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
• • 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
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• • H—ELECTRICITY
  • 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
  • H05K1/18—Printed circuits structurally associated with non-printed electric components
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
  • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
  • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
• • 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
  • C08J2335/00—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 at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
• • 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
  • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the present embodiment relates to a resin composition, a prepreg, a laminated board, a resin film, a printed wiring board, and a semiconductor package.
• the speed and capacity of signals used are increasing year by year.
• the substrate material of the printed wiring board mounted on these electronic devices has a dielectric property that can reduce the transmission loss of a high frequency signal [hereinafter, may be referred to as "high frequency characteristic”. ], That is, a low relative permittivity and a low dielectric loss tangent are required.
• the ITS Intelligent Transport Systems
• the practical application or practical planning of new systems handling high-frequency wireless signals has progressed. There is. Therefore, it is expected that the need for substrate materials having excellent high-frequency characteristics will increase for printed wiring boards used in these fields in the future.
• Patent Document 1 describes at least an inorganic filler and an N-substituted maleimide group as an object of providing a thermosetting resin composition having low dielectric tangent, low thermal expansion, and excellent wire embedding property and flatness.
• a technique for blending a polybutadiene-based elastomer modified with an acid anhydride in a thermosetting resin composition containing a polyimide compound having two structural units derived from a maleimide compound and a structural unit derived from a diamine compound is disclosed. ing.
• thermosetting resin composition disclosed in Patent Document 1 is excellent in dielectric properties, there is room for improvement in terms of achieving both even better dielectric properties and adhesiveness to a conductor.
• the present embodiment is a resin composition having excellent dielectric properties and adhesiveness to a conductor in a high frequency band of 10 GHz or higher, a prepreg using the resin composition, a laminated board, a resin film, and a printed wiring.
• An object of the present invention is to provide a plate and a semiconductor package.
• the present embodiment relates to the following [1] to [11].
• [1] One or more selected from the group consisting of a maleimide compound having a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups and a derivative thereof.
• (B) A resin having a tensile elastic modulus of 10 GPa or less at 25 ° C.
• a resin composition containing [2] The resin composition according to the above [1], wherein the fused ring is an indane ring.
• Ra1 has 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, and 6 to 10 carbon atoms.
• aryloxy group 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
• n1 is an integer of 0 to 3
• R a2 to R a4 are integers of 0 to 3.
• Each independently is an alkyl group having 1 to 10 carbon atoms. * Represents a bond site.
• the component (B) is a polyolefin-based resin obtained by modifying a conjugated diene polymer having a vinyl group in the side chain (b1) with a maleimide compound having two or more N-substituted maleimide groups (b2).
• a prepreg containing the resin composition according to any one of the above [1] to [6] or a semi-cured product of the resin composition.
• a semiconductor package comprising the printed wiring board according to the above [10] and a semiconductor element.
• a resin composition having excellent dielectric properties and adhesiveness to a conductor in a high frequency band of 10 GHz or higher, a prepreg, a laminated board, a resin film, a printed wiring board, and a semiconductor package using the resin composition are provided. Can be provided.
• the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
• the lower and upper limits of the numerical range described herein are optionally combined with the lower and upper limits of the other numerical ranges, respectively.
• the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
• each component and material exemplified in the present specification may be used alone or in combination of two or more.
• the content of each component in the resin composition is such that when a plurality of substances corresponding to each component are present in the resin composition, the plurality of substances present in the resin composition are not specified unless otherwise specified. Means the total amount of.
• An embodiment in which the items described in the present specification are arbitrarily combined is also included in the present embodiment.
• the mechanism of action described herein is speculative and does not limit the mechanism by which the resin composition according to this embodiment is effective.
• phase in the present specification means that the resins are miscible in nano units, micro units, or in appearance, even if they are not necessarily compatible in molecular units.
• the "semi-cured product” is synonymous with the resin composition in the B-stage state in JIS K 6800 (1985), and the "cured product” is C- in JIS K 6800 (1985). It is synonymous with the resin composition in the stage state.
• the number average molecular weight in the present specification means a value measured in polystyrene conversion by gel permeation chromatography (GPC; Gel Permeation Chromatography). Specifically, the number average molecular weight in the present specification can be measured by the method described in Examples.
• the resin composition of this embodiment is (A) One or more selected from the group consisting of a maleimide compound having a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups and a derivative thereof [hereinafter, "" It may be referred to as "(A) component”. ]When, (B) Tension elastic modulus at 25 ° C. [Hereinafter, it may be simply referred to as "25 ° C. tensile elastic modulus”. ] Is 10 GPa or less [hereinafter, may be referred to as “(B) component”. ]When, It is a resin composition containing.
• the resin composition of the present embodiment has dielectric properties in a high frequency band of 10 GHz or higher and adhesiveness to a conductor [hereinafter, may be referred to as "conductor adhesiveness”. ] Is not clear, but it is presumed as follows.
• the component (A) contained in the resin composition of the present embodiment is a maleimide compound containing a fused ring of an aromatic ring and an aliphatic ring in its molecular structure. Since the fused ring contains an aliphatic ring having low polarity in its structure, it contributes to the reduction of the dielectric loss tangent of the cured product obtained from the resin composition of the present embodiment, and its bulky three-dimensional structure has a relative permittivity. It is thought that it contributes to the reduction.
• the component (A) since the condensed ring contained in the component (A) locally lowers the polarity of the maleimide compound, the component (A) is excellent in compatibility not only with a compound having a high polarity but also with a compound having a low polarity. There is a tendency. As a result, the homogeneity of the entire cured product obtained from the resin composition of the present embodiment is improved, and it is considered that the conductor adhesiveness is also improved. Further, the component (B) contained in the resin composition of the present embodiment has a tensile elastic modulus at 25 ° C. of 10 GPa or less. The resin satisfying the 25 ° C. tensile elastic modulus can contribute to the improvement of the dielectric property while having excellent compatibility with the component (A) in terms of rigidity, molecular weight, polarity, etc. of the resin. It is considered that the dielectric properties have been further improved.
• the component (A) is one or more selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and a derivative thereof, which contains a fused ring of an aromatic ring and an aliphatic ring in the molecular structure. be.
• the component (A) one type may be used alone, or two or more types may be used in combination.
• the component (A) is preferably one or more compounds selected from the group consisting of the following (i) and (ii) from the viewpoint of dielectric properties and conductor adhesiveness.
• (I) Maleimide compound (a1) containing a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups [hereinafter, "maleimide compound (a1)” or "(a1)” ) Ingredients.
• aminomaleimide compound (A1) An aminomaleimide compound having a structural unit derived from the maleimide compound (a1) and a structural unit derived from the diamine compound (a2) [hereinafter, may be referred to as "aminomaleimide compound (A1)” or “component (A1)”. be. ]
• the component (a1) contains a fused ring of an aromatic ring and an aliphatic ring in the molecular structure from the viewpoint of dielectric properties, conductor adhesiveness and heat resistance, and has two or more N-substituted maleimide groups. Maleimide compounds are preferred. Further, as the component (a1), an aromatic bismaleimide compound containing a fused ring of an aromatic ring and an aliphatic ring in the molecular structure and having two N-substituted maleimide groups is more preferable.
• aromatic maleimide compound means a compound having an N-substituted maleimide group directly bonded to the aromatic ring
• aromatic bismaleimide compound is directly bonded to the aromatic ring. It means a compound having two N-substituted maleimide groups.
• the condensed ring contained in the component (a1) is preferably one having a condensed bicyclic structure, and more preferably an indane ring, from the viewpoint of dielectric properties, conductor adhesiveness and ease of manufacture.
• an aromatic bismaleimide compound containing an indane ring is preferable.
• the indane ring means a fused bicyclic structure of an aromatic 6-membered ring and a saturated aliphatic 5-membered ring. At least one carbon atom among the ring-forming carbon atoms forming the indane ring has a bonding group for bonding to another group constituting the component (a1).
• the ring-forming carbon atom having the bonding group and other ring-forming carbon atoms may not have a bonding group, a substituent, etc. in addition to the above-mentioned bonding group, but by having a bonding group other than the above, 2 It preferably forms a valence group.
• the indane ring is preferably contained as a divalent group represented by the following general formula (a1-1).
• Ra1 has 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, and 6 to 10 carbon atoms.
• aryloxy group 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
• n1 is an integer of 0 to 3
• R a2 to R a4 are integers of 0 to 3.
• Each independently is an alkyl group having 1 to 10 carbon atoms. * Represents a bond site.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R a1 in the above general formula (a1-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. Examples thereof include an octyl group, a nonyl group and a decyl group. These alkyl groups may be 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 Ra 1 include the same as the alkyl group having 1 to 10 carbon atoms.
• Examples of the aryl group having 6 to 10 carbon atoms represented by Ra 1 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 Ra 1 include the same aryl group as the aryl group having 6 to 10 carbon atoms.
• 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, a cyclodecyl group and the like. ..
• n1 in the above general formula (a1-1) is an integer of 1 to 3
• R a1 has an alkyl group having 1 to 4 carbon atoms and 3 to 6 carbon atoms from the viewpoint of solvent solubility and reactivity.
• a cycloalkyl group and an aryl group having 6 to 10 carbon atoms are preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
• 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. The group etc. can be mentioned. These alkyl groups may be linear or branched.
• R a2 to R a4 are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and even more preferably a methyl group.
• N1 in the above general formula (a1-1) is an integer of 0 to 3, and when n1 is 2 or 3, a plurality of Ra1s may be the same or different. ..
• the divalent group represented by the above general formula (a1-1) has the following formula (a1) in which n1 is 0 and R a2 to R a4 are methyl groups from the viewpoint of ease of manufacture.
• a divalent group represented by -1') is preferable.
• the component (a1) containing a divalent group represented by the general formula (a1-1) is described in the following general formula (a1-2) from the viewpoint of dielectric properties, conductor adhesiveness, heat resistance and ease of manufacture.
• the one represented by is preferable.
• R a1 to R a4 and n1 are the same as those in the above general formula (a1-1).
• R a5 is an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms, respectively. 10 alkyloxy groups, 1-10 carbons alkylthio groups, 6-10 carbons aryl groups, 6-10 carbons aryloxy groups, 6-10 carbons arylthio groups, 3-10 carbons cyclo It is an alkyl group, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, n2 is an independently integer of 0 to 4, and n3 is a number of 0.95 to 10.0.)
• a plurality of Ra1s , a plurality of n1s , a plurality of Ra5s, and a plurality of n2s may be the same or different from each other.
• n3 exceeds 1 the plurality of Ra2s , the plurality of Ra3s , and the plurality of Ra4s may be the same or different from each other.
• Examples of the alkyl group having 1 to 10 carbon atoms represented by R a5 in the above general formula (a1-2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , Nonyl group, decyl group and the like. These alkyl groups may be 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 are the same as those of the above-mentioned alkyl group having 1 to 10 carbon atoms.
• 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 aryl group as the aryl group having 6 to 10 carbon atoms.
• 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, a cyclodecyl group and the like. ..
• Ra5 is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, from the viewpoint of solvent solubility and ease of production. Alkyl groups of numbers 1 to 3 are more preferable, and methyl groups are even more preferable.
• N2 in the above general formula (a1-2) is an integer of 0 to 4, and is preferably 0 to 3 from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesiveness, and ease of manufacture. It is an integer, more preferably 0 or 2.
• n2 is 1 or more, the benzene ring and the N-substituted maleimide group have a twisted conformation, and the solvent solubility tends to be further improved by suppressing stacking between molecules.
• the substitution position of Ra5 is preferably the ortho position with respect to the N-substituted maleimide group.
• n3 in the general formula (a1-2) is preferably a value of 0.98 to 8.0, more preferably 1. It is a value of 0 to 7.0, more preferably a value of 1.1 to 6.0.
• n3 represents the average value of the number of structural units including an indane ring.
• the component (a1) represented by the general formula (a1-2) is represented by the following general formula (a1-3) from the viewpoint of dielectric properties, conductor adhesiveness, solvent solubility and ease of manufacture. Alternatively, it is more preferably represented by the following general formula (a1-4).
• R a1 to R a5 and n1 and n3 are the same as those in the above general formula (a1-2).
• R a1 to R a4 and n1 and n3 are the same as those in the above general formula (a1-2).
• Examples of the component (a1) represented by the general formula (a1-3) include a compound represented by the following general formula (a1-3-1) and a compound represented by the following general formula (a1-3-2). Examples thereof include compounds represented by the following general formula (a1-3-3).
• n3 is the same as that in the above general formula (a1-2).
• Examples of the compound represented by the above general formula (a1-4) include compounds represented by the following general formula (a1-4-1).
• n3 is the same as that in the above general formula (a1-2).
• the number average molecular weight of the component (a1) is not particularly limited, but is preferably 600 to 3,000, more preferably 800 to 2,000, from the viewpoint of compatibility with other resins, conductor adhesiveness, and heat resistance. , More preferably 1,000 to 1,500.
• the component (a1) is, for example, an intermediate amine compound containing a fused ring of an aromatic ring and an aliphatic ring [hereinafter, may be simply abbreviated as "intermediate amine compound”. ] And maleic anhydride are reacted [hereinafter, may be referred to as "maleimidization reaction”. ] Can be manufactured by the method of making.
• the intermediate amine compound of the maleimide compound containing an indane ring may be, for example, a compound represented by the following general formula (a1-5) [hereinafter, may be referred to as “Compound A”. ] And the compound represented by the following general formula (a1-6) [hereinafter, may be referred to as "Compound B”. ] And the reaction in the presence of an acid catalyst [hereinafter, may be referred to as "cyclization reaction”. ], It can be obtained as a compound represented by the following general formula (a1-7).
• R a1 and n1 are the same as those in the above general formula (a1-1).
• R a6 are independently each of the above formula (a1-5-1) or the above formula (a1-5). It is a group represented by -2), and the ortho position of at least one of the two Ra6s is a hydrogen atom.
• R a5 and n2 are the same as those in the above general formula (a1-2). However, at least one of the ortho and para positions of the amino group is a hydrogen atom.
• R a1 , R a5 and n1 to n3 are the same as those in the above general formula (a1-2).
• Examples of the compound A include p- or m-diisopropenylbenzene, p- or m-bis ( ⁇ -hydroxyisopropyl) benzene, 1- ( ⁇ -hydroxyisopropyl) -3-isopropenylbenzene, 1- ( ⁇ ). -Hydroxyisopropyl) -4-isopropenylbenzene, mixtures thereof, nuclear alkyl group substituents of these compounds, nuclear halogen substituents of these compounds and the like.
• Examples of the nuclear alkyl group substituent include diisopropenyltoluene and bis ( ⁇ -hydroxyisopropyl) toluene.
• Examples of the nuclear halogen substituent include chlorodiisopropenylbenzene and chlorobis ( ⁇ -hydroxyisopropyl) benzene. These compounds A may be used alone or in combination of two or more.
• Examples of compound B include aniline, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, chloroaniline, dichloroaniline, toluidine, xylidine, phenylaniline, nitroaniline and aminophenol. , Methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline, phenylthioaniline and the like. These compounds B may be used alone or in combination of two or more.
• the molar ratio of compound A and compound B is preferably 0.1 to 2.0, more preferably 0.15 to 1.5, still more preferable. Is charged at a ratio of 0.2 to 1.0, and the first-stage reaction is carried out. Next, the compound B to be further added is preferably added in terms of the molar ratio (compound B / compound A to be added) to the previously added compound A, preferably 0.5 to 20, more preferably 0.6 to 10, and even more preferably 0. It is preferable to add in a ratio of 7. to 5 and carry out the second step reaction.
• Examples of the acid catalyst used in the cyclization reaction include inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid; Solid acids such as acidic clay, silica alumina, zeolite, and strongly acidic ion exchange resin; heteropolyhydrochloride and the like can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
• inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid
• organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid
• Solid acids such as acidic clay, silica alumina, zeolite, and strongly acidic ion
• the amount of the acid catalyst to be blended is preferably 5 to 40 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the total amount of the first compound A and the compound B to be charged. , More preferably 5 to 30 parts by mass.
• the reaction temperature of the cyclization reaction is preferably 100 to 300 ° C., more preferably 130 to 250 ° C., still more preferably 150 to 230 ° C. from the viewpoint of reaction rate and reaction uniformity.
• the reaction time of the cyclization reaction is preferably 2 to 24 hours, more preferably 4 to 16 hours, still more preferably 8 to 12 hours from the viewpoint of productivity and sufficient progress of the reaction.
• these reaction conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited.
• a solvent such as toluene, xylene, chlorobenzene or the like may be used, if necessary.
• the dehydration reaction may be promoted by using a solvent capable of azeotropic dehydration.
• the component (a1) can be obtained by carrying out this maleimideization reaction.
• the equivalent ratio of maleic anhydride to the primary amino group equivalent of the intermediate amine compound in the maleimidization reaction is not particularly limited, but the amount of unreacted primary amino group. And from the viewpoint of reducing the amount of unreacted maleic anhydride, it is preferably 1.0 to 1.5, more preferably 1.05 to 1.3, and even more preferably 1.1 to 1.2.
• the amount of the organic solvent used in the maleimidization reaction is not particularly limited, but is preferably 50 to 5,000 with respect to 100 parts by mass of the total amount of the intermediate amine compound and maleic anhydride from the viewpoint of reaction rate and reaction uniformity. It is by mass, more preferably 70 to 2,000 parts by mass, and even more preferably 100 to 500 parts by mass.
• the reaction temperature in the first step reaction is preferably 10 to 100 ° C, more preferably 20 to 70 ° C, and even more preferably 30 to 50 ° C.
• the reaction time in the first step reaction is preferably 0.5 to 12 hours, more preferably 0.7 to 8 hours, still more preferably 1 to 4 hours.
• the second-step reaction is preferably carried out after the completion of the first-step reaction and the addition of a catalyst such as toluenesulfonic acid.
• the reaction temperature in the second stage reaction is preferably 90 to 130 ° C, more preferably 100 to 125 ° C, and even more preferably 105 to 120 ° C.
• the reaction time in the second step reaction is preferably 2 to 24 hours, more preferably 4 to 15 hours, still more preferably 6 to 10 hours.
• the above reaction conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited. After the reaction, unreacted raw materials, other impurities and the like may be removed by purifying with water or the like, if necessary.
• the component (a1) obtained by the above method may contain a maleimide compound containing no indane ring as a by-product.
• the maleimide compound containing no indane ring is, for example, a compound in which n3 is 0 in the above general formula (a1-2).
• the content of the maleimide compound containing no indane ring, which is a by-product, in the reaction product can be measured, for example, by measuring the GPC of the reaction product. Specifically, for example, after preparing a calibration line of the elution time for the number of n3 using each of the compounds in which n3 is 0 to 4 in the above general formula (a1-2), a GPC chart of the reaction product is created.
• the component (a1) preferably has a small content of a maleimide compound that does not contain an indane ring as a by-product. Therefore, in the GPC chart of the reaction product, the area ratio of the maleimide compound containing no indane ring as a by-product to the peak area of the entire reaction product is preferably 40% or less, more preferably 30% or less. It is more preferably 20% or less, and particularly preferably 10% or less.
• the aminomaleimide compound (A1) is an aminomaleimide compound having a structural unit derived from the maleimide compound (a1) and a structural unit derived from the diamine compound (a2).
• the component (A1) corresponds to a derivative of the maleimide compound (a1).
• one type may be used alone, or two or more types may be used in combination.
• the structural unit derived from the component (a1) for example, at least one N-substituted maleimide group among the N-substituted maleimide groups of the component (a1) has a Michael addition reaction with the amino group of the diamine compound (a2).
• the structural unit derived from the component (a1) contained in the component (A1) may be one type alone or two or more types.
• the content of the structural unit derived from the component (a1) in the aminomaleimide compound (A1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and further preferably 60 to 90% by mass. %.
• the content of the structural unit derived from the component (a1) in the component (A1) is within the above range, the dielectric property and the film handleability tend to be better.
• the structural unit derived from the component (a2) for example, of the two amino groups possessed by the component (a2), one or both amino groups are added to the N-substituted maleimide group possessed by the maleimide compound (a1) and Michael addition. Examples thereof include structural units formed by reaction.
• the structural unit derived from the component (a2) contained in the component (A1) may be one type alone or two or more types.
• the amino group contained in the component (a2) is preferably a primary amino group.
• Examples of the structural unit derived from the diamine compound (a2) 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). And so on.
• Xa1 in the general formulas (a2-1) and ( a2-2 ) is a divalent organic group, and corresponds to a divalent group obtained by removing two amino groups from the component (a2).
• X a1 in the general formula (a2-1) and the general formula (a2-2) is a divalent group represented by the following general formula (a2-3).
• R a11 and R a12 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms.
• X a2 has 1 carbon atom.
• P1 and p2 are independently integers of 0 to 4. * Represents a binding site.
• R a13 and R a14 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
• X a3 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Alkylidene group, m-phenylenediisopropylidene group, p-phenylenediisopropyridene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond.
• P3 and p4 are 0 independently. It is an integer of ⁇ 4. * represents the binding site.
• R a15 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
• X a4 and X a5 are independently alkylene groups having 1 to 5 carbon atoms and 2 to 5 carbon atoms, respectively. Alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond.
• P5 is an integer of 0 to 4. * Represents the bond site.
• Examples of the aliphatic hydrocarbon group 1 to 5 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 and the like having 1 carbon atom.
• Alkyl groups of up to 5; alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms, and the like can be mentioned.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
• 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 and an ethyl group are further preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• the number of carbon atoms represented by X a2 in the general formula (a2-3), X a3 in the general formula (a2-3-1), and X a4 and X a5 in the general formula (a2-3-2) is 1.
• the alkylene group to 5 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like.
• an alkylene group having 1 to 5 carbon atoms an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is further preferable.
• alkylidene group of 2 to 5 include an etylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group and the like.
• 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 further preferable.
• P1 and p2 in the above general formula (a2-3) are independently integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 3, more preferably 0 to 3. An integer of 2, more preferably 0 or 2.
• p1 or p2 is an integer of 2 or more, the plurality of Ra 11s or the plurality of Ra 12s may be the same or different from each other.
• P3 and p4 in the above general formula (a2-3-1) are independently integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably. It is 0 or 1, more preferably 0.
• p3 or p4 is an integer of 2 or more, the plurality of Ra 13s or the plurality of Ra 14s may be the same or different from each other.
• P5 in the above general formula (a2-3-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0 from the viewpoint of availability. be.
• p5 is an integer of 2 or more, the plurality of Ra 15s may be the same or different from each other.
• the content of the structural unit derived from the component (a2) in the aminomaleimide compound (A1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and further preferably 10 to 40% by mass. %.
• the content of the structural unit derived from the component (a2) in the aminomaleimide compound (A1) is within the above range, the dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.
• Examples of the component (a2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4.
• the component (a2) includes 4,4'-diaminodiphenylmethane and 4,4'-diamino from the viewpoint of excellent solubility in an organic solvent, reactivity with the maleimide compound (a1), and heat resistance.
• the component (a2) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption.
• the component (a2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane from the viewpoint of excellent mechanical properties such as high adhesiveness to a conductor, elongation, and breaking strength.
• the component (a2) is excellent in solubility in an organic solvent, reactivity at the time of synthesis, heat resistance, high adhesion to a conductor, and also excellent in dielectric properties and low hygroscopicity. 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferable.
• the equivalent ratio (Ta2 / Ta1) with the total equivalent of the groups (Ta1) is not particularly limited, but is preferably 0.05 to 10 from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature. Is 0.5 to 7, more preferably 1 to 5.
• the group derived from the N-substituted maleimide group of the maleimide compound (a1) includes the N-substituted maleimide group itself.
• the number average molecular weight of the aminomaleimide compound (A1) is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, still more preferably 600 to 2, from the viewpoint of handleability and moldability. It is 000.
• the component (A1) can be produced, for example, by reacting a maleimide compound (a1) with a diamine compound (a2) in an organic solvent. By reacting the maleimide compound (a1) and the diamine compound (a2), the aminomaleimide compound (A1) obtained by the Michael addition reaction between the maleimide compound (a1) and the diamine compound (a2) is obtained.
• reaction catalyst When the maleimide compound (a1) and the diamine compound (a2) are reacted, a reaction catalyst may be used if necessary.
• the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. .. These may be used alone or in combination of two or more.
• the amount of the reaction catalyst to be blended is not particularly limited, but is preferably 0.01 to 5 with respect to 100 parts by mass of the total amount of the maleimide compound (a1) and the diamine compound (a2) from the viewpoint of reaction rate and reaction uniformity. It is by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.
• the reaction temperature of the Michael addition reaction is preferably 50 to 160 ° C, more preferably 60 to 150 ° C, still more preferably 70 to 140, from the viewpoints of workability such as reaction rate and suppression of gelation of the product during the reaction. °C.
• the reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 2 to 6 hours from the viewpoint of productivity and sufficient progress of the reaction.
• these reaction conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited.
• the solid content concentration and solution viscosity of the reaction solution may be adjusted by adding or concentrating an organic solvent.
• the solid content concentration of the reaction solution is not particularly limited, but is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and further preferably 20 to 80% by mass.
• the solid content concentration of the reaction raw material is at least the above lower limit value, a good reaction rate is obtained, and the productivity tends to be better.
• the solid content concentration of the reaction raw material is not more than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelation of the product during the reaction tends to be further suppressed.
• the resin composition of the present embodiment contains a resin having a tensile elastic modulus at 25 ° C. of 10 GPa or less as the component (B), and thus has excellent dielectric properties and conductor adhesiveness.
• the resin corresponding to the component (A) is not included in the component (B).
• the component (B) one type may be used alone, or two or more types may be used in combination.
• the 25 ° C. tensile elastic modulus is a value measured by the following method. (Measuring method of 25 ° C tensile elastic modulus) A test piece having a width of 10 mm, a length of 80 mm, and a thickness of 0.2 mm is prepared from the resin to be measured, and the length of the test piece is set so that the distance between the gripping tools is 60 mm with the upper and lower grippers. Sandwich both ends in the side direction. Next, using a tensile tester, the tensile elastic modulus of the test piece at 25 ° C. is obtained under the condition of a tensile speed of 5 mm / min under a room temperature environment adjusted to 25 ° C. The tensile elastic modulus is calculated in accordance with the international standard ISO5271 (1993).
• the "resin having a 25 ° C tensile elastic modulus of 10 GPa or less" in the present embodiment means a resin from which the above-mentioned test piece cannot be produced because the 25 ° C tensile elastic modulus is too low, and the same reason. Therefore, even if the above-mentioned test piece can be produced, the tensile test cannot be carried out under the above-mentioned conditions.
• the 25 ° C. tensile elastic modulus of the component (B) is 10 GPa or less, preferably 7 GPa or less, more preferably 5 GPa or less, still more preferably 3 GPa or less, still more preferably 2 GPa or less, particularly preferably 1 GPa or less, and most preferably. It is 0.6 GPa or less.
• the 25 ° C. tensile elastic modulus of the component (B) is not more than the above upper limit value, the dielectric property and the conductor adhesiveness of the obtained resin composition tend to be excellent.
• tensile elastic modulus of the component (B) is not particularly limited, but is preferably 0.005 GPa or more, more preferably 0.01 GPa or more, and further preferably 0.03 GPa or more.
• the 25 ° C. tensile elastic modulus of the component (B) is at least the above lower limit value, the heat resistance and the like of the obtained resin composition tend to be kept good.
• the number average molecular weight of the component (B) is not particularly limited, but is preferably 400 to 500,000, more preferably 600 to 350,000, and even more preferably 700 to 200,000.
• the number average molecular weight of the component (B) is at least the above lower limit value, the heat resistance of the obtained resin composition tends to be kept good. Further, when the number average molecular weight of the component (B) is not more than the above upper limit value, the dielectric property and the conductor adhesiveness of the obtained resin composition tend to be excellent.
• thermoplastic resin and a modified product thereof are preferably mentioned.
• the component (B) may be a thermosetting resin, but the component (B), which is a thermosetting resin, is preferably an elastomer.
• elastomer as used herein means a polymer having a glass transition temperature of 25 ° C. or lower as measured by differential scanning calorimetry according to JIS K 6240: 2011.
• the component (B) examples include a polyolefin resin, a polyphenylene ether resin, a silicone resin, an epoxy resin, a polyurethane resin, a polyester resin, a polyamide resin, and a polyacrylic resin.
• the component (B) is selected from the group consisting of a polyolefin resin, a polyphenylene ether resin, a silicone resin and an epoxy resin from the viewpoint of compatibility with the component (A), dielectric properties and conductor adhesiveness. It is preferable to contain one or more of them, more preferably one or more selected from the group consisting of a polyolefin resin and a polyphenylene ether resin, and further preferably containing a polyolefin resin.
• the polyolefin-based resin is not particularly limited as long as it is a polyolefin-based resin having a tensile elastic modulus at 25 ° C. of 10 GPa or less.
• the polyolefin-based resin one type may be used alone, or two or more types may be used in combination.
• Examples of the polyolefin-based resin include homopolymers or copolymers such as monoolefins and diolefins, and modified products thereof.
• Examples of the monoolefin include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene and the like.
• Examples of the diolefin include non-conjugated diene compounds such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, and ethylidenenorbornene; 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3. Examples thereof include conjugated diene compounds such as -dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.
• the polyolefin-based resin may be referred to as a conjugated diene polymer (B1) [hereinafter, "(B1) component” from the viewpoint of compatibility with other resins, dielectric properties, and conductor adhesiveness. ], Modified conjugated diene polymer (B2) [hereinafter, may be referred to as "(B2) component”. ], Styrene-based elastomer (B3) [hereinafter, may be referred to as "(B3) component”. ] Is preferable.
• the component (B1) may be a polymer of one kind of conjugated diene compound or a polymer of two or more kinds of conjugated diene compounds. Further, the component (B1) may be obtained by copolymerizing one or more kinds of conjugated diene compounds and one or more kinds of monomers other than the conjugated diene compounds.
• the polymerization mode when the component (B1) is a copolymer is not particularly limited, and may be any of random polymerization, block polymerization and graft polymerization. As the component (B1), one type may be used alone, or two or more types may be used in combination.
• a conjugated diene polymer having a vinyl group in the side chain is preferable, and a conjugated diene having a plurality of vinyl groups in the side chain is preferable from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion. Polymers are more preferred.
• the number of vinyl groups contained in one molecule of the component (B1) is not particularly limited, but is preferably 3 or more, more preferably 5 from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion. More than 10 pieces, more preferably 10 pieces or more.
• the upper limit of the number of vinyl groups that the component (B1) has in one molecule is not particularly limited, but may be 100 or less, 80 or less, or 60 or less.
• Examples of the component (B1) include polybutadiene having a 1,2-vinyl group, a butadiene-styrene copolymer having a 1,2-vinyl group, and polyisoprene having a 1,2-vinyl group.
• polybutadiene having a 1,2-vinyl group and a butadiene-styrene copolymer having a 1,2-vinyl group are preferable, and polybutadiene having a 1,2-vinyl group is preferable from the viewpoint of dielectric properties and heat resistance. More preferred.
• a polybutadiene having a 1,2-vinyl group a polybutadiene homopolymer having a 1,2-vinyl group is preferable.
• the 1,2-vinyl group contained in the component (B1) is a vinyl group contained in a structural unit derived from butadiene represented by the following formula (B1-1).
• the content of the structural unit having a 1,2-vinyl group with respect to all the structural units derived from butadiene constituting the polybutadiene [hereinafter, "vinyl”. It may be referred to as "group content”. ] Is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 85 mol, from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesiveness and heat resistance. % Or more. Further, the upper limit of the vinyl group content is not particularly limited, and may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.
• the structural unit having a 1,2-vinyl group a structural unit derived from butadiene represented by the above formula (B1-1) is preferable.
• the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.
• the 25 ° C. tensile elastic modulus of the component (B1) is within the preferable range of the 25 ° C. tensile elastic modulus of the component (B) described above, but further improves the dielectric properties and conductor adhesiveness of the obtained resin composition. It is preferably 0.005 to 0.5 GPa, more preferably 0.01 to 0.3 GPa, and further preferably 0.03 to 0.1 GPa from the viewpoint of allowing the heat resistance to be maintained.
• the number average molecular weight of the component (B1) is not particularly limited, but is preferably 400 to 3,000, more preferably 600 to 3,000 from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion and heat resistance. It is 2,000, more preferably 800 to 1,500.
• the component (B) preferably contains a modified conjugated diene polymer (B2) as a polyolefin resin, and is used in the side chain (b1) from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion.
• a conjugated diene polymer having a vinyl group [hereinafter, may be referred to as "component (b1)”.
• component (b2) May be referred to as (b2) a maleimide compound having two or more N-substituted maleimide groups [hereinafter, “(b2) component”.
• the component (B2) one type may be used alone, or two or more types may be used in combination.
• component (b1) a conjugated diene polymer having a vinyl group in the side chain described as the component (B1) can be used, and the preferred embodiment is also the same.
• component (b1) one type may be used alone, or two or more types may be used in combination.
• the component (b2) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups.
• As the component (b2) one type may be used alone, or two or more types may be used in combination.
• the component (b2) includes an aromatic ring and an aliphatic ring in the molecular structure described as the maleimide compound (a1) from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion.
• Maleimide compounds containing a fused ring and having two or more N-substituted maleimide groups are preferred.
• the preferred embodiment of the maleimide compound is the same as the preferred embodiment of the maleimide compound (a1) described above.
• the component (b2) may be referred to as a maleimide compound other than the maleimide compound (a1) [hereinafter, “(b2i) component”. ] May be.
• a maleimide compound represented by the following general formula (b2-1) is preferable.
• X b1 is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.
• X b1 in the above general formula (b2-1) is a divalent organic group that does not contain a fused ring of an aromatic ring and an aliphatic ring, and contains two N-substituted maleimide groups from the component (b2i). Corresponds to the excluded divalent group.
• Examples of the divalent organic group represented by X b1 in the above general formula (b2-1) include a divalent group represented by the following general formula (b2-2) and the following general formula (b2-3).
• R b1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
• Q1 is an integer of 0 to 4. * Represents a bond site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in the above general formula (b2-2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl.
• Examples thereof include an alkyl group having 1 to 5 carbon atoms such as a 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 linear or branched.
• 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 further preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• Q1 in the general formula (b2-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0 from the viewpoint of availability.
• q1 is an integer of 2 or more, the plurality of R b1s may be the same or different.
• R b2 and R b3 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
• X b2 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms.
• Q2 and q3 are, respectively. Independently, it is an integer from 0 to 4. * Represents the binding site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b2 and R b3 in the above general formula (b2-3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl.
• Alkyl groups having 1 to 5 carbon atoms such as groups, isobutyl groups, t-butyl groups and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms and the like can be mentioned.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be 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 from the viewpoint of compatibility with other resins and suppression of gelation of the product during the reaction.
• An alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are further preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b2 in the above general formula (b2-3) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group and a 1,4-tetramethylene group. Groups, 1,5-pentamethylene groups and the like can be mentioned.
• an alkylene group having 1 to 5 carbon atoms an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is further preferable.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 in the above general formula (b2-3) include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. And so on.
• 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 further preferable.
• Q2 and q3 in the above general formula (b2-3) are independently integers of 0 to 4, and both are easily available, compatible with other resins, and gel of the product during the reaction. From the viewpoint of suppressing the conversion, it is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.
• q2 + q3 is preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and even more preferably 4 from the viewpoint of availability, compatibility with other resins, and suppression of gelation of the product during the reaction. Is.
• the plurality of R b2s or the plurality of R b3s may be the same or different from each other.
• the divalent group represented by the general formula (b2-3-1) represented by X b2 in the general formula (b2-3) is as follows.
• R b4 and R b5 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
• X b3 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. It is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond.
• Q4 and q5 are independently integers of 0 to 4. * Represents a bond site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b4 and R b5 in the above general formula (b2-3-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n.
• -Alkyl groups having 1 to 5 carbon atoms such as butyl groups, isobutyl groups, t-butyl groups and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms and the like can be mentioned.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be 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 further preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• Examples of the alkylene group having 1 to 5 carbon atoms represented by X b3 in the above general formula (b2-3-1) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, and 1,4-. Examples thereof include a tetramethylene group and a 1,5-pentamethylene group.
• an alkylene group having 1 to 5 carbon atoms an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is further preferable.
• Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b3 in the above general formula (b2-3-1) include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopenti. Examples include the reden group. Among these, 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 further preferable.
• 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 further preferable. preferable.
• Q4 and q5 in the above general formula (b2-3-1) are independently integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably. It is 0 or 1, more preferably 0.
• q4 or q5 is an integer of 2 or more, the plurality of R b4s or the plurality of R b5s may be the same or different from each other.
• the X b2 in the general formula (b2-3) includes an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and the general formula (b2-3-1).
• the divalent group to be used is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is further preferable.
• q6 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.
• R b6 and R b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• Q8 is an integer of 1 to 8; * represents a bond site.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b6 and R b7 in the above general formula (b2-6) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as a 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 linear or branched.
• q8 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.
• q8 is an integer of 2 or more, the plurality of R b6s or the plurality of R b7s may be the same or different from each other.
• Examples of the component (b2i) include an aromatic bismaleimide compound having two N-substituted maleimide groups bonded to the aromatic ring, and an aromatic polymaleimide compound having three or more N-substituted maleimide groups bonded to the aromatic ring. , An aliphatic maleimide compound having an N-substituted maleimide group bonded to an aliphatic group, and the like.
• Specific examples of the component (b2i) include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N'-[.
• the modified conjugated diene polymer (B2) is a substituent formed by reacting a vinyl group of the conjugated diene polymer (b1) with an N-substituted maleimide group of the maleimide compound (b2) in the side chain [hereinafter, "" It may be referred to as "substituent (x)". ] It is preferable to have.
• the substituent (x) has the following general formula (B2-11) or (B2) as a structure derived from the maleimide compound (b2) from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is preferable that the group contains the structure represented by -12).
• X B1 is a divalent group consisting of the component (b2) minus two N-substituted maleimide groups
• * B1 is a carbon derived from the vinyl group of the component (b1) in the side chain. It is a site that binds to an atom.
• * B2 is a site that bonds to another atom.
• the modified conjugated diene polymer (B2) preferably has a substituent (x) and a vinyl group (y) in the side chain.
• the extent to which the substituent (x) is present in the modified conjugated diene polymer (B2) is the degree to which the vinyl group of the component (b1) is modified by the component (b2) [hereinafter, "vinyl group modification rate". May be called. ] Can be used as an index.
• the vinyl group modification rate is not particularly limited, but is preferably 20 to 70%, more preferably 30 to 60%, still more preferably, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. Is 35 to 50%.
• the vinyl group modification rate is a value obtained by the method described in Examples.
• the vinyl group (y) is preferably a 1,2-vinyl group having a structural unit derived from butadiene.
• the 25 ° C. tensile elastic modulus of the component (B2) is within the preferable range of the 25 ° C. tensile elastic modulus of the component (B) described above, but the dielectric properties and conductor adhesiveness of the obtained resin composition are further improved. It is preferably 0.01 to 1 GPa, more preferably 0.03 to 0.5 GPa, and further preferably 0.05 to 0.15 GPa from the viewpoint of allowing the heat resistance to be maintained.
• the number average molecular weight of the component (B2) is not particularly limited, but is preferably 700 to 6,000, more preferably 800 to 6,000 from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is 5,000, more preferably 1,000 to 2,500.
• the component (B2) can be produced by reacting a conjugated diene polymer (b1) with a maleimide compound (b2).
• the method for reacting the conjugated diene polymer (b1) with the maleimide compound (b2) is not particularly limited.
• the component (B2) is obtained by charging a conjugated diene polymer (b1), a maleimide compound (b2), a reaction catalyst, and an organic solvent into a reaction vessel and reacting them with heating, heat retention, stirring, etc., if necessary. Can be done.
• the reaction temperature of the above reaction is preferably 70 to 120 ° C., more preferably 80 to 110 ° C., still more preferably 85 to 105 ° C.
• the reaction time of the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, still more preferably 3 to 7 hours from the viewpoint of productivity and sufficient progress of the reaction.
• these reaction conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited.
• organic solvent used in the above reaction examples include alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; and ketone solvents such as acetone, methyl ethyl acetate, methyl isobutyl ketone and cyclohexanone.
• alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether
• ketone solvents such as acetone, methyl ethyl acetate, methyl isobutyl ketone and cyclohexanone.
• Aromatic hydrocarbon solvents such as toluene, xylene, mesitylen; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N Examples thereof include a nitrogen atom-containing solvent such as methyl-2-pyrrolidone.
• the organic solvent one kind may be used alone, or two or more kinds may be used in combination. Among these, toluene is preferable from the viewpoint of resin solubility.
• the total content of the conjugated diene polymer (b1) and the maleimide compound (b2) in the reaction solution is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to. It is 60% by mass, more preferably 20 to 50% by mass.
• the total content of the conjugated diene polymer (b1) and the maleimide compound (b2) is at least the above lower limit, a good reaction rate is obtained and the productivity tends to be better.
• the total content of the conjugated diene polymer (b1) and the maleimide compound (b2) is not more than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelation of the product during the reaction is performed. Tends to be more suppressive.
• reaction catalyst an organic peroxide is preferable from the viewpoint of obtaining sufficient reactivity while suppressing gelation of the product during the reaction, and ⁇ , ⁇ '-bis (t-butylperoxy) diisopropyl is preferable. Benzene is more preferred.
• reaction catalyst one type may be used alone, or two or more types may be used in combination.
• the amount of the reaction catalyst used is not particularly limited, but is preferably 0.01 to 1 with respect to 100 parts by mass of the total amount of the conjugated diene polymer (b1) and the maleimide compound (b2) from the viewpoint of reaction rate and reaction uniformity. It is by mass, more preferably 0.03 to 0.5 parts by mass, and even more preferably 0.05 to 0.2 parts by mass.
• the ratio of the number of moles (M m ) of the N-substituted maleimide group of the maleimide compound (b2) to the number of moles (M v ) of the side chain vinyl group of the conjugated diene polymer (b1) in carrying out the above reaction ( M m / M v ) is not particularly limited, but is preferably 0.001 to 0. From the viewpoint of compatibility of the obtained (B2) component with other resins and suppression of gelation of the product during the reaction. 5, more preferably 0.005 to 0.1, still more preferably 0.008 to 0.05.
• the component (B) preferably contains a styrene-based elastomer (B3) as the polyolefin-based resin.
• the component (B3) is not particularly limited as long as it is an elastomer having a tensile elastic modulus at 25 ° C. of 10 GPa or less and having a structural unit derived from a styrene compound.
• one type may be used alone, or two or more types may be used in combination.
• component (B3) a component having a structural unit derived from a styrene-based compound represented by the following general formula (B3-1) is preferable.
• R b8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R b9 is an alkyl group having 1 to 5 carbon atoms
• K is an integer of 0 to 5).
• Examples of the alkyl group having 1 to 5 carbon atoms represented by R b8 and R b9 in the above general formula (B3-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl. Examples include a group, a t-butyl group, an n-pentyl group and the like.
• the alkyl group having 1 to 5 carbon atoms may be either linear or branched. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is further preferable.
• K1 in the general formula (B3-1) is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• Examples of the structural unit other than the structural unit derived from the styrene compound contained in the component (B3) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride, and the like. Can be mentioned.
• the structural unit derived from butadiene and the structural unit derived from isoprene may be hydrogenated.
• the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed
• the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
• the components (B3) include hydrogenated additives (SEBS, SBBS) and styrene-isoprene of a styrene-butadiene-styrene block copolymer from the viewpoints of dielectric properties, conductor adhesiveness, heat resistance, glass transition temperature and low thermal expansion.
• SEBS hydrogenated additives
• SBBS styrene-isoprene of a styrene-butadiene-styrene block copolymer
• One or more selected from the group consisting of the hydrogenated product of the styrene block copolymer (SEPS) and the styrene-maleic anhydride copolymer (SMA) is preferable, and hydrogenation of the styrene-butadiene-styrene block copolymer is preferable.
• SEBS styrene-isoprene-styrene block copolymer
• SEBS hydrogenated product of a styrene-butadiene-styrene block copolymer
• styrene content the content of structural units derived from styrene
• styrene content Is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, still more preferably 10 from the viewpoint of dielectric properties, conductor adhesiveness, heat resistance, glass transition temperature and low thermal expansion. It is about 20% by mass.
• the melt flow rate (MFR) of SEBS is not particularly limited, but is 230 ° C. and a load of 2.16 kgf (21.2 N) from the viewpoint that the 25 ° C. tensile elastic modulus of the component (B3) can be easily adjusted within a suitable range.
• the measurement conditions are preferably 0.1 to 20 g / 10 min, more preferably 1 to 10 g / 10 min, and even more preferably 3 to 7 g / 10 min.
• the 25 ° C. tensile elastic modulus of the component (B3) is within the preferable range of the 25 ° C. tensile elastic modulus of the component (B) described above, but further improves the dielectric properties and conductor adhesiveness of the obtained resin composition. It is preferably 0.02 to 4 GPa, more preferably 0.05 to 2 GPa, and further preferably 0.1 to 1 GPa from the viewpoint of allowing the heat resistance to be maintained.
• the number average molecular weight of the component (B3) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 10,000 to 500,000 from the viewpoint that the 25 ° C. tensile elastic modulus of the component (B3) can be easily adjusted within a suitable range. It is 50,000 to 350,000, more preferably 100,000 to 200,000.
• the content of one or more selected from the group consisting of the component (B1), the component (B2) and the component (B3) in the total amount of the component (B) is not particularly limited, but has dielectric properties and conductor adhesiveness. From the viewpoint, it is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
• the content of one or more selected from the group consisting of the component (B1), the component (B2) and the component (B3) in the total amount of the component (B) is not particularly limited, but is 100% by mass or less. It may be 98% by mass or less, or 95% by mass or less.
• the component (B) preferably contains the component (B2) and the component (B3) as a polyolefin resin from the viewpoint of dielectric properties and conductor adhesiveness.
• the polyolefin resin contains the component (B2) and the component (B3)
• the content ratio of the component (B2) to the component (B3) [(B2) component / (B3) component] is not particularly limited. From the viewpoint of compatibility, dielectric properties and conductor adhesiveness, it is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.5 to 1.
• the component (B) may be referred to as a polyphenylene ether-based resin (B4) [hereinafter, “component (B4)”. ], Silicone resin (B5) [hereinafter, may be referred to as “(B5) component”. ], Epoxy resin (B6) [hereinafter, may be referred to as "(B6) component”. ] Is also preferable.
• the component (B4) is not particularly limited as long as it is a polyphenylene ether-based resin having a tensile elastic modulus at 25 ° C. of 10 GPa or less.
• the phenylene group contained in the "polyphenylene ether” in the present specification is a concept including not only an unsubstituted phenylene group but also a phenylene group substituted with a substituent.
• the component (B4) one type may be used alone, or two or more types may be used in combination.
• the component (B4) also has at least a phenylene ether bond, and preferably has a structural unit represented by the following general formula (B4-1).
• R b10 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
• S1 is an integer of 0 to 4.
• Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b10 in the above general formula (B4-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group.
• Alkyl groups having 1 to 5 carbon atoms such as isobutyl groups, t-butyl groups and n-pentyl groups; alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms and the like can be mentioned.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
• aliphatic hydrocarbon group having 1 to 5 carbon atoms an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is further preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• s1 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 2.
• the plurality of R b10s may be the same or different from each other.
• s1 is 1 or 2, it is preferable to replace R b10 with the ortho position on the benzene ring (provided that the substitution position of the oxygen atom is used as a reference).
• the structural unit represented by the general formula (B4-1) is preferably a structural unit represented by the following general formula (B4-2).
• the component (B4) may have a structural unit other than the phenylene ether unit, but may not have a structural unit other than the phenylene ether unit.
• the component (B4) may have a phenolic hydroxyl group at one end or both ends.
• the average number of phenolic hydroxyl groups per molecule of the component (B4) is preferably 1 to 2, more preferably 1.4 to 1.9, and even more preferably 1.6 to 1.85.
• the 25 ° C. tensile elastic modulus of the component (B4) is preferably 0 from the viewpoint of improving the dielectric properties and conductor adhesiveness of the obtained resin composition, from the viewpoint of maintaining good heat resistance, and from the viewpoint of availability. It is .5 to 7 GPa, more preferably 1 to 5 GPa, and even more preferably 1.5 to 3 GPa.
• the number average molecular weight of the component (B4) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,000 to 50,000, from the viewpoint that the 25 ° C. tensile elastic modulus of the component (B4) can be easily adjusted within a suitable range. It is 5,000 to 20,000, more preferably 8,000 to 15,000.
• the component (B5) is not particularly limited as long as it is a silicone-based resin having a tensile elastic modulus at 25 ° C. of 10 GPa or less.
• the component (B5) one type may be used alone, or two or more types may be used in combination.
• the component (B5) has at least a siloxane bond, and preferably has a structural unit represented by the following general formula (B5-1).
• R b11 and R b12 are each independently a phenyl group having an alkyl group, a phenyl group or a substituent having 1 to 5 carbon atoms.
• Examples of the alkyl group having 1 to 5 carbon atoms represented by R b11 and R b12 in the above general formula (B5-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl. Examples include a group, a t-butyl group, an n-pentyl group and the like.
• the alkyl group having 1 to 5 carbon atoms may be either linear or branched. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is further preferable.
• Examples of the substituent having the phenyl group in the phenyl group having the substituent represented by R b11 and R b12 in the above general formula (B5-1) include an alkyl group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Examples thereof include an alkenyl group and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group.
• Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group.
• Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group.
• the alkyl group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms and the alkynyl group having 2 to 5 carbon atoms may be either linear or branched.
• R b11 and R b12 in the above general formula (B5-1) are preferably alkyl groups having 1 to 5 carbon atoms, more preferably methyl groups or ethyl groups, and are methyl groups. Is even more preferable. That is, the structural unit represented by the above general formula (B5-1) is preferably a dimethylsiloxane unit.
• the component (B5) may be a linear silicone-based resin or a branched-chain silicone-based resin, but a linear silicone-based resin is preferable.
• the component (B5) may have a reactive group in its molecular structure.
• the reactive group may be one introduced into a part of the side chain of the polysiloxane, or may be introduced into one end or both ends of the polysiloxane. Further, the reactive group may be one introduced into one end or both ends in addition to the side chain of polysiloxane.
• the reactive group examples include an epoxy group, an amino group, a vinyl group, a hydroxyl group, a methacrylic group, a mercapto group, a carboxy group, an alkoxy group, a silanol group and the like.
• the component (B5) may contain one or more of the above reactive groups.
• an amino group and a vinyl group are preferable.
• the amino group a primary amino group and a secondary amino group are preferable, and a primary amino group is more preferable.
• the component (B5) when the component (B5) has an amino group, the component (B5) preferably has one or two primary amino groups, preferably one or two, from the viewpoint of compatibility with other resins. It is more preferable to have two primary amino groups, and it is further preferable to have a diaminopolysiloxane having one primary amino group at each end.
• the 25 ° C. tensile elastic modulus of the component (B5) is within the preferable range of the 25 ° C. tensile elastic modulus of the component (B) described above, but the dielectric properties and conductor adhesiveness of the obtained resin composition are further improved. It is preferably 0.01 to 1 GPa, more preferably 0.03 to 0.5 GPa, and further preferably 0.05 to 0.15 GPa from the viewpoint of allowing the heat resistance to be maintained.
• the reactive group equivalent thereof is not particularly limited, but is preferably 200 to 3,000 g / mol, more preferably 300 to 1,000 g / mol, and further preferably 400 to 400. It is 600 g / mol.
• the component (B6) is not particularly limited as long as it is an epoxy resin having a tensile elastic modulus at 25 ° C. of 10 GPa or less.
• the component (B6) one type may be used alone, or two or more types may be used in combination.
• an epoxy resin having two or more epoxy groups is preferable.
• Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins and the like. Among these, glycidyl ether type epoxy resin is preferable.
• Examples of the component (B6) include an aliphatic chain epoxy resin, a rubber-modified epoxy resin, and an epoxy resin having an alicyclic skeleton.
• an epoxy resin having an alicyclic skeleton is preferable from the viewpoint of improving the dielectric properties and conductor adhesiveness of the obtained resin composition.
• the alicyclic skeleton contained in the component (B6) is not particularly limited, but an alicyclic skeleton having 5 to 20 ring-forming carbon atoms is preferable, and an alicyclic skeleton having 6 to 18 ring-forming carbon atoms is more preferable.
• An alicyclic skeleton having 8 to 14 carbon atoms is particularly preferable.
• the alicyclic skeleton is preferably composed of two or more rings, more preferably 2 to 4 rings, and further preferably 3 rings.
• the alicyclic skeleton composed of two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, a dicyclopentadiene skeleton, and the like.
• a dicyclopentadiene skeleton is preferable.
• Examples of the epoxy resin having an alicyclic skeleton include an epoxy resin represented by the following general formula (B6-1).
• R b13 is an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the alicyclic skeleton.
• R b14 is an alkyl group having 1 to 12 carbon atoms.
• Examples of the alkyl group having 1 to 12 carbon atoms represented by R b13 in the above general formula (B6-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , Nonyl group, decyl group and the like. These alkyl groups may be linear or branched. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
• M1 in the above general formula (B6-1) is an integer of 0 to 6, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and even more preferably 0.
• m1 is an integer of 2 or more
• the plurality of R b13s may be the same or different from each other. Further, the plurality of R b13s may be substituted on the same carbon atom to the extent possible, or may be substituted on different carbon atoms.
• Examples of the alkyl group having 1 to 12 carbon atoms represented by R b14 in the above general formula (B6-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , Nonyl group, decyl group and the like. These alkyl groups may be linear or branched. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
• M2 in the above general formula (B6-1) is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. When m2 is an integer of 2 or more, the plurality of R b14s may be the same or different from each other.
• R in the above general formula (B6-1) represents the number of repetitions of the structural unit in parentheses, and is a number of 0 to 10, preferably 2 to 10.
• the epoxy resin represented by the above general formula (B6-1) is a mixture of those having different numbers of repetitions of the structural units in parentheses, r is expressed as the average value of the mixture.
• the 25 ° C. tensile elastic modulus of the component (B6) is preferably 1 from the viewpoint of improving the dielectric properties and conductor adhesiveness of the obtained resin composition, from the viewpoint of maintaining good heat resistance, and from the viewpoint of availability. It is ⁇ 7 GPa, more preferably 1.5 to 5 GPa, still more preferably 2 to 3 GPa.
• the epoxy group equivalent of the component (B6) is not particularly limited, but is preferably 150 to 1,000 g / mol, more preferably 200 to 500 g / mol, and even more preferably 250 to 300 g / mol.
• component (B) other than the above examples include one or more selected from the group consisting of polyurethane-based resins, polyester-based resins, polyamide-based resins, and polyacrylic-based resins.
• polyurethane resin examples include those having a hard segment composed of a low molecular weight diol and a diisocyanate and a soft segment composed of a high molecular weight diol and a diisocyanate.
• small molecule diol examples include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like.
• polymer diol examples include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexylene carbonate).
• Poly (1,6-hexylene-neopentylene adipate) and the like are examples of polyurethane resins.
• one kind may be used alone, or two or more kinds may be used in combination.
• One type of polyurethane resin may be used alone, or two or more types may be used in combination.
• polyester resin examples include those obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
• dicarboxylic acid examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; an aromatic in which the hydrogen atom of the aromatic nucleus of these aromatic dicarboxylic acids is replaced with a methyl group, an ethyl group, a phenyl group, or the like.
• dicarboxylic acids aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like can be mentioned. These dicarboxylic acids may be used alone or in combination of two or more. Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol; and fats such as 1,4-cyclohexanediol.
• Cyclic diols examples include aromatic diols such as bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcin. These diol compounds may be used alone or in combination of two or more. Further, a multi-block copolymer having an aromatic polyester moiety such as polybutylene terephthalate as a hard segment component and an aliphatic polyester moiety such as polytetramethylene glycol as a soft segment component may be used. As the polyester resin, one type may be used alone, or two or more types may be used in combination.
• polyamide resin polyamide is used as a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylenepropylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, poly.
• block copolymers containing methacrylate, polyurethane, silicone rubber and the like as soft segment components As the polyamide resin, one type may be used alone, or two or more types may be used in combination.
• acrylic resin examples include a polymer obtained by polymerizing a raw material monomer containing an acrylic acid ester as a main component.
• acrylic acid ester examples include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate.
• cross-linking point monomer glycidyl methacrylate, allyl glycidyl ether or the like may be used as a raw material, or acrylonitrile, ethylene or the like may be copolymerized.
• acrylic resin one type may be used alone, or two or more types may be used in combination.
• the content of the component (A) is not particularly limited, but is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of the resin components in the resin composition of the present embodiment. , More preferably 20 to 80 parts by mass, still more preferably 25 to 75 parts by mass.
• the content of the component (A) is at least the above lower limit value, the heat resistance, moldability, processability, flame retardancy and conductor adhesiveness tend to be better. Further, when the content of the component (A) is not more than the above upper limit value, the dielectric property tends to be better.
• the content of the component (A) is not particularly limited, but from the viewpoint of further improving the heat resistance and the like, the total amount of the resin components in the resin composition of the present embodiment is 100 parts by mass. It may be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more.
• the content of the component (A) is not particularly limited, but from the viewpoint of further improving the dielectric properties and the like, the total amount of the resin components in the resin composition of the present embodiment is 100 parts by mass. It may be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less.
• the "resin component” means a resin and a compound that forms a resin by a curing reaction, and for example, the component (A) and the component (B) correspond to the resin component.
• the resin composition of the present embodiment contains, as an optional component, a resin or a compound that forms a resin by a curing reaction in addition to the component (A) and the component (B), these optional components are also included in the resin component. Is done.
• the components (C), (D) and (E), which will be described later, are not included in the resin component.
• the content of the component (B) is not particularly limited, but is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of the resin components in the resin composition of the present embodiment. , More preferably 20 to 80 parts by mass, still more preferably 25 to 75 parts by mass.
• the content of the component (B) is at least the above lower limit value, the dielectric property tends to be better. Further, when the content of the component (B) is not more than the above upper limit value, the heat resistance, moldability, processability, flame retardancy and conductor adhesiveness tend to be better.
• the content of the component (B) is not particularly limited, but from the viewpoint of further improving the dielectric properties and the like, the total amount of the resin components in the resin composition of the present embodiment is 100 parts by mass. It may be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more.
• the content of the component (B) is not particularly limited, but from the viewpoint of further improving heat resistance and the like, the total amount of the resin components in the resin composition of the present embodiment is 100 parts by mass. It may be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less.
• the content ratio [(A) / (B)] of the component (A) to the component (B) is not particularly limited, but is preferably 0.1 to 9 on a mass basis. , More preferably 0.25 to 4, still more preferably 0.3 to 3.
• the content ratio [(A) / (B)] of the component (A) to the component (B) is at least the above lower limit, heat resistance, moldability, processability, flame retardancy and conductor adhesiveness are deteriorated. It tends to be better.
• the content ratio [(A) / (B)] of the component (A) to the component (B) is not more than the above upper limit value, the dielectric property tends to be better.
• the content ratio [(A) / (B)] of the component (A) to the component (B) is not particularly limited, but from the viewpoint of further improving the heat resistance and the like, it is based on the mass. It may be 0.5 or more, 1 or more, or 1.5 or more.
• the content ratio [(A) / (B)] of the component (A) to the component (B) is not particularly limited, but from the viewpoint of further improving the dielectric properties and the like, it is based on the mass. It may be 7 or less, 2 or less, 1 or less, or 0.6 or less.
• the content of the resin component in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 70% by mass from the viewpoint of low thermal expansion property, elastic modulus, heat resistance, flame retardancy and conductor adhesiveness. It is more preferably 20 to 65% by mass, still more preferably 30 to 60% by mass.
• the resin composition of the present embodiment may further contain other components depending on the desired performance.
• the inorganic filler (C) [hereinafter, may be referred to as “(C) component”. ]
• Flame Retardant (D) [Hereinafter, it may be referred to as "(D) component”.
• the curing accelerator (E) [hereinafter, may be referred to as "(E) component”. ]
• the resin composition of the present embodiment contains at least one selected from the group consisting of the inorganic filler (C), the flame retardant (D) and the curing accelerator (E), depending on the desired performance. It does not have to be.
• these components will be described in detail.
• the resin composition of the present embodiment tends to have higher low thermal expansion property, elastic modulus, heat resistance and flame retardancy.
• the inorganic filler (C) may be used alone or in combination of two or more.
• Examples of the inorganic filler (C) include silica, alumina, titanium oxide, mica, verilia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, and silicate.
• Examples thereof include aluminum acetate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide and the like.
• silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is further preferable, from the viewpoints of low thermal expansion, elastic modulus, heat resistance, and flame retardancy.
• silica examples include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing almost no bound water or the like. Further, examples of the dry method silica include crushed silica, fumed silica, molten silica, and the like, depending on the manufacturing method.
• the average particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, still more preferably 0.2, from the viewpoint of dispersibility and fine wiring. It is about 1 ⁇ m, particularly preferably 0.3 to 0.8 ⁇ m.
• the average particle diameter of the inorganic filler (C) is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of particles as 100%. be.
• the particle size of the inorganic filler (C) can be measured by, for example, a particle size distribution measuring device using a laser diffraction / scattering method.
• Examples of the shape of the inorganic filler (C) include a spherical shape, a crushed shape, and the like, and the shape is preferably spherical.
• the content of the inorganic filler (C) in the resin composition is not particularly limited, but has low thermal expansion property, elastic modulus, heat resistance and heat resistance. From the viewpoint of flame retardancy, it is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and further preferably 30 to 60% by mass with respect to the total solid content (100% by mass) of the resin composition. ..
• a coupling agent may be used for the purpose of improving the dispersibility of the inorganic filler (C) and the adhesion with the organic component.
• the coupling agent include a silane coupling agent, a titanate coupling agent and the like.
• a silane coupling agent is preferable.
• the silane coupling agent include an aminosilane coupling agent, a vinylsilane coupling agent, an epoxysilane coupling agent, and the like.
• the inorganic filler (C) is blended in the resin composition, and then the coupling agent is added. It may be an integral blend treatment method, or it may be a method of surface-treating a coupling agent on the inorganic filler (C) in advance by a dry method or a wet method. Among these, from the viewpoint of being able to more effectively exhibit the features of the inorganic filler (C), a method of surface-treating the inorganic filler (C) with a coupling agent in a dry or wet manner is preferable.
• the inorganic filler (C) may be in the state of a slurry dispersed in an organic solvent in advance and then mixed with other components.
• the resin composition of the present embodiment tends to further improve the flame retardancy of the resin composition by containing the flame retardant (D).
• the flame retardant (D) may be used alone or in combination of two or more. Further, the resin composition of the present embodiment may contain a flame retardant aid, if necessary.
• Examples of the flame retardant (D) include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and the like, and phosphorus-based flame retardants and metal hydrates are preferable from the viewpoint of environmental problems.
• the phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those generally used as a flame retardant, and may be an inorganic phosphorus-based flame retardant or an organic-based flame retardant. It may be a phosphorus flame retardant.
• the phosphorus-based flame retardant preferably does not contain a halogen atom from the viewpoint of environmental problems.
• inorganic phosphorus-based flame retardant examples include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. Phosphoric acid; phosphine oxide and the like.
• organic phosphorus-based flame retardant examples include aromatic phosphoric acid esters, mono-substituted phosphonic acid diesters, 2-substituted phosphinic acid esters, metal salts of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compounds, and cyclic organic phosphorus compounds.
• aromatic phosphate ester compounds and metal salts of disubstituted phosphinic acid are preferable.
• the metal salt include lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, zinc salt and the like.
• aluminum salts are preferable.
• aromatic phosphoric acid esters are preferable.
• aromatic phosphate ester examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi-2,6-xylenyl phosphate, resorcinolbis (diphenyl phosphate), 1,3. -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate) and the like can be mentioned.
• Examples of the mono-substituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
• Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphine acid and methyl diphenylphosphine acid.
• Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid and the like. As these metal salts, aluminum salts are preferable.
• organic nitrogen-containing phosphorus compound examples include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
• phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene
• melamine phosphate melamine pyrophosphate
• melamine polyphosphate examples include melam polyphosphate.
• Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-. Examples thereof include 10-phosphaphenanthrene-10-oxide.
• aromatic phosphate esters and metal salts of disubstituted phosphinic acid are preferable, and 1,3-phenylenebis (di-2,6-xylenyl phosphate) and dialkylphosphinic acid are preferable.
• the aluminum salt of is more preferred, and aluminum trisdiethylphosphinate is even more preferred.
• Metal hydrate examples include aluminum hydroxide hydrate and magnesium hydroxide hydrate.
• halogen-based flame retardant examples include chlorine-based flame retardants and brominated flame retardants.
• chlorine-based flame retardant examples include chlorinated paraffin and the like.
• the content of the flame retardant (D) is not particularly limited, but the total amount of the resin components in the resin composition of the present embodiment is 100 parts by mass. On the other hand, it is preferably 1 to 15 parts by mass, more preferably 4 to 12 parts by mass, and further preferably 6 to 10 parts by mass.
• the content of the flame retardant (D) is at least the above lower limit value, the flame retardancy tends to be better. Further, when the content of the flame retardant (D) is not more than the above upper limit value, the moldability, the conductor adhesiveness, the heat resistance and the glass transition temperature tend to be better.
• the flame-retardant aid examples include inorganic flame-retardant aids such as antimony trioxide and zinc molybdate.
• the content thereof is not particularly limited, but is preferably 0 with respect to 100 parts by mass of the total resin components in the resin composition of the present embodiment. It is 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass.
• the content of the flame retardant aid is within the above range, better chemical resistance tends to be obtained.
• the resin composition of the present embodiment tends to have improved curability by containing the curing accelerator (E), and have better dielectric properties, heat resistance, conductor adhesiveness, elastic modulus and glass transition temperature. ..
• the curing accelerator (E) may be used alone or in combination of two or more.
• curing accelerator (E) examples include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; hexamethylenediisocyanate resin and 2-ethyl.
• acidic catalysts such as p-toluenesulfonic acid
• amine compounds such as triethylamine, pyridine and tributylamine
• imidazole compounds such as methylimidazole and phenylimidazole
• hexamethylenediisocyanate resin examples of the curing accelerator (E) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; he
• Isocyanate masked imidazole compounds such as addition reactants of -4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, ⁇ , ⁇ '-bis ( Organic peroxides such as t-butylperoxy) diisopropylbenzene; carboxylates such as manganese, cobalt and zinc can be mentioned.
• imidazole compounds isocyanate masked imidazole compounds, organic peroxides and carboxylates are preferable, organic peroxides are more preferable, and dicumyl peroxide is preferable from the viewpoint of heat resistance, glass transition temperature and storage stability. More preferred.
• the content of the curing accelerator (E) is not particularly limited, but the total mass of the resin components in the resin composition of the present embodiment is 100% by mass. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to parts.
• the content of the curing accelerator (E) is at least the above lower limit value, the dielectric properties, heat resistance, conductor adhesiveness, elastic modulus and glass transition temperature tend to be better. Further, when the content of the curing accelerator (E) is not more than the above upper limit value, the storage stability tends to be better.
• the resin composition of the present embodiment further comprises a resin material other than the above components, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant and other additions, if necessary. It may contain one or more optional components selected from the group consisting of agents. For each of the above optional components, one type may be used alone, or two or more types may be used in combination.
• the content of the above-mentioned optional component 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. Further, 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 the viewpoint of facilitating the production of a prepreg described later.
• an organic solvent one kind may be used alone, or two or more kinds may be used in combination.
• the resin composition containing an organic solvent may be referred to as a resin varnish.
• organic solvent examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; Aromatic hydrocarbon solvents such as toluene, xylene and mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; ester solvents such as ⁇ -butyrolactone Can be mentioned.
• alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
• ketone solvents such as acetone, methyl
• alcohol-based solvents ketone-based solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon-based solvents are preferable, aromatic hydrocarbon-based solvents are more preferable, and toluene is even more preferable.
• the solid content concentration of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and further preferably 40. It is about 60% by mass.
• the solid content concentration is within the above range, the handleability of the resin composition tends to be easy, the impregnation property into the base material and the appearance of the produced prepreg tend to be better.
• the solid content concentration of the resin in the prepreg which will be described later, can be easily adjusted, and the production of a prepreg having a desired thickness tends to be easier.
• the resin composition of the present embodiment can be produced by mixing the component (A), the component (B), and other components used in combination as necessary by a known method.
• each component may be dissolved or dispersed with stirring.
• the conditions such as the order in which the raw materials are mixed, the mixing temperature, and the mixing time are not particularly limited, and may be arbitrarily set according to the type of the raw materials and the like.
• the relative permittivity (Dk) of the cured product of the present embodiment at 10 GHz is not particularly limited, but is preferably 3.0 or less, more preferably 2.9 or less, and further, from the viewpoint of low transmission loss. It is preferably 2.8 or less.
• the conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
• the above-mentioned relative permittivity (Dk) is a value based on the cavity resonator perturbation method, and more specifically, it is a value measured by the method described in Examples.
• the dielectric loss tangent (Df) of the cured product of the present embodiment at 10 GHz is not particularly limited, but is preferably 0.0040 or less, more preferably 0.0030 or less, still more preferably, from the viewpoint of low transmission loss. Is 0.0020 or less.
• the conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
• the dielectric loss tangent (Df) is a value based on the cavity resonator perturbation method, and more specifically, a value measured by the method described in Examples.
• 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. That is, it can be said that the prepreg of the present embodiment contains the resin composition of the present embodiment. In addition, in this specification, "being contained” means the thing formed through at least the state which contains.
• 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-shaped fiber base material is not particularly limited, but is preferably a sheet-shaped fiber reinforced base material used for the purpose of reinforcing the prepreg, for example.
• the sheet-shaped fiber base material contained in the prepreg of the present embodiment a known sheet-shaped fiber base material used for various laminated plates for electrical insulating materials can be used.
• the material of the sheet-like fiber base material include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; and a mixture thereof.
• These sheet-like fiber base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats.
• the thickness of the sheet-like fiber base material is not particularly limited, but is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, still more preferably 0.02 to 0.3 mm, from the viewpoint of mechanical strength and thinning of the prepreg. It is 0.03 to 0.1 mm.
• the sheet-like fiber base material may be surface-treated with a coupling agent or the like from the viewpoints of impregnation property of the resin composition, heat resistance when formed into a laminated board, hygroscopicity and processability, and may be mechanically treated. It may be the one which has been subjected to the fiber opening treatment.
• the prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber base material and then drying it, if necessary.
• a method of impregnating or applying the resin composition to the sheet-shaped fiber base material for example, a hot melt method, a solvent method, or the like can be adopted.
• the hot melt method is a method of impregnating or applying a resin composition containing no organic solvent to a sheet-shaped fiber base material.
• One aspect of the hot melt method is a method in which the resin composition is once coated on coated paper having good peelability, and then the coated resin composition is laminated on a sheet-like fiber base material.
• the solvent method is a method of impregnating or applying a resin composition containing an organic solvent to a sheet-like fiber base material. Specifically, for example, a method of immersing the sheet-like fiber base material in a resin composition containing an organic solvent and then drying it can be mentioned. By drying, the organic solvent is removed and the resin composition is semi-cured (B-staged) to obtain the prepreg of the present embodiment.
• the solid content concentration derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 20 to 90% by mass, more preferably 20 to 90% by mass, from the viewpoint of obtaining better moldability when the laminated board is formed. It is 25 to 80% by mass, more preferably 30 to 75% by mass.
• the thickness of the prepreg of the present embodiment is not particularly limited, but is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, from the viewpoint of formability and enabling high-density wiring. More preferably, it is 0.03 to 0.1 mm.
• 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. That is, it can be said that the resin film of the present embodiment contains the resin composition of the present embodiment.
• 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 heating and drying.
• the support include a plastic film, a metal foil, a release paper, and the like.
• the plastic film include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate [hereinafter, may be referred to as "PET".
• Polyester film such as polyethylene naphthalate; polycarbonate film, polyimide film and the like can be mentioned.
• the metal foil include copper foil and aluminum foil.
• the support may be surface-treated such as matte treatment and corona treatment. Further, the support may be one that has been subjected to a mold release treatment with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like.
• the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and even more preferably 25 to 50 ⁇ m from the viewpoint of handleability and economy.
• a coating device for coating the resin varnish for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. These coating devices may be appropriately selected according to the film thickness to be formed.
• the drying conditions after applying the resin varnish may be appropriately determined according to the content of the organic solvent, the boiling point, and the like, and are not particularly limited. For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited, but the productivity and the resin composition of the present embodiment are appropriately B-staged.
• the drying time is not particularly limited, but is preferably 1 to 30 minutes, more preferably 2 from the viewpoint of productivity and appropriate B-stage formation of the resin composition of the present embodiment. It is ⁇ 15 minutes, more preferably 3-10 minutes.
• the laminated board of the present embodiment is a laminated board having a cured product of the resin composition of the present embodiment or a cured product of a prepreg, and a metal foil. That is, it can be said that the laminated board of the present embodiment contains the resin composition or prepreg of the present embodiment and the metal foil.
• the laminated board having a metal foil may be referred to as a metal-clad laminated board.
• the metal of the metal foil is not particularly limited, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and one or more of these metal elements are used.
• the alloy contained is preferable, copper and aluminum are more preferable, and copper is further preferable.
• the laminated board of the present embodiment can be manufactured, for example, by arranging a metal foil on one side or both sides of the prepreg of the present embodiment and then heat-pressing molding. At that time, only one prepreg may be used, or two or more prepregs may be laminated and used.
• the heating temperature for heat-press molding is not particularly limited, but is preferably 100 to 300 ° C, more preferably 150 to 280 ° C, and even more preferably 200 to 250 ° C.
• the heating and pressurizing time of the heat and pressure molding is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, and further preferably 80 to 150 minutes.
• the pressure for heat-press molding is not particularly limited, but is preferably 1.5 to 5 MPa, more preferably 1.7 to 3 MPa, and even more preferably 1.8 to 2.5 MPa. However, these conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited.
• the printed wiring board of the present embodiment is a printed wiring board having one or more selected from the group consisting of a cured product of the resin composition of the present embodiment, a cured product of the prepreg of the present embodiment, and a laminated board of the present embodiment. It is a board. That is, it can be said that the printed wiring board of the present embodiment contains one or more selected from the group consisting of the resin composition of the present embodiment, the prepreg of the present embodiment, and the laminated board of the present embodiment. ..
• the printed wiring board of the present embodiment has at least a structure and a conductor circuit layer containing the cured product of the resin composition of the present embodiment, the cured product of the prepreg of the present embodiment, or the laminated board of the present embodiment.
• the printed wiring board of the present embodiment is, for example, a group consisting of a cured product of the resin composition of the present embodiment, a cured product of the prepreg of the present embodiment, a cured product of the resin film of the present embodiment, and a laminated board of the present embodiment. It can be manufactured by forming a conductor circuit by a known method for one or more kinds selected from the above.
• a multi-layer printed wiring board by subjecting it to a multi-layer adhesive process or the like, if necessary.
• the conductor circuit can be formed, for example, by appropriately performing drilling, metal plating, etching of a metal foil, or the like.
• the semiconductor package of this embodiment is a semiconductor package including the printed wiring board of this embodiment and a semiconductor element.
• the semiconductor package of the present embodiment can be manufactured, for example, by mounting a semiconductor element, a memory, or the like on the printed wiring board of the present embodiment by a known method.
• the number average molecular weight was measured by the following procedure. (Measurement method of number average molecular weight) The number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC).
• the calibration curve is 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] was used for approximation by a cubic equation.
• the measurement conditions of GPC are shown below.
• test piece having a width of 10 mm, a length of 80 mm, and a thickness of 0.2 mm is prepared from the resin to be measured, and the length of the test piece is set so that the distance between the gripping tools is 60 mm with the upper and lower grippers. I sandwiched both ends in the side direction.
• an autograph manufactured by Shimadzu Corporation, AG-X
• the tensile elastic modulus of the test piece at 25 ° C. was obtained under the condition of a tensile speed of 5 mm / min under a room temperature environment adjusted to 25 ° C. did. Five similar samples were prepared, the tensile elastic modulus at 25 ° C.
• the resin powder obtained above is put into a Teflon (registered trademark) sheet cut into a size of 1 mm in thickness ⁇ 50 mm in length ⁇ 35 mm in width, and low profile copper foil (Mitsui Mining & Smelting Co., Ltd.) with a thickness of 18 ⁇ m is placed above and below the sheet.
• Low profile copper foil Mitsubishi Chemical Company, Ltd.
• the low profile copper foil was arranged with the M side facing the resin powder side.
• the laminate before heat and pressure molding is heat and pressure molded under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes, and the resin powder is molded and cured on a resin plate to obtain double-sided copper.
• a resin plate with foil was produced.
• the thickness of the resin plate portion of the obtained resin plate with double-sided copper foil was 1 mm.
• tensile elastic modulus 0.05 GPa ⁇ (B2) component> -Modified conjugated diene polymer 1: Modified conjugated diene polymer obtained in Production Example 1, 25 ° C.
• Tension modulus 0.1 GPa
• Modified conjugated diene polymer 2 Modified conjugated diene polymer 2 obtained in Production Example 2, 25 ° C.
• the resin compositions obtained in Examples 1 to 8 of this embodiment have low relative permittivity and dielectric loss tangent, and high peel strength is obtained. From this, it can be seen that the resin composition of the present embodiment is excellent in dielectric properties and conductor adhesiveness in a high frequency band of 10 GHz band or higher. On the other hand, the resin compositions obtained in Comparative Examples 1 to 3 were inferior in any of the relative permittivity, the dielectric loss tangent and the peel strength, and both the dielectric property and the conductor adhesiveness were insufficient.
• the cured product produced from the resin composition of the present embodiment is excellent in dielectric properties and conductor adhesiveness in a high frequency band of 10 GHz band or higher. Therefore, the resin composition of the present embodiment is used for a fifth generation mobile communication system (5G) antenna in which radio waves in the frequency band exceeding 6 GHz are used, and a millimeter-wave radar in which radio waves in the frequency band of 30 to 300 GHz are used. It is useful for printed wiring boards and the like.
• 5G fifth generation mobile communication system

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• 2021
  • 2021-12-24 JP JP2022573059A patent/JP7722392B2/ja active Active
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