Classifications

• • 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
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • 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
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • 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
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
• • 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
  • C08K3/10—Metal compounds
  • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
• • 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
  • C08K3/10—Metal compounds
  • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/07—Parts immersed or impregnated in a matrix
  • B32B2305/076—Prepregs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • 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
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/24—Homopolymers or copolymers of amides or imides
• • 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
• • 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
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C08J2463/00—Characterised by the use of epoxy resins; 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0183—Dielectric layers
  • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure

Definitions

• This embodiment relates to prepregs, laminates, printed wiring boards, and semiconductor packages.
• insulating material for printed wiring boards prepregs obtained by impregnating a fiber base material such as glass cloth with a resin composition are used.
• a cured product of the prepreg may be subjected to drilling processing, but when the fiber base material has a large basis weight, the hardness of the fiber base material may cause deterioration in drilling processability, such as a decrease in the positional accuracy of the drill holes.
• a high inorganic filler content or a harder fiber base material may be used, and in such cases, the deterioration of drilling processability becomes more pronounced.
• Patent Document 1 discloses a resin composition containing a molybdenum compound supported on inorganic particles.
• the objective of this embodiment is to provide a prepreg that has excellent drilling processability and copper foil adhesion, and a laminate, printed wiring board, and semiconductor package that use the prepreg.
• this embodiment relates to the following [1] to [11].
• a resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate, and a fiber substrate; The prepreg, wherein the fiber base material has a basis weight of 50 g/ m2 or more.
• thermosetting resin contains one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins.
• thermosetting resin further contains an epoxy resin.
• a semiconductor package comprising the printed wiring board according to [10] above and a semiconductor element.
• a prepreg that has excellent drilling processability and copper foil adhesion, as well as a laminate, a printed wiring board, and a semiconductor package that use the prepreg.
• a numerical range indicated using “to” indicates a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
• a numerical range of "X to Y" (X and Y are real numbers) means a numerical range of not less than X and not more than Y.
• the expression “not less than X” means X and a numerical value exceeding X.
• the expression “not more than Y” means Y and a numerical value less than Y.
• Each lower limit and upper limit of a numerical range described herein may be arbitrarily combined with the lower limit or upper limit of any other numerical range. In the numerical ranges described in this specification, the lower or upper limit of the numerical range may be replaced with values shown in the examples.
• each of the components and materials exemplified in this specification may be used alone or in combination of two or more.
• the content of each component in a resin composition means, when a plurality of substances corresponding to each component are present in the resin composition, the total amount of the plurality of substances present in the resin composition, unless otherwise specified.
• solids refers to components other than the solvent, and includes those that are liquid, syrup-like, or waxy at room temperature.
• room temperature refers to 25°C.
• containing XX used in this specification includes both the meaning of containing XX in a reacted state if XX is capable of reacting, and the meaning of simply containing XX.
• the weight average molecular weight (Mw) in this specification means a value measured in polystyrene equivalent terms by gel permeation chromatography (GPC). Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in the Examples.
• cured product is synonymous with a resin composition in the C-stage state as defined in JIS K 6800 (2006).
• This embodiment also includes any combination of the items described in this specification.
• the prepreg of this embodiment is The present invention comprises a resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate, and a fiber substrate,
• the prepreg has a basis weight of 50 g/ m2 or more.
• the components constituting the prepreg of the present embodiment will be described in order.
• the prepreg of the present embodiment contains (A) a thermosetting resin and (B) a resin composition containing spherical zinc molybdate.
• thermosetting resins include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.
• the thermosetting resin (A) may be used alone or in combination of two or more kinds. Among these, from the viewpoints of heat resistance and copper foil adhesion, the thermosetting resin (A) is preferably a maleimide resin, an epoxy resin, or a cyanate resin, and more preferably a maleimide resin or an epoxy resin.
• the maleimide resin is preferably at least one selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins.
• maleimide-based resins “maleimide-based resins”.
• a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin (AX)” or an “(AX) component.”
• AX maleimide resin
• AX a derivative of a maleimide resin having one or more N-substituted maleimide groups
• AY maleimide resin derivative
• the maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. From the viewpoints of copper foil adhesion and heat resistance, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups.
• aromatic maleimide resin refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring.
• aromatic bismaleimide resin means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring.
• aromatic polymaleimide resin means a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring.
• aliphatic maleimide resin means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.
• maleimide resin (AX) a maleimide resin represented by the following general formula (A1-1) [hereinafter referred to as "maleimide resin (A1)"] is preferred.
• X A11 is a divalent organic group.
• X A11 in the above general formula (A1-1) is a divalent organic group.
• Examples of the divalent organic group represented by X A11 in the above general formula (A1-1) include a divalent group represented by the following general formula (A1-2), a divalent group represented by the following general formula (A1-3), a divalent group represented by the following general formula (A1-4), a divalent group represented by the following general formula (A1-5), and a divalent group represented by the following general formula (A1-6).
• R A11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• n A11 is an integer of 0 to 4. * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A11 in general formula (A1-2) above include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• n A11 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• the multiple R A11 's may be the same or different.
• R A12 and R A13 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X A12 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A1-3-1).
• n A12 and n A13 each independently represent an integer of 0 to 4. * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A12 and R A13 in the above general formula (A1-3) include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group; an alkenyl group having 2 to 5 carbon atoms; and an alkynyl group having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• an aliphatic hydrocarbon group having 1 to 5 carbon atoms an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is even more preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X A12 in general formula (A1-3) above include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc.
• the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X in general formula (A1-3) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc.
• an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
• n A12 and n A13 each independently represent an integer of 0 to 4.
• n A12 or n A13 is an integer of 2 or greater
• a plurality of R A12s or a plurality of R A13s may be the same or different.
• the divalent group represented by X A12 in the above general formula (A1-3) and represented by general formula (A1-3-1) is as follows.
• R A14 and R A15 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X A13 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n A14 and n A15 each independently represent an integer of 0 to 4. * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R and R in general formula (A1-3-1) above include alkyl groups having 1 to 5 carbon atoms, such as methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X A13 in general formula (A1-3-1) above include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc.
• the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X A13 in the above general formula (A1-3-1) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc.
• an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
• an alkylidene group having 2 to 5 carbon atoms is preferable, an alkylidene group having 2 to 4 carbon atoms is more preferable, and an isopropylidene group is even more preferable.
• n A14 and n A15 each independently represent an integer of 0 to 4. From the viewpoint of availability, each is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• n A14 or n A15 is an integer of 2 or greater, a plurality of R A14s or a plurality of R A15s may be the same or different.
• an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, or a divalent group represented by the above general formula (A1-3-1) is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is even more preferable.
• n A16 is an integer of 0 to 10. * represents a binding site.
• n A16 is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3, from the viewpoint of availability.
• n A17 is a number from 0 to 5. * represents a binding site.
• R A16 and R A17 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; n A18 represents an integer of 1 to 8; * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A16 and R A17 in general formula (A1-6) above include alkyl groups having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• n A18 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1.
• n A18 is an integer of 2 or greater, multiple R A16s or multiple R A17s may be the same or different.
• maleimide resin (A1) examples include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins.
• Specific examples of the maleimide resin (A1) include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene) bismaleimide, N,N'-[1,3-(2-methylphenylene)] bismaleimide, N,N'-[1,3-(4-methylphenylene)] bismaleimide, N,N'-(1,4-phenylene) bismaleimide, bis(4-maleimidophenyl)methane, and bis(3-methyl-4-maleimidophenyl)methane.
• AY -Maleimide resin derivative (AY)-
• a resin having a structure derived from the above-mentioned maleimide resin (AX) and a structure derived from a diamine compound (hereinafter, sometimes referred to as "aminomaleimide resin (A2)” or “component (A2)”.] is preferable.
• the aminomaleimide resin (A2) has a structure derived from the maleimide resin (AX) and a structure derived from a diamine compound.
• An example of a structure derived from the maleimide resin (AX) is a structure formed by a Michael addition reaction between at least one N-substituted maleimide group among the N-substituted maleimide groups contained in the maleimide resin (AX) and an amino group contained in a diamine compound.
• the structure derived from the maleimide resin (AX) contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
• the content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95 mass %, more preferably 30 to 93 mass %, and even more preferably 60 to 90 mass %.
• the content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, the dielectric properties and the handleability when made into a resin film tend to be better.
• ⁇ Structure derived from diamine compound An example of the structure derived from a diamine compound is a structure formed by a Michael addition reaction between one or both of two amino groups contained in a diamine compound and an N-substituted maleimide group contained in the maleimide resin (AX).
• the structure derived from the diamine compound contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
• the amino group contained in the diamine compound is preferably a primary amino group.
• Examples of the structure derived from a diamine compound having two primary amino groups include a group represented by the following general formula (A2-1) and a group represented by the following general formula (A2-2).
• X A21 in the above general formula (A2-1) and the above general formula (A2-2) is a divalent organic group, and corresponds to the divalent group obtained by removing two primary amino groups from a diamine compound.
• X A21 in the above general formula (A2-1) and the above general formula (A2-2) is preferably a divalent group represented by the following general formula (A2-3).
• R A21 and R A22 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom.
• X A22 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (A2-3-1) or the following general formula (A2-3-2).
• n A21 and n A22 each independently represent an integer of 0 to 4. * represents a bonding site.
• R A23 and R A24 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X A23 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n A23 and n A24 each independently represent an integer of 0 to 4. * represents a bonding site.
• R A25 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X A24 and X A25 each independently is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n A25 is an integer of 0 to 4. * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A21 , R A22 , R A23 , R A24 and R A25 in the above general formula (A2-3), the above general formula (A2-3-1) and the above general formula (A2-3-2) include alkyl groups having 1 to 5 carbon atoms such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group or an ethyl group.
• Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X in general formula ( A2-3 ), X in general formula (A2-3-1), and X and X in general formula ( A2-3-2 ) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc.
• the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X in general formula ( A2-3 ), X in general formula ( A2-3-1 ), and X and X in general formula (A2-3-2) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc.
• alkylidene group having 2 to 5 carbon atoms an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and an isopropylidene group is even more preferable.
• n A21 and n A22 each independently represent an integer of 0 to 4. From the viewpoint of availability, each is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2.
• n A21 or n A22 is an integer of 2 or greater, a plurality of R A21s or a plurality of R A22s may be the same or different.
• n A23 and n A24 each independently represent an integer of 0 to 4. From the viewpoint of availability, each is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• n A23 or n A24 is an integer of 2 or greater, a plurality of R A23s or a plurality of R A24s may be the same or different.
• n A25 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• n A25 is an integer of 2 or more, the multiple R A25 's may be the same or different.
• X in the general formula (A2-1) and the general formula (A2-2) may be a divalent group containing a structure represented by the following general formula (A2-4), or may be a divalent group represented by the following general formula (A2-5).
• R A26 and R A27 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. * represents a bonding site.
• R A26 and R A27 are the same as those in general formula (A2-4) above, R A28 and R A29 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group.
• X A26 and X A27 each independently represent a divalent organic group, and n A26 is an integer from 2 to 100. * represents a bonding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A26 to R A29 in the above general formulae (A2-4) and (A2-5) include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group; an alkenyl group having 2 to 5 carbon atoms; and an alkynyl group having 2 to 5 carbon atoms.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched.
• an aliphatic hydrocarbon group having 1 to 5 carbon atoms an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable.
• the substituent on the phenyl group in the substituted phenyl group represented by R A26 to R A29 include the above-mentioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.
• Examples of the divalent organic group represented by X A26 and X A27 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, --O--, or a divalent linking group formed by combining these groups.
• Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, and a propylene group.
• the alkenylene group includes, for example, alkenylene groups having 2 to 10 carbon atoms.
• the alkynylene group includes, for example, alkynylene groups having 2 to 10 carbon atoms.
• arylene group examples include arylene groups having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group.
• X A26 and X A27 are preferably an alkylene group or an arylene group, and more preferably an alkylene group.
• n A26 is an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and further preferably an integer of 5 to 30.
• n A26 is an integer of 2 or greater, a plurality of R A26s or a plurality of R A27s may be the same or different.
• the content of the structure derived from the diamine compound in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95 mass %, more preferably 7 to 70 mass %, and even more preferably 10 to 40 mass %.
• the content of the structure derived from the diamine compound in the aminomaleimide resin (A2) is within the above range, the dielectric characteristics, heat resistance, flame retardancy, and glass transition temperature tend to be better.
• diamine compound examples include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diamino
• the diamine compounds are preferably 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, and more preferably 3,3'-diethyl-4,4'-diaminodiphenylmethane. From the viewpoint of low thermal expansion, silicone compounds having two primary amino groups are preferred.
• the silicone compound having two primary amino groups a silicone compound having primary amino groups at both ends is preferred.
• the primary amino group equivalent of the silicone compound having two primary amino groups is not particularly limited, but is preferably 300 to 2,000 g/mol, more preferably 400 to 1,500 g/mol, and even more preferably 500 to 1,000 g/mol.
• the equivalent ratio (Ta2/Ta1) between the total equivalent (Ta2) of the groups derived from the -NH 2 groups of the diamine compound and the total equivalent (Ta1) of the groups derived from the N-substituted maleimide groups of the maleimide resin (AX) is not particularly limited, but is preferably 0.05 to 10, more preferably 1 to 8, and even more preferably 3 to 7, from the viewpoints of dielectric properties, heat resistance, flame retardancy, and glass transition temperature.
• the group derived from the -NH 2 group of the diamine compound includes -NH 2 itself.
• the group derived from the N-substituted maleimide group of the maleimide resin (AX) includes the N-substituted maleimide group itself.
• the weight average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but from the viewpoint of ease of handling and moldability, it is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.
• the aminomaleimide resin (A2) can be produced, for example, by reacting the maleimide resin (AX) with a diamine compound in an organic solvent. By reacting the maleimide resin (AX) with a diamine compound, an aminomaleimide resin (A2) is obtained through a Michael addition reaction between the maleimide resin (AX) and the diamine compound. When reacting the maleimide resin (AX) with the diamine compound, a reaction catalyst may be used as necessary.
• the reaction temperature for the Michael addition reaction is preferably 50 to 160° C., more preferably 60 to 150° C., and even more preferably 70 to 140° C., from the viewpoints of workability such as reaction rate, and suppression of gelation of the product during the reaction.
• the reaction time for the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours, from the viewpoints of productivity and allowing the reaction to proceed sufficiently.
• these reaction conditions can be appropriately adjusted depending on the types of raw materials used, and are not particularly limited.
• Epoxy resin is preferably an epoxy resin having two or more epoxy groups.
• Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.
• Epoxy resins are classified into various types according to the difference in the main skeleton. Specifically, the epoxy resins are classified into bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; novolac type epoxy resins such as bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl novolac type epoxy resins, and naphthol novolac type epoxy resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins; stilbene type epoxy resins; naphthylene ether type epoxy resins; biphenyl type epoxy resins; dihydroanthracene type epoxy resins; epoxy resins containing a saturated dicyclopentadiene skeleton; cyclo
• the resin composition of the present embodiment preferably contains, as the (A) thermosetting resin, one or more types selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins, and preferably further contains an epoxy resin.
• the content of one or more types selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins in the thermosetting resin (A) is not particularly limited, but is preferably 50 to 95 mass%, more preferably 60 to 90 mass%, and even more preferably 70 to 85 mass%.
• the content of the epoxy resin in the (A) thermosetting resin is not particularly limited, but is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %.
• the content of the (A) thermosetting resin is not particularly limited, but is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, and even more preferably 80 to 100 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of the (A) thermosetting resin is within the above range, the heat resistance, moldability, processability, and copper foil adhesion tend to be improved.
• resin component refers to resin and compounds that form resin through a curing reaction.
• the curing accelerator is not included in the resin component.
• the content of the resin component in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 90 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 50 mass%, relative to the total solid content (100 mass%) of the resin composition of the present embodiment.
• the content of the resin component is equal to or more than the lower limit, the heat resistance, moldability, processability, and copper foil adhesion tend to be improved.
• the content of the resin component is equal to or less than the upper limit, the low thermal expansion property tends to be improved.
• the prepreg of this embodiment is excellent not only in drilling processability but also in copper foil adhesion because the resin composition contains (B) spherical zinc molybdate.
• the reason why the prepreg of this embodiment has excellent copper foil adhesion is not clear, but it is presumed that one of the reasons is that (B) spherical zinc molybdate has the effect of making the surface of the prepreg uniform, which improves the adhesion between the prepreg and the copper foil.
• zinc molybdate is a salt of molybdic acid and zinc, and its composition formula is, for example, ZnXMoYO4 (0.5 ⁇ X ⁇ 2.5, 0.5 ⁇ Y ⁇ 2.5), ZnXMoYO4( OH ) Z (0.5 ⁇ X ⁇ 2.5, 0.5 ⁇ Y ⁇ 2.5, 0.5 ⁇ Z ⁇ 2.5), etc.
• the circularity of the spherical zinc molybdate (B) of this embodiment is preferably 90 to 100, more preferably 93 to 100, and even more preferably 95 to 100, from the viewpoint of copper foil adhesion. A more specific method for measuring the circularity is as described in the Examples.
• the average particle size (D 50 ) of the spherical zinc molybdate (B) is not particularly limited, but from the viewpoint of copper foil adhesion, it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 5 ⁇ m, and particularly preferably 0.5 to 1.5 ⁇ m.
• the average particle diameter ( D50 ) of particles refers to the particle diameter at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle diameters is calculated assuming the total volume of the particles to be 100%.
• the average particle diameter ( D50 ) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.
• the content of (B) spherical zinc molybdate is not particularly limited, but is preferably 0.1 to 10 mass%, more preferably 0.2 to 7 mass%, and even more preferably 0.5 to 5 mass%, relative to the total solid content (100 mass%) of the resin composition.
• the content of (B) spherical zinc molybdate is within the above range, drilling processability and copper foil adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (C) an inorganic filler.
• the resin composition of the present embodiment tends to easily obtain superior low thermal expansion properties and heat resistance.
• the concept of (C) inorganic filler does not include (B) spherical zinc molybdate.
• the inorganic filler (C) may be used alone or in combination of two or more kinds.
• inorganic fillers examples include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc.
• silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred.
• silica examples include precipitated silica produced by a wet method, which has a high water content, and dry method silica produced by a dry method, which contains almost no bound water. Dry method silica can also be classified into crushed silica, fumed silica, fused silica, etc., depending on the production method. Among these, fused silica is preferred from the viewpoints of dispersibility and moldability.
• the average particle diameter (D 50 ) of the inorganic filler (C) is not particularly limited, but from the viewpoint of the dispersibility and fine wiring property of the inorganic filler (C), it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 5 ⁇ m, and particularly preferably 0.3 to 2 ⁇ m.
• the shape of the (C) inorganic filler may be, for example, spherical or crushed, with the spherical shape being preferred.
• a coupling agent may be used for the purpose of improving the dispersibility of the inorganic filler (C) and the adhesion between the inorganic filler (C) and the organic component.
• Examples of coupling agents include silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred.
• the content of the inorganic filler (C) is not particularly limited, but is preferably 10 to 80 mass%, more preferably 30 to 75 mass%, even more preferably 40 to 70 mass%, still more preferably 50 to 67 mass%, and particularly preferably 55 to 65 mass%, relative to the total solid content (100 mass%) of the resin composition.
• the content of the (C) inorganic filler is equal to or more than the lower limit, the low thermal expansion property and the heat resistance tend to be improved.
• the content of the (C) inorganic filler is equal to or less than the upper limit, the moldability and the copper foil adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (D) a curing accelerator.
• a curing accelerator By including the curing accelerator (D) in the resin composition of the present embodiment, the curing property is improved, and there is a tendency that better copper foil adhesion can be easily obtained.
• the curing accelerator (D) may be used alone or in combination of two or more kinds.
• Examples of the curing accelerator include acid catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate mask imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane,
• the content of the curing accelerator (D) is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass relative to 100 parts by mass of the thermosetting resin (A).
• the content of the curing accelerator (D) is equal to or more than the lower limit, a sufficient curing acceleration effect tends to be easily obtained.
• the content of the curing accelerator (D) is equal to or less than the upper limit, the storage stability tends to be more improved.
• the resin composition of the present embodiment may further contain, as necessary, one or more other optional components selected from the group consisting of resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, organic solvents, and other additives.
• the above-mentioned optional components may each be used alone or in combination of two or more.
• the content of the above-mentioned optional components in the resin composition of the present embodiment is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.
• the resin composition of the present embodiment may not contain the above-mentioned optional components depending on the desired performance.
• the resin composition of the present embodiment may contain an organic solvent from the viewpoint of facilitating handling and facilitating production of a prepreg.
• the organic solvent may be used alone or in combination of two or more kinds.
• a resin composition containing an organic solvent may be referred to as a resin varnish.
• organic solvent examples include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethylsulfoxide; and ester-based solvents such as ⁇ -butyrolactone.
• alcohol solvents, ketone solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon solvents are preferred, aromatic hydrocarbon solvents are more preferred, and toluene is even
• the resin composition of the present embodiment can be produced by mixing the components. At this time, the components may be dissolved or dispersed while being stirred.
• the mixing order, temperature, time, and other conditions are not particularly limited and may be set arbitrarily depending on the type of raw material, etc.
• the fiber base material contained in the prepreg of this embodiment has a basis weight of 50 g/ m2 or more. By setting the basis weight of the fiber base material to 50 g/m 2 or more, the prepreg of this embodiment has excellent mechanical strength.
• the basis weight of the fiber base material is, from the viewpoint of the mechanical strength of the prepreg, preferably 60 g/ m2 or more, more preferably 70 g/ m2 or more, and even more preferably 80 g/ m2 or more, and from the viewpoint of high-density wiring, preferably 150 g/ m2 or less, more preferably 140 g/ m2 or less, even more preferably 130 g/ m2 or less, and particularly preferably 120 g/ m2 or less.
• the basis weight of the fiber base material is preferably 50 to 150 g/m 2 , more preferably 60 to 140 g/m 2 , even more preferably 70 to 130 g/m 2 , and particularly preferably 80 to 120 g/m 2 .
• the thickness of the fiber base material is preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more, even more preferably 70 ⁇ m or more, and particularly preferably 80 ⁇ m or more, and from the viewpoint of high-density wiring, the thickness is preferably 150 ⁇ m or less, more preferably 140 ⁇ m or less, even more preferably 130 ⁇ m or less, and particularly preferably 120 ⁇ m or less.
• the thickness of the fiber base material is not particularly limited, but from the viewpoint of the mechanical strength of the prepreg and high-density wiring, it is preferably 50 to 150 ⁇ m, more preferably 60 to 140 ⁇ m, even more preferably 70 to 130 ⁇ m, and particularly preferably 80 to 120 ⁇ m.
• the fiber substrate may have the form of, for example, a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, a surfacing mat, or the like.
• the fiber base material may be surface-treated with a coupling agent, or may be mechanically opened.
• the fibers constituting the fiber substrate include, for example, inorganic fibers such as glass fibers; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures of these. Among these, from the viewpoint of low thermal expansion, inorganic fibers are preferred, and glass fibers are more preferred. From the same viewpoint, the fiber substrate is preferably glass cloth.
• Examples of glass fibers include E glass, D glass, T glass, S glass, etc. Among these, from the viewpoint of low thermal expansion, one or more types selected from the group consisting of D glass, T glass, and S glass are preferred.
• Representative compositions of E glass, D glass, T glass and S glass are as follows: E glass: SiO 2 (52 to 56 mass%), Al 2 O 3 (12 to 16 mass%), Fe 2 O 3 (0 to 0.8 mass%), B 2 O 3 (5 to 10 mass%), CaO (16 to 25 mass%), MgO (0 to 6 mass%), Na 2 O+K 2 O (0 to 2 mass%), TiO 2 (0 to 1.5 mass%), F 2 (0 to 1 mass%) D glass: SiO 2 (74% by mass), Al 2 O 3 (0.5% by mass), B 2 O 3 (22% by mass), CaO (0.5% by mass), Na 2 O (1% by mass), K 2 O (1.5% by mass), Li 2 O (0.5% by mass), T glass: SiO 2 (64 to 66 mass%), Al 2 O 3 (24 to 26 mass%)
• the SiO 2 content in the glass fiber is not particularly limited, but is preferably 30 to 95 mass%, more preferably 40 to 90 mass%, even more preferably 50 to 80 mass%, and particularly preferably 60 to 75 mass%.
• the prepreg tends to have excellent low thermal expansion and low warpage properties.
• the prepreg tends to have better drill processability.
• the prepreg of the present embodiment can be produced, for example, by impregnating a fiber base material with a resin composition and then B-staging the resin composition.
• Methods that can be used to impregnate the fiber substrate with the resin composition include, for example, the hot melt method and the solvent method.
• the hot melt method is a method in which a fiber substrate is impregnated with a resin composition that does not contain an organic solvent.
• One aspect of the hot melt method is to first coat the resin composition of the present embodiment, which does not contain an organic solvent, onto a coated paper having good peelability, and then laminate the coated resin composition onto a fiber substrate to impregnate the same.
• Another embodiment of the hot melt method includes a method in which the resin composition of the present embodiment, which does not contain an organic solvent, is directly applied to a fiber substrate using a die coater or the like to impregnate the fiber substrate.
• the solvent method is a method of impregnating a fiber substrate with a resin composition containing an organic solvent.
• a method of immersing a fiber substrate in the resin composition of the present embodiment containing an organic solvent, and then drying the fiber substrate to remove the organic solvent and to bring the resin composition into a B-stage can be mentioned.
• the drying temperature is not particularly limited, but from the viewpoints of productivity and appropriately bringing the resin composition into the B-stage, it is preferably 50 to 200°C, more preferably 100 to 190°C, and even more preferably 150 to 180°C.
• the drying time is not particularly limited, but from the viewpoints of productivity and appropriately bringing the resin composition to the B-stage, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.
• the amount of resin composition contained in the prepreg of this embodiment is not particularly limited, but from the viewpoint of moldability, it is preferably 30 to 80% by mass, more preferably 35 to 70% by mass, and even more preferably 40 to 60% by mass.
• the laminate of the present embodiment is a laminate having a cured product of the prepreg of the present embodiment and a metal foil.
• a laminate having a metal foil is sometimes called a metal-clad laminate.
• the metal of the metal foil is not particularly limited, and examples include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.
• the laminate of this embodiment can be produced, for example, by arranging metal foil on one or both sides of the prepreg of this embodiment and then hot-pressing and molding it.
• the B-staged prepreg is cured by this hot press molding to obtain the laminate of this embodiment.
• the hot pressure molding for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used.
• the conditions for the hot pressing are not particularly limited, but may be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.
• the printed wiring board of this embodiment is a printed wiring board having a cured product of the prepreg of this embodiment.
• the printed wiring board of this embodiment can be manufactured, for example, by forming a conductor circuit on the cured product of the prepreg of this embodiment by a known method.
• a multi-layer printed wiring board can be manufactured by further performing a multi-layer adhesive process as necessary.
• the conductor circuit can be formed, for example, by appropriately performing a hole drilling process, a metal plating process, an etching process of a metal foil, or the like.
• the semiconductor package of this embodiment is a semiconductor package that includes the printed wiring board of this embodiment and a semiconductor element.
• the semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, and the like on the printed wiring board of this embodiment by a known method.
• the weight average molecular weight (Mw) was measured by the following method.
• the values were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
• the calibration curve was approximated by a third order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name].
• TSKstandard POLYSTYRENE Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 [manufactured by Tosoh Corporation, trade name].
• the measurement conditions for GPC are shown below.
• Production Example 1 Production of aminomaleimide resin
• a 5-liter reaction vessel equipped with a thermometer, a stirrer, and a moisture content meter with a reflux condenser, capable of heating and cooling 100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 5.6 parts by mass of a silicone compound (primary amino group equivalent: 750 g/mol) having primary amino groups at both ends, 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were added and reacted for 2 hours under reflux. The mixture was concentrated at the reflux temperature for 3 hours to produce an aminomaleimide resin solution with a solid content concentration of 65% by mass.
• the weight average molecular weight (Mw) of the obtained aminomaleimide resin was about 2,700.
• the varnish-like resin composition obtained above was impregnated into glass cloth (basis weight: 114 g/m 2 , glass type: T-glass, glass cloth thickness: 98 ⁇ m) and heated and dried at 120° C. for 3 minutes to obtain a prepreg.
• the content of the resin composition in the prepreg was 50% by mass.
• the amount of hole position deviation on the lower side of the third sheet was measured using a hole position accuracy measuring machine (manufactured by Via Mechanics Co., Ltd., product name "HT-1AM"), and the average of the amount of position deviation of 10,000 holes + 3 ⁇ ( ⁇ : standard deviation) was calculated and used as an index of drill hole position accuracy.
• a hole position accuracy measuring machine manufactured by Via Mechanics Co., Ltd., product name "HT-1AM”
• the copper foil of the copper-clad laminate prepared above was etched into a straight line shape of 5 mm width to prepare a test piece.
• the straight line-shaped copper foil thus formed was attached to a small tabletop tester (manufactured by Shimadzu Corporation, product name "EZ-TEST") and peeled off in a 90° direction at room temperature (25°C) to measure the copper foil peel strength.
• the pulling speed when peeling off the copper foil was 50 mm/min.
• Thermosetting resin 1 Aminomaleimide resin prepared in Production Example 1
• Thermosetting resin 2 Biphenylaralkyl type epoxy resin, "NC-3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275 g/eq
• Zinc molybdate-supported talc flaky, circularity less than 90, zinc molybdate support amount 20% by mass
• Component (C) Fused silica: average particle size ( D50 ) 0.5 ⁇ m, spherical fused silica
• Curing accelerator isocyanate masked imidazole, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "G-8009L"
• the prepregs of Examples 1 and 2 of this embodiment are able to reduce the amount of drill hole position deviation while maintaining the copper foil peel strength, compared to the prepreg of Comparative Example 1, which does not contain (B) spherical zinc molybdate.
• the prepreg of Comparative Example 2 which contains (B) talc carrying zinc molybdate, which is not spherical zinc molybdate is able to reduce the amount of drill hole position deviation, but the copper foil peel strength is significantly reduced.

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