more preferably 3.0 ⁇ 10 3 to 2.0 ⁇ 10 in terms of polystyrene in gel permeation chromatography. 4 is more preferred. With a weight-average molecular weight of 3.0 ⁇ 10 3 or more, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be expressed. When the weight average molecular weight is 5.0 ⁇ 10 4 or less, the curable composition of the second embodiment tends to exhibit even better compatibility.
• the content of the structural unit A in the polymer E is preferably 5 to 50% by mass with respect to the total mass of the polymer E.
• the content of the structural unit A is within the above range, the curable composition of the second embodiment tends to exhibit even better compatibility.
• the content of structural unit A is more preferably 10 to 45% by mass, even more preferably 15 to 40% by mass.
• the content of the structural unit B in the polymer E is preferably 20 to 60% by mass with respect to the total mass of the polymer E.
• the content of the structural unit B is within the above range, the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner.
• the content of structural unit B is more preferably 25 to 55% by mass, even more preferably 30 to 50% by mass.
• Structural unit B is an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g/mol (low equivalent epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g/mol (high equivalent epoxy-modified silicone B2). It preferably contains a structural unit derived from. Low-equivalent epoxy-modified silicone B1 and high-equivalent epoxy-modified silicone B2 have an epoxy equivalent of 140-250 g/mol (low-equivalent epoxy-modified silicone B1′) and 450-3000 g/mol, respectively. Epoxy-modified silicone (high-equivalent epoxy-modified silicone B2') is more preferable.
• the content of the structural unit B1 derived from the low-equivalent epoxy-modified silicone B1 in the polymer E is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, relative to the total mass of the polymer E. is more preferable, and 10 to 17% by mass is even more preferable.
• the content of the structural unit B2 derived from the high-equivalent epoxy-modified silicone B2 in the polymer E is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, relative to the total mass of the polymer E. and more preferably 25 to 50% by mass.
• the mass ratio of the content of the structural unit B2 to the content of the structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and 1.9 to 3.1. is more preferable.
• the curable composition of the second embodiment tends to have improved low thermal expansion and copper foil peel strength.
• the compound represented by the above formula (b1), the compound represented by the above formula (b2), the compound represented by the above formula (b3), and the above formula (b4) It is preferably a unit derived from at least one selected from the group consisting of the compounds represented.
• the content of the structural unit C in the polymer E is preferably 5 to 40% by mass with respect to the total mass of the polymer E.
• the curable composition of the second embodiment has better compatibility, better heat resistance, chemical resistance, low thermal expansion, copper foil It tends to be able to develop peel strength and insulation reliability.
• the content of structural unit C is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
• the content of the structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, relative to the total mass of the structural unit B and the structural unit C, and 15 to 60% by mass. % by mass is more preferred, and 20 to 50% by mass is particularly preferred.
• the curable composition of the second embodiment has even better compatibility, heat resistance, chemical resistance, low thermal expansion, copper Foil peel strength and insulation reliability tend to be further improved.
• the content of the structural unit D in the polymer E is preferably 3 to 20% by mass with respect to the total mass of the polymer E.
• the curable composition of the second embodiment tends to exhibit even better low thermal expansion and copper foil peel strength in a well-balanced manner.
• the content of structural unit D is more preferably 5 to 15% by mass, even more preferably 5 to 10% by mass.
• the content of the structural unit F in the polymer E is preferably 3 to 40% by mass relative to the total mass of the polymer E.
• the content of the structural unit F is within the above range, the curable composition of the second embodiment exhibits even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. tend to be able.
• the content of structural unit F is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.
• the content of the structural unit A' in the polymer E is It is preferably 5 to 30% by mass relative to the total mass of E.
• the content of the structural unit A' is within the above range, the curable composition of the second embodiment has even better heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability. tend to be expressed.
• the content of the structural unit A' is preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass.
• the alkenyl group equivalent weight of the polymer E is preferably 300-1500 g/mol.
• the alkenyl group equivalent is 300 g/mol or more, the cured product of the curable composition of the second embodiment tends to have a further decreased elastic modulus, and as a result, substrates and the like obtained using the cured product There is a tendency that the coefficient of thermal expansion can be further reduced.
• the alkenyl group equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability of the curable composition of the second embodiment tend to be further improved. It is in. From the same point of view, the alkenyl group equivalent is preferably 350-1200 g/mol, more preferably 400-1000 g/mol.
• the content of the polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, relative to 100% by mass of the resin solid content. , more preferably 15 to 40% by mass.
• the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
• Polymer E can be obtained, for example, by reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and optionally compound F in the presence of polymerization catalyst G. can get.
• the reaction may be performed in the presence of an organic solvent. More specifically, in the above steps, the addition reaction between the epoxy group of the epoxy-modified silicone B and the epoxy compound C and the hydroxyl group of the alkenylphenol A, and the hydroxyl group of the resulting addition reaction product and the epoxy-modified silicone B and After the addition reaction with the epoxy group of the epoxy compound C proceeds, the addition reaction between the terminal hydroxyl group and the epoxy group and the acid anhydride D proceeds to obtain the polymer E.
• the method for producing the curable composition of the present embodiment is obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C; a step of reacting an acid anhydride D with the prepolymer; is preferably included.
• an acid anhydride D is reacted with this prepolymer to obtain a low thermal expansion property and a copper foil. There is a tendency to obtain curable compositions with even better peel strength.
• the polymerization catalyst G is not particularly limited, and includes, for example, one or more of imidazole compounds and organophosphorus compounds. These catalysts are used individually by 1 type or in combination of 2 or more types. Among these, imidazole compounds are preferred.
• the imidazole compound is not particularly limited, and examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, imidazoles such as 2-a]benzimidazole ("TBZ", a product of Shikoku Kasei Kogyo Co., Ltd.) and 2,4,5-triphenylimidazole ("TPIZ", a product of Tokyo Kasei Kogyo Co., Ltd.); Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-tripheny
• the amount of the polymerization catalyst G (preferably an imidazole compound) used is not particularly limited. It is 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer E, the amount of the polymerization catalyst G used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.
• Organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used.
• Polar solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, ethyl acetate and acetic acid.
• Ester solvents such as butyl, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide.
• the nonpolar solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents are used singly or in combination of two or more.
• the amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass with respect to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D and compound F. .
• the reaction temperature is not particularly limited, and may be, for example, 100-170°C.
• the reaction time is also not particularly limited, and may be, for example, 3 to 8 hours.
• polymer E may be separated and purified from the reaction mixture by a conventional method.
• the curable composition of the second embodiment may further contain compound F in addition to polymer E, if necessary.
• the curable composition of the second embodiment tends to further improve heat resistance, chemical resistance, low thermal expansion and copper foil peel strength. .
• the content of the polymer E in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F On the other hand, it is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass.
• the curable composition tends to have more excellent compatibility and can exhibit low thermal expansion and copper foil peel strength in a well-balanced manner.
• the content of the compound F in the curable composition of the second embodiment is a total of 100 mass% of the polymer E and the compound F It is preferably 20 to 80% by mass, more preferably 35 to 75% by mass, even more preferably 45 to 65% by mass.
• the curable composition of the present embodiment may further contain other resins as long as the effects of the present embodiment are not impaired.
• Other resins include, for example, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, and the like. These resins are used singly or in combination of two or more.
• oxetane resins include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3- '-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, products of Toagosei Co., Ltd. "OXT-101", “OXT-121" etc.
• benzoxazine compound refers to a compound having two or more dihydrobenzoxazine rings in one molecule.
• benzoxazine compounds include "Bisphenol F-type benzoxazine BF-BXZ” and "Bisphenol S-type benzoxazine BS-BXZ” manufactured by Konishi Chemical Co., Ltd., and the like.
• Examples of compounds having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( Monovalent meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. or polyhydric alcohol (meth)acrylates; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin and the like.
• vinyl compounds such as ethylene, propylene, styrene, divinylbenzene
• the curable composition in the present embodiment preferably further contains an inorganic filler.
• the inorganic filler is not particularly limited, and examples thereof include silicas, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides.
• boron nitride aggregated boron nitride, silicon nitride, aluminum nitride, etc.
• metal sulfates e.g., barium sulfate, etc.
• metal hydroxides e.g., aluminum hydroxide, aluminum hydroxide heat-treated products (e.g., aluminum hydroxide heat-treated to reduce a portion of the water of crystallization), boehmite, magnesium hydroxide, etc.
• molybdenum compounds e.g., molybdenum oxide, zinc molybdate, etc.
• zinc compounds e.g., zinc borate, zinc stannate, etc.
• the inorganic filler is preferably at least one selected from the group consisting of silicas, metal hydroxides and metal oxides, from the viewpoint of further improving low thermal expansion properties. Silicas, boehmite and alumina, and more preferably silicas.
• silicas examples include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually by 1 type or in combination of 2 or more types. Among these, fused silica is preferable from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferable from the viewpoint of filling properties and fluidity.
• the content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of further improving the low thermal expansion property. , more preferably 100 to 300 parts by mass.
• the curable composition of this embodiment may further contain a silane coupling agent.
• a silane coupling agent By containing a silane coupling agent, the curable composition of the present embodiment further improves the dispersibility of the inorganic filler, and the components of the curable composition of the present embodiment and the substrate described later. There is a tendency that the adhesive strength can be further improved.
• the silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, aminosilane compounds (eg, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxysilane compounds (eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.), acrylsilane compounds (eg, ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (eg, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane hydrochloride), styrylsilane compounds, phenylsilane compounds, and the like.
• aminosilane compounds eg, ⁇ -aminopropyltriethoxysilane, N-
• a silane coupling agent is used individually by 1 type or in combination of 2 or more types.
• the silane coupling agent is preferably an epoxysilane compound.
• epoxysilane compounds include Shin-Etsu Chemical Co., Ltd. products "KBM-403", “KBM-303", “KBM-402”, and "KBE-403".
• the content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solid content.
• the curable composition of this embodiment may further contain a wetting and dispersing agent.
• the curable composition tends to further improve the dispersibility of the filler by containing a wetting and dispersing agent.
• any known dispersing agent used to disperse the filler may be used. 161, BYK-W996, W9010, W903 and the like.
• the content of the wetting and dispersing agent is not particularly limited, it is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin solid content.
• the curable composition of this embodiment may further contain a solvent.
• a solvent By containing a solvent, the curable composition of the present embodiment has a lower viscosity during preparation of the curable composition, further improved handling properties (handleability), and further improved impregnating properties into the substrate. tend to fall.
• the solvent is not particularly limited as long as it can dissolve a part or all of each component in the curable composition. xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, and the like. These solvents are used singly or in combination of two or more.
• the method for producing the curable composition of the present embodiment is not particularly limited, and includes, for example, a method of collectively or sequentially blending each of the components described above with a solvent and stirring the mixture. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.
• the curable composition of the present embodiment has excellent compatibility and can exhibit even better low thermal expansion and copper foil peel strength. Therefore, the curable composition of the present embodiment is suitably used for metal foil-clad laminates and printed wiring boards. That is, the curable composition of this embodiment can be suitably used as a curable composition for printed wiring boards.
• the curable composition of the second embodiment contains, in addition to the polymer E, at least an epoxy compound C (epoxy compound C existing separately from the structural unit C in the polymer E).
• the polymer E preferably has units derived from the above-described bifunctional epoxy compound as units derived from the epoxy compound C, and more preferably has units derived from the above-described biphenyl-type epoxy compound.
• the epoxy compound C present separately from the structural unit C in the polymer E the above-mentioned naphthylene ether type epoxy resin (commercially available products, for example, "HP-6000” manufactured by DIC Corporation) and / Or naphthalene cresol novolak type epoxy resin (commercially available, for example, "HP-9540" manufactured by DIC Corporation) is preferably included.
• the prepreg of this embodiment includes a substrate and the curable composition of this embodiment impregnated or applied to the substrate.
• the prepreg may be a prepreg obtained by a known method, as described above. It is obtained by semi-curing (to B stage) by heating and drying at.
• the prepreg of the present embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg under conditions of a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.
• the content of the curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and still more preferably 40% by volume in terms of the solid content of the prepreg with respect to the total amount of the prepreg. ⁇ 80% by volume.
• the calculation of the content of the curable composition herein includes the cured product of the curable composition of the present embodiment.
• the solid content of the prepreg as used herein refers to a component obtained by removing the solvent from the prepreg.
• the filler is included in the solid content of the prepreg.
• the base material is not particularly limited, and includes, for example, known base materials used as materials for various printed wiring boards.
• the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, wholly aromatic polyamide, polyester , polyparaphenylenebenzoxazole, and organic base materials composed of organic fibers such as polyimide). These substrates are used singly or in combination of two or more. Among these, a glass substrate is preferable from the viewpoint of being more excellent in dimensional stability under heating.
• Fibers constituting the glass substrate include, for example, E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, HME glass, and the like.
• the fibers constituting the glass substrate are the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass and HME glass, from the viewpoint of being more excellent in strength and low water absorption.
• One or more selected fibers are preferred.
• the form of the substrate is not particularly limited, but examples include forms such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.
• the weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. .
• glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used.
• the thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.1 mm is suitably used.
• the resin sheet of this embodiment includes a support and the curable composition of this embodiment disposed on the surface of the support.
• the resin sheet of the present embodiment may be formed, for example, by applying the curable composition of the present embodiment to one side or both sides of a support.
• the resin sheet of the present embodiment can be produced, for example, by directly coating a support such as a metal foil or film with a curable composition used for prepreg or the like and drying the composition.
• the support is not particularly limited, for example, known materials used in various printed wiring board materials can be used, and a resin sheet or metal foil is preferable.
• resin sheets and metal foils include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, etc. and metal foils such as aluminum foil, copper foil and gold foil.
• the support is preferably an electrolytic copper foil or a PET film.
• the resin sheet of the present embodiment can be obtained, for example, by applying the curable composition of the present embodiment to a support and then semi-curing (to B-stage).
• the method for producing the resin sheet of the present embodiment is generally preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example, after the curable composition is applied to a support such as a copper foil, it is semi-cured by a method of heating for 1 to 60 minutes in a dryer at 100 to 200 ° C. to form a resin sheet. A manufacturing method and the like can be mentioned.
• the adhesion amount of the curable composition to the support is preferably in the range of 1.0 ⁇ m or more and 300 ⁇ m or less in terms of resin thickness of the resin sheet.
• the resin sheet of this embodiment can be used as a build-up material for printed wiring boards.
• the metal foil-clad laminate of the present embodiment includes a laminate formed using one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a including metal foil.
• the laminate may be formed of one prepreg or resin sheet, or may be formed of a plurality of prepregs and/or resin sheets.
• the metal foil may be any metal foil that is used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper foil, such as foil, is mentioned.
• the thickness of the conductor layer is, for example, 1 to 70 ⁇ m, preferably 1.5 to 35 ⁇ m.
• the molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied.
• a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a laminate (laminate described above) or a metal foil-clad laminate.
• the temperature is 100 to 300° C.
• the pressure is 2 to 100 kgf/cm 2
• the heating time is 0.05 to 5. Time ranges are common.
• post-curing can be performed at a temperature of 150-300°C.
• the temperature is preferably 200° C. to 250° C.
• the pressure is 10 to 40 kgf/cm 2
• the heating time is 80 minutes to 130 minutes
• the temperature is 215° C. to 215° C., from the viewpoint of sufficiently accelerating the curing of the prepreg.
• the temperature is 235° C.
• the pressure is 25 to 35 kgf/cm 2
• the heating time is 90 to 120 minutes.
• the printed wiring board of the present embodiment has an insulating layer formed of one or more selected from the group consisting of the prepreg and the resin sheet of the present embodiment, and a conductor layer formed on the surface of the insulating layer. .
• the printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
• the printed wiring board of the present embodiment can be manufactured, for example, by the following method.
• An inner layer board having a conductor layer (inner layer circuit) is produced by etching the metal foil of the metal foil clad laminate into a predetermined wiring pattern.
• a laminate is obtained.
• the laminate molding method and molding conditions are the same as the laminate molding method and molding conditions for the laminate and the metal foil-clad laminate described above.
• the laminate is perforated for through holes and via holes, and the wall surfaces of the holes thus formed are plated with a metal film for conducting the conductor layer (internal circuit) and the metal foil for the outer layer circuit.
• the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is thus manufactured.
• a printed wiring board may be produced by forming a conductor layer that becomes a circuit on the insulating layer. At this time, an electroless plating technique can be used to form the conductor layer.
• Example 1 In a three-necked flask equipped with a thermometer and a Dimroth, 5.0 parts by mass of diallyl bisphenol A (DABPA, Daiwa Kasei Kogyo Co., Ltd.), 5.5 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), epoxy Modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / eq.) 4.1 parts by mass, epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional Base equivalent 500 g / eq.) 8.4 parts by mass, biphenyl type epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation) 5.5 parts by mass, propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan) as a solvent Co., Ltd.) was added, and the mixture was heated to 120° C.
• DABPA dially
• diallyl bisphenol A corresponds to "alkenylphenol A”
• epoxy-modified silicone compound A and epoxy-modified silicone compound B correspond to "epoxy-modified silicone B”
• biphenyl-type epoxy compound A corresponds to "epoxy compound C Equivalent to The phenoxy polymer solution contained a polymer containing structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C.
• the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that The polymer modification step can also be performed continuously with the polymer production step.
• the weight average molecular weight Mw of the modified phenoxy polymer obtained as described above was measured as follows. Analysis was performed by injecting 20 ⁇ L of a solution prepared by dissolving 0.5 g of the modified phenoxy polymer solution in 2 g of THF into a high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD). The columns were Shodex GPC KF-804 (length 30 cm x inner diameter 8 mm) manufactured by Showa Denko, Shodex GPC KF-803 (length 30 cm x inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm x inner diameter 8 mm), Shodex GPC.
• the weight average molecular weight Mw was obtained by GPC method using standard polystyrene as a standard substance.
• the weight average molecular weight Mw of the modified phenoxy polymer measured as described above was 12,000.
• a varnish was obtained (varnish production step). This varnish was impregnated and coated on an S glass woven cloth (thickness 100 ⁇ m), dried by heating at 150 ° C. for 3 minutes, and a prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained. was obtained (prepreg manufacturing process).
• Example 2 In the polymer production step, the amount of diallyl bisphenol A added was 5.0 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added was 5.5 parts by mass to 5.2 parts by mass, and epoxy-modified silicone A was added. The amount added is 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy-modified silicone B added is 8.4 parts by mass to 8.1 parts by mass, and the amount of biphenyl type epoxy compound A added is 5.5 parts by mass. In the same manner as in Example 1, except that the amount of acid anhydride D added in the polymer modification step was changed from 1.5 parts by mass to 5.2 parts by mass, and was changed to 3.0 parts by mass.
• a prepreg having a curable composition solid content (including filler) content of 58.2% by volume was obtained.
• the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that Moreover, the weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the method described above was 12,000.
• Example 3 In the polymer modification step, the curable composition solid content was adjusted in the same manner as in Example 2, except that the acid anhydride D was replaced with 3.0 parts by mass of succinic anhydride and 3.0 parts by mass of phthalic anhydride. A prepreg with a content of 58.2% by volume (including filler) was obtained.
• the modified phenoxy polymer solution contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, structural units derived from epoxy compound C, and structural units derived from acid anhydride D. It contained a polymer that The weight average molecular weight Mw of the modified phenoxy polymer in Example 3, measured by the method described above, was 12,000.
• the copper foil clad laminates (Examples 1 to 3) using the curable composition of the present embodiment had excellent low thermal expansion and copper foil peel strength.

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