Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
  • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
• • 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

Definitions

• This embodiment relates to a resin composition, a prepreg, a laminate, a printed wiring board, and a semiconductor package.
• thermosetting resins have been used as insulating materials for printed wiring boards.
• Epoxy resins which offer an excellent balance of insulation properties, heat resistance, cost, etc., have been commonly used as thermosetting resins for insulating materials.
• maleimide resin which is a thermosetting resin having superior heat resistance, is used as an insulating material for printed wiring boards (for example, see Patent Document 1, etc.).
• the present embodiment aims to provide a resin composition that uses maleimide resin as a thermosetting resin but has a low minimum melt viscosity, and a prepreg, laminate, resin film, printed wiring board, and semiconductor package that use the resin composition.
• this embodiment provides the following [1] to [11].
• [1] (A) one or more selected from the group consisting of maleimide resins having a group containing a condensed ring of an aromatic ring and an aliphatic ring and two or more N-substituted maleimide groups, and derivatives of the maleimide resins; (B) a phosphate compound having two or more phosphorus atoms, in which a group connecting at least two of the phosphorus atoms contains two or more aromatic rings;
• a resin composition comprising: [2] The resin composition according to the above [1], wherein the group containing a fused ring of an aromatic ring and an aliphatic ring contained in the component (A) is a group containing an indane ring as the fused ring.
• R A1 represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group.
• R A1 represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a hal
• n A1 represents an integer of 0 to 3.
• R A2 to R A4 each independently represent an alkyl group having 1 to 10 carbon atoms. * represents a bonding site.
• component (B) is a compound represented by the following general formula (B-1): (In the formula, R B1 to R B4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X B1 is a divalent group containing two or more aromatic rings.
• n B1 to n B4 each independently represent an integer of 0 to 5, and n B5 is an integer of 1 to 5.
• the content of the (B) component is 0.1 to 10 parts by mass relative to the total amount (100 parts by mass) of the resin components in the resin composition.
• [6] The resin composition according to any one of the above [1] to [5], further comprising (C) a compound having two or more functional groups containing an ethylenically unsaturated bond.
• a laminate comprising a cured product of the resin composition according to any one of [1] to [6] above and a metal foil.
• a resin film comprising the resin composition according to any one of [1] to [6] above or a semi-cured product of the resin composition.
• a printed wiring board having a cured product of the resin composition according to any one of [1] to [6] above.
• a semiconductor package comprising the printed wiring board according to [10] above and a semiconductor element.
• 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 means 25°C.
• the number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification refer to values measured in polystyrene equivalent by gel permeation chromatography (GPC). Specifically, the number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification can be measured by the method described in the Examples.
• si-cured product is synonymous with a resin composition in the B-stage state in JIS K 6800 (1985), and “cured product” is synonymous with a resin composition in the C-stage state in JIS K 6800 (1985).
• This embodiment also includes any combination of the items described in this specification.
• the resin composition of the present embodiment is (A) one or more selected from the group consisting of maleimide resins having a group containing a condensed ring of an aromatic ring and an aliphatic ring and two or more N-substituted maleimide groups, and derivatives of the maleimide resins; (B) a phosphate compound having two or more phosphorus atoms, in which a group connecting at least two of the phosphorus atoms contains two or more aromatic rings (hereinafter also referred to as "(B) phosphate compound");
• the resin composition comprises:
• each component may be abbreviated as component (A), component (B), etc., and other components may be abbreviated in the same manner.
• component (A), component (B), etc. each component that may be contained in the resin composition of the present embodiment will be described in order.
• the component (A) is at least one member selected from the group consisting of maleimide resins having a group containing a condensed ring of an aromatic ring and an aliphatic ring, and two or more N-substituted maleimide groups, and derivatives of the maleimide resins.
• the component (A) may be used alone or in combination of two or more types.
• component (A) is preferably an aromatic maleimide resin having a group containing a condensed ring of an aromatic ring and an aliphatic ring, and two or more N-substituted maleimide groups directly bonded to the aromatic ring, and more preferably an aromatic bismaleimide resin having a group containing a condensed ring of an aromatic ring and an aliphatic ring, and two N-substituted maleimide groups directly bonded to the aromatic ring.
• the group containing a fused ring of an aromatic ring and an aliphatic ring in component (A) is preferably a group containing a fused bicyclic structure as the fused ring, more preferably a group containing a fused ring of a benzene ring and an aliphatic ring, and even more preferably a group containing an indane ring.
• component (A) is preferably a maleimide resin having a group containing an indane ring and two or more N-substituted maleimide groups.
• the group containing an indan ring is preferably a divalent group represented by the following general formula (A-1):
• R A1 represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group.
• n A1 represents an integer of 0 to 3.
• R A2 to R A4 each independently represent an alkyl group having 1 to 10 carbon atoms. * represents a bonding site.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R A1 in the above general formula (A-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. These alkyl groups may be either linear or branched. Examples of the alkyl group contained in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by R A1 include the same as the alkyl group having 1 to 10 carbon atoms described above.
• Examples of the aryl group having 6 to 10 carbon atoms represented by R A1 include a phenyl group and a naphthyl group.
• Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms represented by R A1 include the same as the aryl group having 6 to 10 carbon atoms described above.
• Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R A1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
• R A1 is, from the viewpoint of solvent solubility and reactivity, preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R A2 to R A4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. These alkyl groups may be either linear or branched.
• R A2 to R A4 are preferably alkyl groups having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
• n A1 is an integer of 0 to 3
• multiple R A1 may be the same or different.
• the divalent group represented by the above general formula (A-1) is preferably a divalent group represented by the following formula (A-1a) in which n A1 is 0 and R A2 to R A4 are methyl groups, and more preferably a divalent group represented by the following formula (A-1a') or a divalent group represented by the following formula (A-1a'').
• (A) component containing a divalent group represented by the above general formula (A-1) from the viewpoints of dielectric properties, conductor adhesion, heat resistance, and ease of manufacture, the one represented by the following general formula (A-2) is preferred.
• R A1 to R A4 and n A1 are the same as those in the above general formula (A-1).
• Each R A5 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group.
• Each n A2 independently represents an integer of 0 to 4.
• n A3 represents a number of 0.95 to 10.0.
• a plurality of R A1 's, a plurality of n A1 's, a plurality of R A5 's, and a plurality of n A2's may be the same or different.
• n A3 exceeds 1 a plurality of R A2 's, a plurality of R A3 's, and a plurality of R A4's may be the same or different from each other.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R in the above general formula (A-2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. These alkyl groups may be either linear or branched. Examples of the alkyl group contained in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by R A5 include the same alkyl groups as those having 1 to 10 carbon atoms described above.
• Examples of the aryl group having 6 to 10 carbon atoms represented by R A5 include a phenyl group and a naphthyl group.
• Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms represented by R A5 include the same as the aryl group having 6 to 10 carbon atoms described above.
• Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R A5 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
• R A5 is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
• n A2 is an integer of 0 to 4, and from the viewpoints of compatibility with other resins, dielectric properties, conductor adhesion and ease of production, is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 2.
• the benzene ring and the N-substituted maleimide group have a twisted conformation, and intermolecular stacking is suppressed, which tends to further improve solvent solubility.
• the substitution position of R A5 is preferably the ortho position with respect to the substitution position of the N-substituted maleimide group.
• n A3 is preferably a number from 0.98 to 8.0, more preferably a number from 1.0 to 7.0, and even more preferably a number from 1.1 to 6.0, from the viewpoints of dielectric characteristics, conductor adhesion, solvent solubility, handleability, and heat resistance. Note that n A3 represents the average value of the number of structures containing indan rings.
• the component (A) represented by the above general formula (A-2) is more preferably one represented by the following general formula (A-3) or one represented by the following general formula (A-4) from the viewpoints of dielectric properties, conductor adhesion, solvent solubility, and ease of manufacture.
• Examples of the component (A) represented by the above general formula (A-3) include maleimide resins represented by the following general formula (A-3-1):
• each R A6 is independently a methyl group, an ethyl group, or an isopropyl group.
• n A3 is the same as in the above general formula (A-2).
• the component (A) represented by the above general formula (A-4) is preferably the one represented by the following general formula (A-4-1) from the viewpoints of dielectric properties, conductor adhesion, solvent solubility, and ease of manufacture.
• n A3 is the same as in the above general formula (A-2).
• an aminomaleimide resin containing a structure derived from the maleimide resin exemplified as component (A) and a structure derived from a diamine compound is preferred.
• the aminomaleimide resin can be produced, for example, by subjecting the maleimide resin exemplified as the component (A) to a Michael addition reaction with a diamine compound.
• diamine compounds include aromatic diamine compounds having two amino groups directly bonded to the aromatic ring, such as 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 silicone compounds having two primary amino groups.
• aromatic diamine compounds having two amino groups directly bonded to the aromatic ring such as 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'
• the number average molecular weight (Mn) of component (A) is not particularly limited, but from the viewpoints of compatibility with other resins, conductor adhesion, and heat resistance, it is preferably 600 to 3,000, more preferably 800 to 2,000, and even more preferably 1,000 to 1,500.
• the content of component (A) in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 80 mass%, more preferably 30 to 75 mass%, and even more preferably 50 to 70 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of component (A) is equal to or greater than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved.
• the content of component (A) is equal to or less than the upper limit, the dielectric properties tend to be improved.
• the resin composition of the present embodiment may further contain (A') 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, in addition to the component (A).
• the component (A') is preferably a maleimide resin represented by the following general formula (A'-1).
• X Ad1 is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.
• X Ad1 in the above general formula (A'-1) is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.
• Examples of the divalent organic group represented by X Ad1 in the above general formula (A'-1) include a divalent group represented by the following general formula (A'-2), a divalent group represented by the following general formula (A'-3), a divalent group represented by the following general formula (A'-4), a divalent group represented by the following general formula (A'-5), and a divalent group represented by the following general formula (A'-6).
• R Ad1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• n Ad1 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 Ad1 in general formula (A'-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 Ad1 is an integer of 2 or more, the multiple R Ad1 's may be the same or different.
• R Ad2 and R Ad3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X Ad2 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 (A'-3-1).
• n Ad2 and n Ad3 each independently represent an integer of 0 to 4. * represents a bonding site.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X Ad2 in the above general formula (A'-3) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X Ad2 in the above general formula (A'-3) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
• n Ad2 or n Ad3 is an integer of 2 or more, a plurality of R Ad2s or a plurality of R Ad3s may be the same or different.
• the divalent group represented by X Ad2 in the above general formula (A'-3) and represented by general formula (A'-3-1) is as follows.
• R Ad4 and R Ad5 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X Ad3 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 Ad4 and n Ad5 each independently represent an integer of 0 to 4. * represents a bonding site.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms or halogen atom represented by R Ad4 and R Ad5 in the above general formula (A'-3-1) are explained in the same way as those represented by R Ad1 in the above general formula (A'-2).
• the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X Ad3 in the above general formula (A'-3-1) are explained in the same way as those represented by X Ad2 in the above general formula (A'-3).
• n Ad4 or n Ad5 is an integer of 2 or more, the multiple R Ad4s or the multiple R Ad5s may be the same or different.
• n Ad6 is an integer from 0 to 10. * represents a binding site.
• n Ad7 is a number from 0 to 5. * represents a binding site.
• R Ad6 and R Ad7 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• n Ad8 represents an integer of 1 to 8. * represents a binding site.
• R Ad6 and R Ad7 in the above general formula (A'-6) are explained in the same manner as those represented by R Ad1 in the above general formula (A'-2).
• n Ad8 is an integer of 2 or greater, a plurality of R Ad6 or a plurality of R Ad7 may be the same or different.
• component (A') examples include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins.
• component (A') is preferably an aromatic polymaleimide resin, and more preferably a biphenylaralkyl type maleimide resin.
• an aminomaleimide resin containing a structure derived from the maleimide resin listed as component (A') and a structure derived from a diamine compound is preferred.
• the aminomaleimide resin can be produced, for example, by subjecting the maleimide resin exemplified as the component (A') to a Michael addition reaction with a diamine compound.
• diamine compound examples include the same diamine compounds as those exemplified as the raw material components of the maleimide resin derivative having a group containing a condensed ring of an aromatic ring and an aliphatic ring and two or more N-substituted maleimide groups, which is explained as component (A).
• the content of the (A) component relative to the total amount of the (A) component and the (A') component is not particularly limited, but is preferably 20 mass% or more, more preferably 50 mass% or more, and even more preferably 70 mass% or more.
• the content of the (A) component is equal to or more than the lower limit, a lower minimum melt viscosity tends to be obtained.
• the upper limit of the content of the (A) component may be 99% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on 100% by mass of the total amount of the (A) component and the (A') component.
• the content of component (A') is not particularly limited, but is preferably 5 to 80 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 30 mass%, relative to 100 mass% of the combined amount of components (A) and (A'). When the content of component (A') is within the above range, the characteristics of components (A) and (A') tend to be easily and sufficiently exhibited.
• the total content of the (A) component and the (A') component is not particularly limited, but is preferably 20 to 97 mass%, more preferably 50 to 95 mass%, and even more preferably 70 to 90 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of this embodiment.
• the total content of the (A) and (A') components is equal to or greater than the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved.
• the total content of the (A) and (A') components is equal to or less than the upper limit, the dielectric properties tend to be improved.
• the term "resin component” refers to a resin and a compound that forms a resin through a curing reaction.
• the components (A), (A'), (C) and (D) correspond to the resin components.
• the resin composition of the present embodiment contains, as optional components, a resin or a compound that forms a resin through a curing reaction in addition to the above components, these optional components are also included in the resin component.
• the components (B), (E) and (F) are 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 20 to 95 mass%, more preferably 40 to 92 mass%, and even more preferably 70 to 90 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 conductor 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 phosphate compound is a phosphate compound which has two or more phosphorus atoms and in which the group linking at least two of the phosphorus atoms contains two or more aromatic rings.
• the (B) phosphate ester compound may be used alone or in combination of two or more kinds.
• the resin composition of the present embodiment contains the phosphate ester compound (B), and thus has a low minimum melt viscosity even though it uses a maleimide resin as the thermosetting resin. Although the reason for this is unclear, it is speculated that one factor is that the (B) phosphate ester compound traps radicals present in the system when the resin composition is melted, thereby suppressing the curing reaction of component (A).
• the number of phosphorus atoms in the phosphate ester compound is 2 or more, preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 or 3.
• phosphate ester bond refers to a bond represented by any one of the following formulas (B-3) to (B-5). Among these, it is preferable to form a phosphate ester bond represented by the following formula (B-5).
• Examples of the organic group bonded to the phosphate bond include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, an aromatic hydrocarbon group is preferable. That is, the (B) phosphate compound is preferably an aromatic phosphate compound.
• Examples of the aromatic hydrocarbon group bonded to the phosphate ester bond include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, etc.
• substituents examples include a hydrocarbon 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, an n-pentyl group, etc.; a halogen atom, etc.
• a hydrocarbon 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, an n-pentyl group, etc.
• a halogen atom etc.
• an unsubstituted phenyl group or a 2,5-dimethylphenyl group is preferred.
• the group linking the two phosphorus atoms contains two or more aromatic rings.
• the two or more aromatic rings preferably form a divalent aromatic hydrocarbon group having a structure in which two or more aromatic rings are bonded by a single bond or a linking group having 5 or less carbon atoms (hereinafter also referred to as an "aromatic hydrocarbon group (Z1)”), or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic rings (hereinafter also referred to as an "aromatic hydrocarbon group (Z2)”), and more preferably form an aromatic hydrocarbon group (Z1).
• Aromaatic Hydrocarbon Group (Z1) examples of the aromatic rings contained in the aromatic hydrocarbon group (Z1) include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring is preferable.
• linking groups having 5 or less carbon atoms that the aromatic hydrocarbon group (Z1) may contain include divalent hydrocarbon groups having 1 to 5 carbon atoms, divalent heteroatom-containing groups having 5 or less carbon atoms, and divalent groups having 1 to 5 carbon atoms in which a hydrocarbon group and a heteroatom-containing group are linked. Note that the term "5 or less carbon atoms" as used herein also includes cases in which the number of carbon atoms is 0.
• divalent hydrocarbon groups having 1 to 5 carbon atoms include alkylene groups having 1 to 5 carbon atoms, such as methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, and 1,5-pentamethylene, and alkylidene groups having 2 to 5 carbon atoms, such as ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene.
• divalent heteroatom-containing groups having 5 or less carbon atoms include ether groups, sulfide groups, sulfonyl groups, carbonyloxy groups, and keto groups.
• the aromatic hydrocarbon group (Z1) is preferably a divalent group represented by the following general formula (B-2).
• R B5 and R B6 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X B2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
• n B6 and n B7 each independently represent an integer of 0 to 4.
• n B8 represents an integer of 1 to 3. * represents a bonding site.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X B2 in the above general formula (B-2) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X B2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
• a methylene group, an isopropylidene group and a single bond are preferred, and a single bond is more preferred.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R B5 and R B6 in general formula (B-2) above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group.
• n B6 and n B7 are preferably integers of 0 to 3, more preferably 0 or 1, and even more preferably 0.
• n B6 or n B7 is an integer of 2 or more, a plurality of R B5s or a plurality of R B6s may be the same or different.
• n B8 is preferably 1 or 2, and more preferably 1.
• n B8 is an integer of 2 or more
• a plurality of X B2s and a plurality of n B7s may be the same or different.
• the divalent group represented by the above general formula (B-2) is preferably a divalent group represented by the following formula (B-2-1) or a divalent group represented by the following formula (B-2-2), and more preferably a divalent group represented by the following formula (B-2-2).
• the aromatic hydrocarbon group (Z2) is a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic rings.
• the term "condensed polycyclic aromatic hydrocarbon” refers to an aromatic hydrocarbon having two or more ring structures, which has a condensed ring in which two or more rings share two or more atoms, and examples thereof include naphthalene, anthracene, pyrene, etc. Therefore, examples of the aromatic hydrocarbon group (Z2) include divalent groups obtained by removing two hydrogen atoms from these condensed polycyclic aromatic hydrocarbons. These condensed polycyclic aromatic hydrocarbons may or may not be substituted by a substituent. Examples of the substituent include the same substituents that may be possessed by the aromatic ring contained in the aromatic hydrocarbon group (Z1).
• the phosphate ester compound is preferably a compound represented by the following general formula (B-1):
• R B1 to R B4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
• X B1 is a divalent group containing two or more aromatic rings.
• n B1 to n B4 each independently represent an integer of 0 to 5, and n B5 is an integer of 1 to 5.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R B1 to R B4 in general formula (B-1) above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.
• 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.
• n B1 to n B4 are preferably 0 to 2, more preferably 0 or 2.
• n B1 to n B4 are integers of 2 or more, multiple R B1 's, R B2 's, R B3 's, or R B4 's may be the same or different.
• n B5 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
• n B5 is an integer of 2 or more, a plurality of X B1s and a plurality of n B4s may be the same or different.
• Examples of the divalent group containing two or more aromatic rings represented by X in the above general formula (B- 1 ) include the above aromatic hydrocarbon group (Z1) and aromatic hydrocarbon group (Z2).
• X is preferably the aromatic hydrocarbon group (Z1), more preferably the divalent group represented by the above general formula (B-2), and even more preferably the divalent group represented by the above formula (B-2-2).
• Examples of the phosphoric acid ester compound (B) include 4,4'-biphenol-diphenyl phosphate, bisphenol A-diphenyl phosphate, 4,4'-biphenol-dicresyl phosphate, bisphenol A-dicresyl phosphate, 4,4'-biphenol-di(2,6-xylenyl phosphate), bisphenol A-di(2,6-xylenyl phosphate), 4,4'-biphenol-polyphenyl phosphate, bisphenol A-polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A-polycresyl phosphate, 4,4'-biphenol-poly(2,6-xylenyl phosphate), bisphenol A-poly(2,6-xylenyl phosphate), etc.
• poly in the above example compounds means a compound having 2 or more repeating units (for example, in the above general formula (B-1), the structural units whose structural unit number is indicated by n B5 ) composed of a structure derived from a divalent phenol compound and a structure derived from phosphoric acid that constitute the phosphate ester compound, and may also mean a compound in which the average number of the repeating units exceeds 1 by containing such a compound.
• the average particle size (D 50 ) of the (B) phosphate ester compound is not particularly limited, but from the viewpoints of dispersibility and handleability, it is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, and even more preferably 0.5 to 3 ⁇ m.
• the average particle size (D 50 ) refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%.
• the content of the (B) phosphoric acid ester compound is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 7 parts by mass, and even more preferably 0.3 to 4 parts by mass relative to the total amount (100 parts by mass) of the resin components in the resin composition of the present embodiment.
• the content of the (B) phosphate ester compound is equal to or greater than the above lower limit, the minimum melt viscosity tends to be better.
• the content of the (B) phosphate ester compound is equal to or less than the above upper limit, the adhesion to the conductor tends to be better.
• the resin composition of the present embodiment further contains (C) a compound having two or more functional groups containing an ethylenically unsaturated bond.
• the resin composition of the present embodiment tends to have better dielectric properties.
• ethylenically unsaturated bond means a carbon-carbon double bond capable of undergoing an addition reaction, and does not include a double bond in an aromatic ring.
• a functional group containing an ethylenically unsaturated bond may be referred to as an "ethylenically unsaturated group.”
• the ethylenically unsaturated group include a vinyl group, an allyl group, a 1-methylallyl group, an isopropenyl group, a 2-butenyl group, a 3-butenyl group, a styryl group, a maleimide group, and a (meth)acryloyl group.
• the component (C) may be used alone or in combination of two or more types.
• the component (C) is preferably a polymer having two or more functional groups containing an ethylenically unsaturated bond.
• the polymer having two or more functional groups containing an ethylenically unsaturated bond include (C1) a conjugated diene polymer having two or more ethylenically unsaturated groups (hereinafter also simply referred to as "(C1) conjugated diene polymer”), (C2) a modified conjugated diene polymer having two or more ethylenically unsaturated groups (hereinafter also simply referred to as "(C2) modified conjugated diene polymer”), and (C3) a polyphenylene ether having two or more ethylenically unsaturated groups (hereinafter also simply referred to as "(C3) modified polyphenylene ether”).
• conjugated diene polymer means a polymer of a conjugated diene compound.
• the conjugated diene polymer (C1) is a conjugated diene polymer having two or more ethylenically unsaturated groups. From the viewpoints of compatibility with other resins and dielectric properties, the conjugated diene polymer (C1) preferably has a vinyl group in a side chain as an ethylenically unsaturated group.
• the number of side chain vinyl groups that the conjugated diene polymer (C1) has in one molecule is not particularly limited, but from the viewpoints of compatibility with other resins and dielectric properties, it is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more, and may be 100 or less, 80 or less, or 60 or less.
• Examples of the conjugated diene polymer (C1) include polybutadiene having a 1,2-vinyl group, butadiene-styrene copolymer having a 1,2-vinyl group, and polyisoprene having a 1,2-vinyl group.
• polybutadiene having a 1,2-vinyl group is preferred from the viewpoint of dielectric properties and heat resistance.
• a polybutadiene homopolymer having a 1,2-vinyl group is preferred.
• the 1,2-vinyl group derived from butadiene contained in the conjugated diene polymer (C1) is a vinyl group contained in a structural unit derived from 1,3-butadiene represented by the following formula (C1-1).
• the content of structural units having a 1,2-vinyl group relative to all structural units derived from butadiene constituting the polybutadiene (hereinafter also referred to as the "vinyl group content”) is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties and heat resistance, it is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 85 mol% or more.
• the upper limit of the vinyl group content may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.
• the number average molecular weight (Mn) of the (C1) conjugated diene polymer is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties, and heat resistance, it is preferably 400 to 3,000, more preferably 600 to 2,000, and even more preferably 800 to 1,500.
• the modified conjugated diene polymer (C2) is a modified conjugated diene polymer having two or more ethylenically unsaturated groups.
• the modified conjugated diene polymer (C2) is preferably one obtained by modifying the above-mentioned conjugated diene polymer (C1) with a maleimide resin having two or more N-substituted maleimide groups (hereinafter, also simply referred to as "maleimide resin").
• the conjugated diene polymer (C1) which is the raw material for the modified conjugated diene polymer (C2) is preferably a conjugated diene polymer having a vinyl group in the side chain.
• maleimide resin which is the raw material for the modified conjugated diene polymer (C2)
• those listed as components (A) and (A') can be used, and the preferred embodiments are also the same.
• the modified conjugated diene polymer (C2) preferably has, in its side chain, a substituent formed by a reaction between a side-chain vinyl group of a conjugated diene polymer having a vinyl group in its side chain and an N-substituted maleimide group of a maleimide resin [hereinafter, this may be referred to as a "maleimide resin-derived substituent.”], and more preferably has, in its side chain, a maleimide resin-derived substituent and a vinyl group.
• the maleimide resin-derived substituent is preferably a group containing a structure represented by the following general formula (C2-1) or (C2-2) as a structure derived from a maleimide resin:
• X C1 is a divalent group obtained by removing two N-substituted maleimide groups from a maleimide resin
• * C1 is a moiety that bonds to a carbon atom derived from a side chain vinyl group of a conjugated diene polymer having a vinyl group in the side chain
• * C2 is a moiety that bonds to another atom.
• the number average molecular weight (Mn) of the modified conjugated diene polymer (C2) is not particularly limited, but is preferably 700 to 6,000, more preferably 800 to 5,000, and even more preferably 1,000 to 2,500.
• the reaction conditions for the conjugated diene polymer (C1) and the maleimide resin are not particularly limited.
• the raw materials and the organic solvent are charged into a reaction vessel, and the reaction is carried out while heating, stirring, etc., as necessary, to obtain the modified conjugated diene polymer (C2).
• the ratio (M m /M v ) of the number of moles (M m ) of N-substituted maleimide groups in the maleimide resin to the number of moles (M v ) of side chain vinyl groups in the conjugated diene polymer having a vinyl group in the side chain is not particularly limited, but is preferably 0.001 to 0.5 , more preferably 0.005 to 0.1, and even more preferably 0.008 to 0.05, from the viewpoints of compatibility of the resulting (C2) modified conjugated diene polymer with other resins and suppression of gelation of the product during the reaction.
• the modified polyphenylene ether (C3) is a polyphenylene ether having two or more ethylenically unsaturated groups.
• (C3) Modified polyphenylene ether is not particularly limited, but preferably has a structural unit represented by the following general formula (C3-1):
• the ethylenically unsaturated group contained in the (C3) modified polyphenylene ether is preferably a (meth)acryloyl group, and more preferably a methacryloyl group.
• the number of ethylenically unsaturated groups in the (C3) modified polyphenylene ether is not particularly limited, but from the viewpoints of heat resistance and fluidity, it is preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.
• the modified polyphenylene ether preferably has an ethylenically unsaturated group at at least one end, more preferably at both ends, and even more preferably at only both ends.
• the weight average molecular weight (Mw) of the modified polyphenylene ether (C3) is not particularly limited, but is preferably 500 to 7,000, more preferably 800 to 5,000, even more preferably 1,000 to 3,000, and particularly preferably 1,200 to 2,500.
• the content of the (C) component is not particularly limited, but is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, and even more preferably 8 to 20 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of component (C) is equal to or greater than the lower limit, the dielectric properties tend to be improved.
• the content of component (C) is equal to or less than the upper limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (D) a styrene-based thermoplastic resin.
• the resin composition of the present embodiment tends to have better dielectric properties by containing the styrene-based thermoplastic resin (D).
• the styrene-based thermoplastic resin (D) may be used alone or in combination of two or more kinds.
• the styrene-based thermoplastic resin has structural units derived from a styrene-based compound.
• styrene-based compounds include styrene; and alkyl-substituted styrenes such as ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene.
• the number of carbon atoms in the alkyl group of the alkyl-substituted styrene is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
• styrene content is not particularly limited, but is preferably 5 to 60 mass%, more preferably 7 to 40 mass%, and even more preferably 10 to 20 mass%, from the viewpoints of dielectric properties, conductor adhesion, heat resistance, glass transition temperature, and low thermal expansion.
• Examples of structural units other than structural units derived from styrene compounds contained in styrene-based thermoplastic resins include structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, structural units derived from maleic anhydride, etc.
• styrene-based thermoplastic resins include hydrogenated styrene-butadiene-styrene block copolymers (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA).
• SEBS hydrogenated styrene-butadiene-styrene block copolymers
• SEBS hydrogenated styrene-butadiene-styrene block copolymers
• the number average molecular weight (Mn) of the (D) styrene-based thermoplastic resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 100,000 to 200,000.
• the content of the (D) styrene-based thermoplastic resin is not particularly limited, but is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, and even more preferably 8 to 20 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.
• the content of the (D) styrene-based thermoplastic resin is equal to or greater than the lower limit, the dielectric properties tend to be improved.
• the content of the (D) styrene-based thermoplastic resin is equal to or less than the upper limit, the heat resistance, moldability, processability, and conductor adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (E) an inorganic filler.
• E an inorganic filler.
• the inorganic filler (E) 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 crushed silica, fumed silica, and fused silica. Among these, fused silica is preferred from the viewpoints of dispersibility and moldability.
• the shape of the (E) inorganic filler may be, for example, spherical or crushed, with the spherical shape being preferred.
• the (E) inorganic filler may be one that has been surface-treated with a coupling agent such as a silane coupling agent.
• the average particle diameter (D 50 ) of the (E) inorganic filler is not particularly limited, but from the viewpoint of dispersibility and fine wiring property of the (E) inorganic filler, it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 1 ⁇ m, and particularly preferably 0.3 to 0.8 ⁇ m.
• the content of the inorganic filler (E) in the resin composition of the present embodiment is not particularly limited, but is preferably 5 to 80 mass%, more preferably 7 to 50 mass%, and even more preferably 10 to 30 mass%, relative to the total solid content (100 mass%) of the resin composition.
• the content of the (E) inorganic filler is equal to or greater than the lower limit, the low thermal expansion and heat resistance tend to be improved.
• the content of the (E) inorganic filler is equal to or less than the upper limit, the moldability and conductor adhesion tend to be improved.
• the resin composition of the present embodiment preferably further contains (F) a curing accelerator.
• a curing accelerator By including the curing accelerator (F), the resin composition of the present embodiment tends to have improved curability and to easily obtain better dielectric properties, heat resistance, and conductor adhesion.
• the curing accelerator (F) may be used alone or in combination of two or more kinds.
• curing accelerators include acidic 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 the 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 (F) is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass relative to the total amount (100 parts by mass) of the resin components in the resin composition of the present embodiment.
• the content of the curing accelerator (F) 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 (F) 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 one or more selected from the group consisting of resin materials other than the above components, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, flame retardants, organic solvents, and other additives, as necessary. Each of these may be used alone or in combination of two or more. The amount of these used is not particularly limited, and may be used as necessary within a range that does not inhibit the effects of the present embodiment.
• the resin composition of the present embodiment may contain an organic solvent from the viewpoint of facilitating handling and facilitating production of a prepreg, which will be described later.
• 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 above-mentioned components.
• the components When mixing the components, the components may be dissolved or dispersed while being stirred.
• the order in which the raw materials are mixed, the mixing temperature, the mixing time, and other conditions are not particularly limited and may be set arbitrarily depending on the types of raw materials, etc.
• the prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured product of the resin composition.
• the prepreg of the present embodiment contains, for example, the resin composition of the present embodiment or a semi-cured product of the resin composition, and a sheet-like fiber base material.
• the sheet-like fiber base material contained in the prepreg of this embodiment for example, a known sheet-like fiber base material used in various laminates for electrical insulating materials can be used.
• the material for the sheet-like fiber substrate include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; mixtures of these; etc.
• These sheet-like fiber substrates have shapes such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.
• the prepreg of the present embodiment can be produced, for example, by impregnating or coating a sheet-like fiber substrate with the resin composition of the present embodiment, and then heating and drying to bring it to a B-stage.
• the temperature and time for heat drying are not particularly limited, but from the viewpoint of productivity and appropriately bringing the resin composition of the present embodiment into the B-stage, the temperature and time for heat drying can be, for example, 50 to 200° C. and 1 to 30 minutes.
• the solids concentration derived from the resin composition in the prepreg of this embodiment is not particularly limited, but from the viewpoint of obtaining better moldability when made into a laminate, it is preferably 20 to 90 mass%, more preferably 25 to 80 mass%, and even more preferably 30 to 75 mass%.
• the resin film of the present embodiment is a resin film containing the resin composition of the present embodiment or a semi-cured product of the resin composition.
• the resin film of the present embodiment can be produced, for example, by applying the resin composition of the present embodiment containing an organic solvent, that is, a resin varnish, to a support and then drying by heating.
• the support include a plastic film, a metal foil, and a release paper.
• the temperature and time for heat drying are not particularly limited, but from the viewpoints of productivity and appropriately bringing the resin composition of the present embodiment into the B-stage, the temperature and time for heat drying can be set to 50 to 200° C. and 1 to 30 minutes.
• the resin film of this embodiment is preferably used to form an insulating layer when manufacturing a printed wiring board.
• the laminate of the present embodiment is a laminate having a cured product of the resin composition 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 the present embodiment is a printed wiring board having a cured product of the resin composition of the present embodiment.
• the printed wiring board of the present embodiment can be manufactured, for example, by forming a conductor circuit on one or more selected from the group consisting of the cured product of the prepreg of the present embodiment, the cured product of the resin film of the present embodiment, and a laminated board by a known method.
• a multilayer printed wiring board can be manufactured by further performing a multilayer 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 number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by the following methods.
• the values were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
• the calibration curve was approximated by a third order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name].
• TSKstandard POLYSTYRENE Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 [manufactured by Tosoh Corporation, product name].
• the measurement conditions for GPC are shown below.
• the mixture was reacted under a nitrogen atmosphere at 90 to 100°C for 5 hours with stirring to obtain a solution of a modified conjugated diene polymer (solid content concentration: 35% by mass).
• the number average molecular weight (Mn) of the obtained modified conjugated diene polymer was 2,000.
• the vinyl group modification rate of the bismaleimide resin was then calculated by the following formula.
• the vinyl group modification rate corresponds to the rate of decrease in the peak area derived from the bismaleimide resin due to the reaction.
• Vinyl group modification rate (%) [(peak area derived from bismaleimide resin before reaction) ⁇ (peak area derived from bismaleimide resin after reaction)] ⁇ 100/(peak area derived from bismaleimide resin before reaction)
• the vinyl group modification rate calculated from the above formula was 40%.
• the resin film obtained above was peeled off from the PET film and then pulverized to obtain a resin powder in a B-stage state.
• the resin powder was placed on a Teflon (registered trademark) sheet punched to a size of 0.5 mm thick x 50 mm long x 35 mm wide, and low-profile copper foils (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-VLP-18") having a thickness of 18 ⁇ m were placed on the top and bottom of the Teflon (registered trademark) sheet.
• the low-profile copper foil was placed with the M surface (roughened surface) facing the resin powder.
• the laminate before the heat and pressure molding was heated and pressurized under conditions of a temperature of 230° C., a pressure of 2.0 MPa, and a time of 120 minutes, and the resin powder was molded into a resin plate while being cured, thereby producing a resin plate with copper foil on both sides.
• the thickness of the resin plate portion of the obtained resin plate with copper foil on both sides was 0.5 mm.
• Method for evaluating non-adhesion between prepregs Fifteen prepregs prepared in each example were stacked and placed in an aluminum deposition pack, and left to stand for one week in a pressure-bonded state at 1 MPa. After the pressure was released, the non-adhesion between the prepregs was evaluated according to the following evaluation criteria.
• B When the prepregs were peeled off by hand, a crack occurred in part of the prepreg.
• C The overlapping prepregs were integrated with each other and could not be peeled off by hand.
• the resin plate with copper foil on both sides prepared in each example was immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution, to remove the copper foil.
• the resin plate obtained was cut into a size of 2 mm x 50 mm, and dried at 105°C for 1 hour to prepare a test piece.
• the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were then measured at an ambient temperature of 25°C and in the 10 GHz band according to the cavity resonator perturbation method.
• the resin plate with copper foil on both sides produced in each example was immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution, to remove the copper foil.
• the resin plate obtained was cut into a size of 200 mm length x 50 mm width as a test piece, and a flammability test was performed in accordance with the UL standard (UL94VTM).
• Maleimide resin 1 Aromatic bismaleimide resin having an indane ring-containing group represented by the above general formula (A-2): Number average molecular weight (Mn) 1,300
• Maleimide resin 2 biphenylaralkyl type maleimide (manufactured by Nippon Kayaku Co., Ltd., product name "MIR-3000”)
• Modified polyphenylene ether polyphenylene ether having methacryloyl groups at both ends, weight average molecular weight (Mw) 1,700
• Modified conjugated diene polymer Modified conjugated diene polymer obtained in Production Example 1
• Component (D) Styrene-based thermoplastic resin: styrene-ethylene-butylene-styrene (SEBS) copolymer (Kraton Polymer Japan Co., Ltd., product name "Kraton (registered trademark) MD1653", melt flow rate 5.0 g / 10 min, styrene content 30 mass%, hydrogenation rate 100%)
• SEBS styrene-ethylene-butylene-styrene copolymer
• Component (F) Organic peroxide: ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene
• Imidazole-based hardening accelerator Isocyanate masked imidazole (addition product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "G-8009L”)
• the resin composition of the present embodiment has a low minimum melt viscosity while using a maleimide resin as a thermosetting resin. Therefore, prepregs, laminates, printed wiring boards, semiconductor packages, and the like obtained using the resin composition are suitable for electronic component applications.

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• 2023
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