WO2022059625A1 - 樹脂組成物、並びに、それを用いたプリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板及び配線基板 - Google Patents

樹脂組成物、並びに、それを用いたプリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板及び配線基板 Download PDF

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WO2022059625A1
WO2022059625A1 PCT/JP2021/033408 JP2021033408W WO2022059625A1 WO 2022059625 A1 WO2022059625 A1 WO 2022059625A1 JP 2021033408 W JP2021033408 W JP 2021033408W WO 2022059625 A1 WO2022059625 A1 WO 2022059625A1
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group
resin composition
compound
resin
styrene
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English (en)
French (fr)
Japanese (ja)
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誼群 王
宏典 齋藤
博晴 井上
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202180062840.9A priority Critical patent/CN116323725A/zh
Priority to JP2022550534A priority patent/JP7748634B2/ja
Priority to US18/026,292 priority patent/US20230357558A1/en
Publication of WO2022059625A1 publication Critical patent/WO2022059625A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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

Definitions

  • the present invention relates to a resin composition, and a prepreg using the resin composition, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring substrate.
  • the substrate material for forming the base material of the wiring board used in various electronic devices is required to have a low dielectric constant and a low dielectric loss tangent in order to increase the signal transmission speed and reduce the loss during signal transmission. ..
  • Polyphenylene ether has excellent dielectric properties such as low dielectric constant and dielectric loss tangent, and excellent dielectric properties such as dielectric constant and dielectric loss tangent even in the high frequency band (high frequency region) from MHz band to GHz band. It has been known. Therefore, polyphenylene ether is being studied for use as, for example, a molding material for high frequencies. More specifically, it is preferably used as a substrate material for constituting a base material of a wiring board provided in an electronic device using a high frequency band.
  • Patent Document 1 discloses a resin composition containing a modified polyphenylene ether compound and a styrene-based thermoplastic elastomer having a weight average molecular weight of 10,000 or more.
  • Patent Document 1 According to the resin composition as disclosed in Patent Document 1, it is reported that the film forming ability can be imparted without impairing the low dielectric property and heat resistance.
  • the present invention has been made in view of such circumstances, and has excellent low dielectric properties, low thermal expansion rate, high Tg, and other properties in the cured product, and also has circuit filling properties when used as a substrate material. It is an object of the present invention to provide an excellent resin composition. Another object of the present invention is to provide a prepreg using the resin composition, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board.
  • the resin composition according to one aspect of the present invention includes a styrene-based block copolymer, a radically polymerizable compound, a compound (A) represented by the following formula (1), and a compound represented by the following formula (2). (B) and at least selected from the group consisting of the compound (C) having at least one group selected from the groups represented by the following formulas (3-1) and (3-2). It is characterized by containing one free radical compound.
  • X A and X B are independently hydrogen atom, amino group, cyano group, hydroxy group, isothiocyanate, methoxy group, carboxy group, carbonyl group and amide group, respectively. , Or a benzoyloxy group.
  • FIG. 1 is a schematic cross-sectional view showing the configuration of a prepreg according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing the configuration of a metal-clad laminate according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing the configuration of a wiring board according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing the structure of the metal leaf with resin according to the embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing the structure of the resin film according to the embodiment of the present invention.
  • the resin composition according to the embodiment of the present invention (hereinafter, also simply referred to as a resin composition) includes a styrene-based block copolymer, a radically polymerizable compound, and a compound (A) represented by the above formula (1).
  • heat resistance is one of the factors for further improvement in a material having a high Tg of a cured product.
  • the fact that the material has a high Tg in the cured product has an advantage that the coefficient of thermal expansion of the material in a higher temperature region is small. Generally, when the temperature exceeds the glass transition temperature, the thermal expansion rapidly increases. Therefore, when the glass transition temperature is low, the coefficient of thermal expansion increases in the high temperature region exceeding the glass transition temperature. If the coefficient of thermal expansion in the high temperature region is large, the reliability of interlayer connection (barrel crack generation of through holes, etc.) in the wiring board may deteriorate, and the printed circuit board may not function.
  • a resin composition which has excellent low dielectric properties, low thermal expansion rate, high Tg and other properties in the cured product, and also has excellent circuit filling properties when used as a substrate material. Can be done. Further, by using the resin composition, it is possible to provide a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board having excellent characteristics.
  • the resin composition of the present embodiment contains a styrene-based block copolymer. This is considered to have advantages such as further lowering the dielectric constant of the resin and improving the handling property (film property) when the resin composition or the semi-cured product (B stage) of the resin composition is formed.
  • the styrene-based block copolymer used in the present embodiment is, for example, a copolymer obtained by block-polymerizing a monomer containing a styrene-based monomer.
  • the styrene-based copolymer can be obtained, for example, by block-polymerizing one or more of styrene-based monomers and one or more of other monomers copolymerizable with the styrene-based monomers. Examples thereof include copolymers.
  • Examples of the styrene-based monomer include styrene and styrene derivatives.
  • the weight average molecular weight of the styrene-based block copolymer of the present embodiment is preferably about 10,000 to 200,000, more preferably about 50,000 to 180,000.
  • the weight average molecular weight may be measured by a general molecular weight measuring method, and specifically, a value measured by gel permeation chromatography measurement (GPC: Gel Permeation Chromatography). And so on.
  • the styrene-based block polymer of the present embodiment is preferably a styrene-based block copolymer having a hardness of 20 to 100. Further, the hardness of the styrene-based block copolymer is preferably 30 to 80. By containing a styrene-based block copolymer having a hardness within the above range, it is considered that when cured, a resin composition having a lower dielectric property and a lower coefficient of thermal expansion can be obtained. ..
  • the hardness may be, for example, a durometer hardness or the like, and more specifically, a durometer hardness or the like measured using a type A durometer compliant with JIS K6253.
  • styrene-based block copolymer As a specific styrene-based block copolymer, conventionally known ones can be widely used and are not particularly limited, but for example, a structural unit represented by the following formula (5) (structure derived from a styrene-based monomer) can be used. Examples thereof include polymers contained in molecules.
  • R 2 to R 4 independently represent a hydrogen atom or an alkyl group
  • R 5 represents a hydrogen atom, an alkyl group, an alkenyl group, or an isopropenyl group.
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
  • the alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • the styrene-based block copolymer of the present embodiment preferably contains at least one structural unit represented by the above formula (5), but may contain two or more different types in combination. Further, it may include a structure in which the structural unit represented by the above formula (5) is repeated.
  • the styrene-based block copolymer of the present embodiment has the following formula (6) as another monomer copolymerizable with the styrene-based monomer in addition to the structural unit represented by the above formula (5).
  • )-(8) may have at least one of the structural units.
  • R 6 to R 23 each independently represent any group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an isopropenyl group. ..
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
  • the alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • the styrene-based block copolymer of the present embodiment preferably contains at least one structural unit represented by the above formulas (6) to (8), and contains two or more different types in combination. You may be. Further, it may include a structure in which the structural units represented by the above formulas (6), (7) and / or formula (8) are repeated.
  • the structural unit represented by the above formula (5) more specifically, for example, the structural unit represented by the following formulas (9) to (11) can be mentioned.
  • the structural unit represented by the above formula (5) may be one of these alone or a combination of two or more different types. Further, a structure or the like in which the structural units represented by the following formulas (9) to (11) are repeated may be used.
  • examples of the structural unit represented by the above formula (6) include structural units represented by the following formulas (12) to (18).
  • the structural unit represented by the above formula (6) may be one of these alone or a combination of two or more different types. Further, a structure or the like in which the structural units represented by the following formulas (12) to (18) are repeated may be used.
  • the structural unit represented by the above formula (7) more specifically, for example, the structural unit represented by the following formulas (19) to (20) can be mentioned.
  • the structural unit represented by the above formula (7) may be one of these alone or a combination of two or more different types. Further, a structure or the like in which the structural units represented by the following formulas (19) to (20) are repeated may be used.
  • structural unit represented by the above formula (8) more specifically, for example, structural units represented by the following formulas (21) to (22) can be mentioned.
  • the structural unit represented by the above formula (8) may be one of these alone or a combination of two or more different types. Further, a structure in which the structural units represented by the following formulas (21) to (22) are repeated may be used.
  • styrene-based block copolymer As a preferable example of the styrene-based block copolymer, one or more styrene-based monomers such as styrene, styrene ethylene, vinyl toluene, ⁇ -methyl styrene, isopropenyl toluene, divinyl benzene, and allyl styrene are polymerized or copolymerized. Examples thereof include the copolymer thus obtained.
  • methylstyrene (ethylene / butylene) methylstyrene copolymer methylstyrene (ethylene-ethylene / propylene) methylstyrene copolymer, styreneisoprene copolymer, styreneisoprenestyrene copolymer, styrene (ethylene).
  • styrene copolymer examples include syrup.
  • the above-exemplified one may be used alone, or two or more kinds thereof may be used in combination.
  • the styrene-based block copolymer contains at least one of the structural units represented by the formulas (9) to (11), its mass fraction (that is, the content of the styrene-derived structural unit) is determined. It is preferably about 10 to 60%, more preferably about 20 to 40%, based on the whole polymer. As a result, there is an advantage that better dielectric properties can be obtained when the resin composition is cured while maintaining good compatibility with the radically polymerizable compound.
  • styrene-based block copolymers of the present embodiment can also be used, for example, "Septon V9827” and “Septon 2063” manufactured by Kuraray Corporation, and “Tough Tech (registered trademark)” manufactured by Asahi Kasei Corporation. Examples thereof include “H1052”, “Tough Tech (registered trademark) H1041” and “Tough Tech (registered trademark) H1221", and “Dynaroon9901P” manufactured by JSR Corporation.
  • the radically polymerizable compound used in the present embodiment is not particularly limited as long as it is a radically polymerizable compound, and includes a polyphenylene ether compound terminally modified to a substituent having a carbon-carbon unsaturated double bond. It is preferable to be.
  • the polyphenylene ether compound that can be used in the present embodiment is preferably a modified polyphenylene ether compound that can exhibit excellent low dielectric properties when cured, and is a polyphenylene ether compound having a group represented by the following formula (4). It is preferable to have. It is considered that the inclusion of such a modified polyphenylene ether compound provides a resin composition capable of obtaining a cured product having low dielectric properties and high heat resistance.
  • R 1 represents a hydrogen atom or an alkyl group.
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • the polyphenylene ether compound of the present embodiment may be a polyphenylene ether compound having a group represented by the following formula (23).
  • p represents an integer of 0 to 10.
  • Z represents an arylene group.
  • R 1 to R 3 are independent of each other. That is, R 24 to R 26 may be the same group or different groups, respectively. Further, R 24 to R 26 represent a hydrogen atom or an alkyl group.
  • the above-mentioned Z allylene group is not particularly limited.
  • the arylene group include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group in which the aromatic is not a monocyclic but a polycyclic aromatic such as a naphthalene ring.
  • the arylene group also includes a derivative in which the hydrogen atom bonded to the aromatic ring is replaced with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. ..
  • the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • Examples of the substituent represented by the above formula (4) include an acrylate group and a methacrylate group. Moreover, as a preferable specific example of the substituent represented by the above formula (23), for example, a substituent containing a vinylbenzyl group and the like can be mentioned. Examples of the substituent containing the vinylbenzyl group include a substituent represented by the following formula (24).
  • a vinylbenzyl group such as a p-ethenylbenzyl group and an m-ethenylbenzyl group, a vinylphenyl group, an acrylate group, a methacrylate group and the like.
  • the polyphenylene ether compound has a polyphenylene ether chain in the molecule, and for example, it is preferable that the repeating unit represented by the following formula (25) is contained in the molecule.
  • t represents 1 to 50.
  • R 27 to R 30 are independent of each other. That is, R 27 to R 30 may be the same group or different groups, respectively.
  • R 27 to R 30 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Of these, a hydrogen atom and an alkyl group are preferable.
  • R 27 to R 30 Specific examples of the functional groups listed in R 27 to R 30 include the following.
  • the alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • the alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include a vinyl group, an allyl group, a 3-butenyl group and the like.
  • the alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include an ethynyl group and a propa-2-in-1-yl group (propargyl group).
  • the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group and the like.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specific examples thereof include an acryloyl group, a methacryloyl group, and a crotonoyl group.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, a propioloyl group and the like can be mentioned.
  • the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and even more preferably 1000 to 3000.
  • the weight average molecular weight may be measured by a general molecular weight measuring method, and specific examples thereof include values measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • t is a numerical value such that the weight average molecular weight of the polyphenylene ether compound is within such a range. It is preferable to have. Specifically, t is preferably 1 to 50.
  • the polyphenylene ether compound When the weight average molecular weight of the polyphenylene ether compound is within such a range, the polyphenylene ether has excellent low dielectric properties, and not only the heat resistance of the cured product is excellent, but also the moldability is excellent. Become. This is considered to be due to the following. When the weight average molecular weight of ordinary polyphenylene ether is within such a range, the heat resistance of the cured product tends to decrease because it has a relatively low molecular weight. In this respect, since the polyphenylene ether compound according to the present embodiment has one or more unsaturated double bonds at the ends, it is considered that a cured product having sufficiently high heat resistance can be obtained.
  • the polyphenylene ether compound when the weight average molecular weight of the polyphenylene ether compound is within such a range, the polyphenylene ether compound has a relatively low molecular weight and is considered to be excellent in moldability. Therefore, it is considered that such a polyphenylene ether compound is not only excellent in heat resistance of the cured product but also excellent in moldability.
  • the average number of substituents (number of terminal functional groups) at the molecular ends per molecule of the polyphenylene ether compound is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. Further, if the number of terminal functional groups is too large, the reactivity becomes too high, and there is a possibility that problems such as deterioration of the storage stability of the resin composition and deterioration of the fluidity of the resin composition may occur. .. That is, when such a polyphenylene ether compound is used, molding defects such as voids generated during multi-layer molding occur due to insufficient fluidity, etc., and it is difficult to obtain a highly reliable printed wiring board. Problems may occur.
  • the number of terminal functional groups of the polyphenylene ether compound may be a numerical value representing the average value of the substituents per molecule of all the modified polyphenylene ether compounds present in 1 mol of the polyphenylene ether compound.
  • the number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups of the polyphenylene ether before this modification is the number of terminal functional groups.
  • the method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to the solution of the modified polyphenylene ether compound and measure the UV absorbance of the mixed solution. By doing so, it can be obtained.
  • a quaternary ammonium salt tetraethylammonium hydroxide
  • the intrinsic viscosity of the polyphenylene ether compound of this embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. .. If this intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as low dielectric constant and low dielectric loss tangent. Further, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be realized.
  • the intrinsic viscosity here is the intrinsic viscosity measured in methylene chloride at 25 ° C., more specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) is used with a viscometer. These are the values measured in. Examples of this viscometer include AVS500 Visco System manufactured by Shott.
  • polyphenylene ether compound of the present embodiment examples include modified polyphenylene ether compounds represented by the following formulas (26) to (28). Moreover, as the polyphenylene ether compound of this embodiment, these modified polyphenylene ether compounds may be used alone, or these modified polyphenylene ether compounds may be used in combination.
  • R 30 to R 37 , R 38 to R 45 , and R 46 to R 49 are independent of each other. That is, R 30 to R 37 , R 38 to R 45 , and R 46 to R 49 may be the same group or different groups, respectively.
  • R 30 to R 37 , R 38 to R 45 and R 46 to R 49 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • s indicates an integer from 1 to 100.
  • R 30 to R 37 , R 38 to R 45 , and R 46 to R 49 include the following.
  • the alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.
  • the alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include a vinyl group, an allyl group, a 3-butenyl group and the like.
  • the alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include an ethynyl group and a propa-2-in-1-yl group (propargyl group).
  • the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. .. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group and the like.
  • the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. .. Specific examples thereof include an acryloyl group, a methacryloyl group, and a crotonoyl group.
  • the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. .. Specifically, for example, a propioloyl group and the like can be mentioned.
  • a and B indicate repeating units represented by the following formulas (29) and the following formulas (30), respectively.
  • Y represents a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms.
  • m and n represent 0 to 20, respectively. Further, it is preferable that m and n represent numerical values in which the total value of m and n is 1 to 30. Therefore, it is more preferable that m indicates 0 to 20, n indicates 0 to 20, and the total of m and n indicates 1 to 30.
  • R 50 to R 53 and R 54 to R 57 are independent of each other, and R 50 to R 53 and R 54 to R 57 are each based on the same group. It may be a different group or a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
  • Y is a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms, as described above.
  • Examples of Y include groups represented by the following formula (31).
  • R 58 and R 59 each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group include a methyl group and the like.
  • the group represented by the formula (31) include a methylene group, a methylmethylene group, a dimethylmethylene group and the like, and among these, a dimethylmethylene group is preferable.
  • X 1 to X 3 are, for example, independently represented by the substituents represented by the above formula (4) and / or the above formula (23). Indicates a substituent.
  • X 1 to X 3 may be the same substituent or may be different substituents.
  • modified polyphenylene ether compound represented by the above formula (26) for example, a modified polyphenylene ether compound represented by the following formula (32) can be mentioned.
  • modified polyphenylene ether compound represented by the formula (26) include, for example, the modified polyphenylene ether compound represented by the following formula (33) and the modified polyphenylene represented by the following formula (34).
  • examples include ether compounds.
  • m and n have the same meaning as m and n in the formula (29) and the formula (30).
  • R 24 to R 26 , p and Z are the same as R 24 to R 26 , p and Z in the above formula (23), respectively.
  • Y is the same as Y in the above formula (27).
  • R 1 is the same as R 1 in the above formula (4).
  • the modified polyphenylene ether compounds represented by the formulas (32) to (34) preferably have a group represented by the above formula (4) at the end. ..
  • Examples of the method for synthesizing the polyphenylene ether compound used in the present embodiment include a method for synthesizing a polyphenylene ether compound terminally modified by a group represented by the formula (4) and / or the formula (23). More specifically, a method of reacting a polyphenylene ether with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded can be mentioned.
  • Examples of the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded include the substituent represented by the above formulas (4), (23) and (24) and the halogen atom. Examples thereof include bound compounds. Specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and among these, a chlorine atom is preferable. More specific examples of the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene and m-chloromethylstyrene.
  • the polyphenylene ether as a raw material is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether compound.
  • a polyphenylene ether composed of at least one of 2,6-dimethylphenol, bifunctional phenol and trifunctional phenol, and polyphenylene ether such as poly (2,6-dimethyl-1,4-phenylene oxide) can be used. Examples thereof include those having a main component.
  • the bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like.
  • the trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.
  • Examples of the method for synthesizing the polyphenylene ether compound of the present embodiment include the methods described above. Specifically, the above-mentioned polyphenylene ether and a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded are dissolved in a solvent and stirred. By doing so, the polyphenylene ether is reacted with the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded to obtain the polyphenylene ether compound used in the present embodiment.
  • the alkali metal hydroxide functions as a dehalogenating agent, specifically, a dehydrochlorating agent. That is, the alkali metal hydroxide desorbs hydrogen halide from the phenol group of the polyphenylene ether and the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded to do so. Thereby, it is considered that the substituent having a carbon-carbon unsaturated double bond is bonded to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of the polyphenylene ether.
  • the alkali metal hydroxide is not particularly limited as long as it can act as a dehalogenating agent, and examples thereof include sodium hydroxide. Further, the alkali metal hydroxide is usually used in the state of an aqueous solution, and specifically, it is used as an aqueous solution of sodium hydroxide.
  • Reaction conditions such as reaction time and reaction temperature differ depending on the compound or the like in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and the above-mentioned reaction may proceed favorably.
  • the reaction temperature is preferably room temperature to 100 ° C, more preferably 30 to 100 ° C.
  • the reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.
  • the solvent used in the reaction can dissolve the polyphenylene ether and the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded, and the polyphenylene ether and the carbon-carbon unsaturated double bond can be dissolved. It is not particularly limited as long as it does not inhibit the reaction between the substituent having a bond and the compound to which the halogen atom is bonded. Specific examples thereof include toluene and the like.
  • the above reaction is preferably carried out in the presence of not only the alkali metal hydroxide but also the phase transfer catalyst. That is, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. By doing so, it is considered that the above reaction proceeds more preferably. This is considered to be due to the following.
  • the phase transfer catalyst has a function of taking up an alkali metal hydroxide and is soluble in both a phase of a polar solvent such as water and a phase of a non-polar solvent such as an organic solvent. It is thought that it is a catalyst that can move.
  • aqueous sodium hydroxide solution when used as the alkali metal hydroxide and an organic solvent such as toluene, which is incompatible with water, is used as the solvent, the aqueous sodium hydroxide solution is subjected to the reaction. It is considered that the solvent and the aqueous sodium hydroxide solution are separated even when the solution is added dropwise to the solvent, and it is difficult for the sodium hydroxide to transfer to the solvent. In that case, it is considered that the sodium hydroxide aqueous solution added as the alkali metal hydroxide is less likely to contribute to the reaction promotion.
  • the reaction when the reaction is carried out in the presence of the alkali metal hydroxide and the phase transfer catalyst, the alkali metal hydroxide is transferred to the solvent in a state of being incorporated into the phase transfer catalyst, and the aqueous sodium hydroxide solution reacts. It is thought that it will be easier to contribute to promotion. Therefore, it is considered that the above reaction proceeds more preferably when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst.
  • phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.
  • the resin composition used in this embodiment preferably contains the modified polyphenylene ether compound obtained as described above as the radically polymerizable compound.
  • the resin composition according to the present embodiment may contain a compound as exemplified below as a radically polymerizable compound.
  • a compound having an acryloyl group in the molecule a compound having a methacryloyl group in the molecule, a compound having a vinyl group in the molecule, a compound having an allyl group in the molecule, and a compound having an acenaphtylene structure in the molecule.
  • examples thereof include a compound, a compound having a maleimide group in the molecule, and an isocyanurate compound having an isocyanurate group in the molecule.
  • the compound having an acryloyl group in the molecule is an acrylate compound.
  • the acrylate compound include a monofunctional acrylate compound having one acryloyl group in the molecule and a polyfunctional acrylate compound having two or more acryloyl groups in the molecule.
  • the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
  • Examples of the polyfunctional acrylate compound include diacrylate compounds such as tricyclodecanedimethanol diacrylate.
  • the compound having a methacryloyl group in the molecule is a methacrylate compound.
  • the methacrylate compound include a monofunctional methacrylate compound having one methacryloyl group in the molecule and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule.
  • the monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like.
  • the polyfunctional methacrylate compound include a dimethacrylate compound such as tricyclodecanedimethanol dimethacrylate, and a trimethacrylate compound such as trimethylolpropane trimethacrylate.
  • the compound having a vinyl group in the molecule is a vinyl compound.
  • the vinyl compound include a monofunctional vinyl compound (monovinyl compound) having one vinyl group in the molecule and a polyfunctional vinyl compound having two or more vinyl groups in the molecule.
  • the polyfunctional vinyl compound include divinylbenzene and polybutadiene.
  • the compound having an allyl group in the molecule is an allyl compound.
  • the allyl compound include a monofunctional allyl compound having one allyl group in the molecule and a polyfunctional allyl compound having two or more allyl groups in the molecule.
  • the polyfunctional allyl compound include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).
  • the compound having an acenaphthylene structure in the molecule is an acenaphthylene compound.
  • the acenaphthylene compound include acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes.
  • the alkyl acenaftylenes include 1-methylacenaftylene, 3-methylacenaftylene, 4-methylacenaftylene, 5-methylacenaftylene, 1-ethylacenaftylene, and 3-ethylacena.
  • Examples thereof include phthalene, 4-ethylacenaftylene, 5-ethylacenaftylene and the like.
  • Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaftylene, 4-chloroacenaftylene, 5-chloroacenaftylene, 1-bromoacenaftylene and 3-bromoacenaphthylene. Examples thereof include len, 4-bromoacenaphthylene and 5-bromoacenaphthylene.
  • phenylacenaftylenes examples include 1-phenylacenaftylene, 3-phenylacenaftylene, 4-phenylacenaftylene, 5-phenylacenaftylene and the like.
  • the acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule. ..
  • the compound having a maleimide group in the molecule is a maleimide compound.
  • the maleimide compound include a monofunctional maleimide compound having one maleimide group in the molecule, a polyfunctional maleimide compound having two or more maleimide groups in the molecule, and a modified maleimide compound.
  • the modified maleimide compound include a modified maleimide compound in which a part of the molecule is modified with an amine compound, a modified maleimide compound in which a part of the molecule is modified with a silicone compound, and a part of the molecule in an amine compound. And modified maleimide compounds modified with silicone compounds.
  • the compound having an isocyanurate group in the molecule is an isocyanurate compound.
  • the isocyanurate compound include compounds having an alkenyl group in the molecule (alkenyl isocyanurate compound), and examples thereof include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC).
  • radically polymerizable compound other than the above-mentioned modified polyphenylene ether compound an allyl compound, a vinyl compound, a maleimide compound and the like are preferably exemplified.
  • the above-mentioned radically polymerizable compound may be used alone or in combination of two or more.
  • the terminal-modified polyphenylene ether compound When two or more kinds are combined, it is preferable to contain one or more kinds of the above-mentioned terminal-modified polyphenylene ether compound and, for example, an allyl compound having an allyl group in the molecule as described above.
  • an allyl compound an allyl isocyanurate compound having two or more allyl groups in the molecule is preferable, and triallyl isocyanurate (TAIC) is more preferable.
  • TAIC triallyl isocyanurate
  • the free radical compound used in this embodiment includes the compound (A) represented by the following formula (1), the compound (B) represented by the following formula (2), and the following formulas (3-1) and formula (1). It contains at least one selected from the group consisting of the compound (C) having two or more groups at least one selected from the groups represented by 3-2).
  • the resin composition of the present embodiment has excellent formability (resin flowability capable of filling a circuit pattern) while having properties such as low dielectric properties and high Tg. That is, it is considered that the circuit filling property) can be exhibited.
  • X A and X B are independently hydrogen atom, amino group, cyano group, hydroxy group, isothiocyanate, methoxy group, carboxy group, carbonyl group and amide group, respectively. , Or a benzoyloxy group.
  • the compound (C) having two or more at least one group selected from the groups represented by the formulas (3-1) and (3-2) is not particularly limited, and is not particularly limited to the formula (3-). Whether it is a compound having both the groups represented by 1) and the formula (3-2) or a compound having two or more groups represented by the formula (3-1), the formula (3-2) ) May be a compound having two or more groups. Specific examples thereof include compounds represented by the following formula (3-3).
  • XC represents an alkylene group, an aromatic structure, a carbonyl group, an amide group or an ether bond.
  • More specific free radical compounds preferably used in the present embodiment include 4-amino-2,2,6,6-tetramethylpiperidin 1-oxyl free radical, 4-acetamide-2,2,6,6. -Tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl free Radical, 4-glycidyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2 , 2,6,6-Tetramethylpiperidin 1-oxylbenzoate free radical, 4-isothiocianato-2,2,6,6-tetramethylpiperidine1-oxyl free radical, 4- (2-iodoacetamide) -2, 2,6,6-Tetramethylpiperidin 1-oxyl free radical, 4- [2- [2- (4-iodophenoxy) e
  • the free radical compound as described above in this embodiment a commercially available one can be used, and it can be obtained from, for example, Tokyo Chemical Industry Co., Ltd.
  • the resin composition according to the present embodiment may further contain an inorganic filler.
  • the inorganic filler include those added to enhance heat resistance and flame retardancy of the cured product of the resin composition, and the present invention is not particularly limited. It is considered that the inclusion of the inorganic filler can further enhance the heat resistance, flame retardancy and the like, and suppress the increase in the coefficient of thermal expansion.
  • metal oxides such as alumina, titanium oxide, and mica
  • metal hydroxides such as aluminum hydroxide and magnesium hydroxide.
  • examples thereof include talc, aluminum borate, barium sulfate, calcium carbonate and the like.
  • silica, mica, and talc are preferable, and spherical silica is more preferable.
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler as described above may be used as it is, or may be surface-treated with an epoxysilane type, vinylsilane type, methacrylicsilane type, or phenylaminosilane type silane coupling agent.
  • silane coupling agent it can be used by adding it to the filler by an integral blending method instead of the method of surface-treating the filler in advance.
  • the resin composition according to the present embodiment may contain a reaction initiator (initiator).
  • the resin composition can proceed with a curing reaction even if it does not contain a reaction initiator.
  • a reaction initiator may be added.
  • the reaction initiator is not particularly limited as long as it can accelerate the curing reaction of the resin composition. Specific examples thereof include metal oxides, azo compounds, peroxides and the like.
  • metal oxide examples include a carboxylic acid metal salt and the like.
  • peroxide examples include ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine, benzoyl peroxide, 3 , 3', 5,5'-tetramethyl-1,4-diphenoquinone, chloranyl, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile, etc. Can be mentioned.
  • azo compound examples include 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (N-butyl-2-methylpropionamide), and 2,2'-.
  • examples thereof include azobis (2-methylbutyronitrile).
  • ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene is preferably used as a preferable reaction initiator. Since ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene has low volatility, it does not volatilize during drying or storage, and has good stability. Further, since ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene has a relatively high reaction start temperature, it suppresses the promotion of the curing reaction at a time when curing is not necessary, such as during prepreg drying. Can be done. By suppressing this curing reaction, it is possible to suppress a decrease in the storage stability of the resin composition.
  • reaction initiator as described above may be used alone or in combination of two or more.
  • the content of the free radical compound is preferably 0.001 to 1 part by mass with respect to 100 parts by mass in total of the styrene-based block copolymer and the radically polymerizable compound in the resin composition. It is more preferably 0.01 to 0.5 parts by mass, and further preferably 0.001 to 0.2 parts by mass.
  • the content of the free radical compound is within the above range, a cured product having a low dielectric property, a high Tg, and a low coefficient of thermal expansion can be obtained, and a resin composition having excellent moldability can be obtained more reliably. Conceivable.
  • the content of the styrene-based block copolymer is preferably 10 to 60 parts by mass, preferably 15 to 50 parts by mass with respect to 100 parts by mass of the resin component (organic component) in the resin composition. More preferably, it is 20 to 40 parts by mass. That is, the content of the styrene-based block copolymer is preferably 10 to 60% by mass with respect to the components other than the inorganic filler (inorganic component) in the resin composition.
  • the content of the radically polymerizable compound is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the resin component (organic component) in the resin composition. , 50 to 70 parts by mass is more preferable. That is, the content of the radically polymerizable compound is preferably 30 to 90% by mass with respect to the components other than the inorganic filler (inorganic component) in the resin composition.
  • the content of the preferred radically polymerizable compound is 10 parts by mass of the resin component (organic component) in the resin composition. It is preferably about 50 parts by mass, more preferably 20 to 50 parts by mass, and even more preferably 30 to 40 parts by mass.
  • the radically polymerizable compound contains a radically polymerizable compound (allyl compound or the like) other than the above, the content of these other radically polymerizable compounds is 100 parts by mass of the resin component (organic component) in the resin composition. On the other hand, it is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass.
  • the content thereof is not particularly limited, but is, for example, 0.01 with respect to 100 parts by mass of the resin component (organic component) in the resin composition. It is preferably up to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass. If the content of the reaction initiator is too small, the curing reaction of the resin composition tends not to be suitably started. Further, if the content of the initiator is too large, the dielectric loss tangent of the obtained cured product of the prepreg becomes large, and it tends to be difficult to exhibit excellent low dielectric properties. Therefore, if the content of the reaction initiator is within the above range, a cured prepreg having excellent low dielectric properties can be obtained.
  • the content (filler content) thereof is preferably 30 to 300% by mass, preferably 50 to 200% by mass, based on the entire resin composition. More preferably, it is by mass%.
  • the resin composition according to the present embodiment may contain components (other components) other than the above-mentioned components, if necessary, as long as the effects of the present invention are not impaired.
  • Other components contained in the resin composition according to the present embodiment include, for example, a curing agent, a silane coupling agent, a flame retardant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, and an ultraviolet absorber.
  • Additives such as dyes, pigments, dispersants and lubricants may be further included.
  • the resin composition of the present embodiment may contain other thermosetting resins such as an epoxy resin and a phenol resin in addition to the polyphenylene ether compound, the allyl compound, and the styrene-based block copolymer. good.
  • FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present invention.
  • each reference numeral is 1 prepreg, 2 resin composition or semi-cured product of resin composition, 3 fibrous base material, 11 metal-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring. , 21 Wiring board, 31 Metal foil with resin, 32, 42 Resin layer, 41 Film with resin, 43 Support film.
  • the prepreg 1 includes the resin composition containing the heat-expandable microcapsules or the semi-cured product 2 of the resin composition, and the fibrous base material 3.
  • the prepreg 1 include those in which the fibrous base material 3 is present in the resin composition or the semi-cured product 2 thereof. That is, the prepreg 1 includes the resin composition or a semi-cured product thereof, and the fibrous base material 3 present in the resin composition or the semi-cured product 2 thereof.
  • the "semi-cured product” is a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a semi-cured (B-staged) resin composition. For example, when the resin composition is heated, the viscosity gradually decreases first, then curing starts, and the viscosity gradually increases. In such a case, the semi-curing state includes a state between the time when the viscosity starts to increase and the time before it is completely cured.
  • the prepreg obtained by using the resin composition according to the present embodiment may include the semi-cured product of the resin composition as described above, or the resin composition which has not been cured. It may be provided with itself. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition of the B stage) and a fibrous base material, or the resin composition before curing (the resin composition of the A stage). It may be a prepreg including a thing) and a fibrous base material. Specific examples thereof include those in which a fibrous base material is present in the resin composition.
  • the resin composition or a semi-cured product thereof may be a heat-dried resin composition.
  • the resin composition according to the present embodiment is often prepared in the form of a varnish and used as a resin varnish when manufacturing the prepreg, a metal leaf with a resin, a metal-clad laminate, or the like described later.
  • a resin varnish is prepared, for example, as follows.
  • each component that can be dissolved in an organic solvent such as a resin component and a reaction initiator is put into an organic solvent and dissolved. At this time, it may be heated if necessary.
  • an inorganic filler or the like which is a component that does not dissolve in an organic solvent, is added and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill or the like until a predetermined dispersion state is obtained, thereby forming a varnish-like resin composition.
  • the thing is prepared.
  • the organic solvent used here is not particularly limited as long as it dissolves the styrene-based block copolymer, the radically polymerizable compound and the like and does not inhibit the curing reaction. Specific examples thereof include toluene, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate and the like. These may be used alone or in combination of two or more.
  • the fibrous base material 3 is impregnated with the resin varnish-like resin composition 2 and then dried.
  • the method can be mentioned.
  • the fibrous substrate used in producing the prepreg include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) non-woven fabric, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, and pulp paper. And linter paper and the like.
  • a glass cloth is used, a laminated board having excellent mechanical strength can be obtained, and a flattened glass cloth is particularly preferable.
  • the glass cloth used in the present embodiment is not particularly limited, and examples thereof include low dielectric constant glass cloths such as E glass, S glass, NE glass, Q glass, L glass, L2 glass, and T glass.
  • the flattening process can be performed by, for example, continuously pressing the glass cloth with a press roll at an appropriate pressure to flatten the yarn.
  • the thickness of the fibrous base material for example, one having a thickness of 0.01 to 0.3 mm can be generally used.
  • the impregnation of the resin varnish (resin composition 2) into the fibrous base material 3 is performed by dipping and coating. This impregnation can be repeated multiple times as needed. Further, at this time, it is also possible to repeat impregnation using a plurality of resin varnishes having different compositions and concentrations to finally adjust the desired composition (content ratio) and the amount of resin.
  • the fibrous base material 3 impregnated with the resin varnish (resin composition 2) is heated under desired heating conditions, for example, 80 ° C. or higher and 180 ° C. or lower for 1 minute or longer and 10 minutes or shorter.
  • desired heating conditions for example, 80 ° C. or higher and 180 ° C. or lower for 1 minute or longer and 10 minutes or shorter.
  • the solvent is volatilized from the varnish and the solvent is reduced or removed to obtain a pre-cured (A stage) or semi-cured (B stage) prepreg 1.
  • the resin-attached metal foil 31 of the present embodiment has a structure in which a resin layer 32 containing the above-mentioned resin composition or a semi-cured product of the resin composition and a metal foil 13 are laminated.
  • the metal foil with resin of the present embodiment may be a metal foil with resin including the resin layer containing the resin composition (the resin composition of the A stage) before curing and the metal foil. It may be a metal foil with a resin including a resin layer containing a semi-cured product of the resin composition (the resin composition of the B stage) and a metal foil.
  • Examples of the method for producing such a metal leaf 31 with a resin include a method in which the resin composition in the form of a resin varnish as described above is applied to the surface of a metal leaf 13 such as a copper foil and then dried.
  • Examples of the coating method include a bar coater, a comma coater, a die coater, a roll coater, a gravure coater, and the like.
  • metal foil 13 metal foil used in a metal-clad laminate, a wiring substrate, or the like can be used without limitation, and examples thereof include copper foil and aluminum foil.
  • the resin-attached film 41 of the present embodiment a resin layer 42 containing the above-mentioned resin composition or a semi-cured product of the resin composition and a film-supporting base material 43 are laminated.
  • the resin-attached film of the present embodiment may be a resin-attached film including the resin composition (the resin composition of the A stage) before curing and the film-supporting base material, or the resin composition.
  • a resin-attached film including the semi-cured product (the resin composition of the B stage) and a film-supporting base material may be used.
  • a film with a resin before curing (A stage) or in a semi-cured state (B stage) can be obtained by allowing the resin to be removed or removing the solvent.
  • the film supporting base material includes an electrically insulating film such as a polyimide film, a PET (polyethylene terephthalate) film, a polyester film, a polyparavanic acid film, a polyether ether ketone film, a polyphenylene sulfide film, an aramid film, a polycarbonate film, and a polyarylate film. And so on.
  • an electrically insulating film such as a polyimide film, a PET (polyethylene terephthalate) film, a polyester film, a polyparavanic acid film, a polyether ether ketone film, a polyphenylene sulfide film, an aramid film, a polycarbonate film, and a polyarylate film. And so on.
  • the resin composition or the semi-cured product thereof may be a dried or heat-dried resin composition as in the above-mentioned prepreg.
  • the thickness of the metal foil 13 and the film supporting base material 43 can be appropriately set according to a desired purpose.
  • a metal leaf 13 having a thickness of about 0.2 to 70 ⁇ m can be used as the metal foil 13.
  • a copper foil with a carrier provided with a release layer and a carrier may be used in order to improve handleability.
  • the application of the resin varnish to the metal foil 13 or the film supporting base material 43 is performed by coating or the like, but it can be repeated a plurality of times as necessary. Further, at this time, it is also possible to repeat the coating using a plurality of resin varnishes having different compositions and concentrations to finally adjust the desired composition (content ratio) and the amount of the resin.
  • the drying or heat-drying conditions in the method for producing the resin-attached metal foil 31 and the resin film 41 are not particularly limited, but are desired after the resin varnish-like resin composition is applied to the metal foil 13 or the film support base material 43.
  • the heating conditions of the above for example, heating at 50 to 170 ° C. for about 0.5 to 10 minutes to volatilize the solvent from the varnish to reduce or remove the solvent, thereby pre-curing (stage A) or semi-curing state (B).
  • stage A pre-curing
  • B semi-curing state
  • the metal foil 31 with resin and the resin film 41 may be provided with a cover film or the like, if necessary.
  • a cover film By providing a cover film, it is possible to prevent foreign matter from entering.
  • the cover film is not particularly limited as long as it can be peeled off without impairing the form of the resin composition, but for example, a polyolefin film, a polyester film, a TPX film, and a mold release agent for these films.
  • a film formed by providing a layer, and a paper obtained by laminating these films on a paper substrate can be used.
  • the metal-clad laminate 11 of the present embodiment is characterized by having an insulating layer 12 containing a cured product of the above-mentioned resin composition or a cured product of the above-mentioned prepreg, and a metal foil 13. do.
  • the metal foil 13 used in the metal-clad laminate 11 the same metal foil 13 as described above can be used.
  • the metal-clad laminate 11 of the present embodiment can also be manufactured by using the above-mentioned metal foil 31 with resin or resin film 41.
  • the prepreg 1, the metal foil 31 with resin, or the resin film 41 obtained as described above is used alone or.
  • a laminated body of double-sided metal foil or single-sided metal foil is formed by stacking a plurality of sheets, further stacking metal foils 13 such as copper foil on both upper and lower surfaces or one side, and laminating and integrating them by heat and pressure molding. It can be manufactured.
  • the heating and pressurizing conditions can be appropriately set depending on the thickness of the laminated board to be manufactured, the type of resin composition, and the like. For example, the temperature is 170 to 230 ° C., the pressure is 0.5 to 5.0 MPa, and the time is 60. It can be up to 150 minutes.
  • the metal-clad laminate 11 may be manufactured by forming a film-shaped resin composition on the metal foil 13 and heating and pressurizing it without using the prepreg 1 or the like.
  • the wiring board 21 of the present embodiment has an insulating layer 12 containing a cured product of the above-mentioned resin composition or a cured product of the above-mentioned prepreg, and wiring 14.
  • the resin composition of this embodiment is suitably used as a material for an insulating layer of a wiring board.
  • a method for manufacturing the wiring board 21 for example, the metal foil 13 on the surface of the metal-clad laminate 13 obtained above is etched to form a circuit (wiring), thereby forming a circuit on the surface of the laminate 13.
  • a wiring board 21 provided with a conductor pattern (wiring 14) can be obtained.
  • Examples of the method for forming a circuit include circuit formation by a semi-additive method (SAP: Semi Adaptive Process) and a modified semi-additive method (MSAP: Modified Semi Adaptive Process), in addition to the methods described above.
  • SAP Semi Adaptive Process
  • MSAP Modified Semi Adaptive Process
  • the prepreg, the film with the resin, and the metal foil with the resin obtained by using the resin composition of the present embodiment have low dielectric properties, low thermal expansion rate, and high Tg in the cured product, and have formability (circuit filling property). It is very useful for industrial use because it is excellent in plastics. Further, the metal-clad laminate and the wiring board obtained by curing them have the advantages of low dielectric property, high Tg, and excellent handleability.
  • Styrene block copolymer Styrene-based block copolymer 1: Styrene isoprene Styrene copolymer (Septon2063 manufactured by Kuraray Co., Ltd., durometer hardness: 36, content of structural units derived from styrene: 13% by mass, weight average molecular weight: 95000)
  • Styrene-based block copolymer 2 Hydrogenated styrene (ethylene / butylene) styrene copolymer (Tuftec H1052 manufactured by Asahi Kasei Co., Ltd., durometer hardness: 67, content of styrene-derived constituent units 20% by mass, weight average Molecular weight 91000)
  • PPE1 A modified polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether is modified with a methacryloyl group (represented by the above formula (34), Y in the formula (34) is represented by a dimethylmethylene group (formula (31), and the formula (31). ) Is a modified polyphenylene ether compound in which R 58 and R 59 are methyl groups), SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw2000, and 2 terminal functional groups).
  • PPE2 A polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) at the terminal (OPE-2st 1200, Mn1200 manufactured by Mitsubishi Gas Chemicals Co., Ltd., represented by the above formula (32), where Z is a phenylene group. , R 24 -R 26 are hydrogen atoms and p is 1 polyphenylene ether compound)
  • (Free radical compound) -Free radical compound 1 4-benzoyloxy tempo, a free radical compound represented by the following formula ("H0878" manufactured by Tokyo Chemical Industry Co., Ltd.)
  • -Free radical compound 2 sebacic acid bis-tempo, free radical compound represented by the following formula ("B5642” manufactured by Tokyo Chemical Industry Co., Ltd. "
  • -Free radical compound 3 tempo, a free radical compound represented by the following formula ("T3751" manufactured by Tokyo Chemical Industry Co., Ltd.
  • Silica particles "SC2300-SVJ” Vinylsilane-treated spherical silica (manufactured by Admatex Co., Ltd.)
  • a metal leaf with resin and evaluation board A metal leaf with a resin was prepared using the resin varnishes of the examples and comparative examples prepared above.
  • the obtained varnish is applied to a metal foil (copper foil, 3EC-VLP manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 ⁇ m) so as to have a thickness of 20 ⁇ m, and heated at 80 ° C. for 2 minutes to form a resin. Obtained a metal leaf.
  • two of the obtained metal foils with resin were stacked so that the resin layers were in contact with each other.
  • the resin layer of the metal foil with resin was cured by heating and pressurizing under the conditions of vacuum at 200 ° C. and pressure of 4 MPa for 2 hours. This was used as an evaluation substrate (a cured product of a metal foil with resin).
  • the thickness of the resin layer (thickness other than the metal foil) on the evaluation substrate was 40 ⁇ m.
  • Tg Glass transition temperature
  • DMA dynamic viscoelasticity measurement
  • Dk Relative permittivity
  • Line expansion coefficient (CTE) The linear expansion coefficient in the plane direction of the laminated plate from which the copper foil of the evaluation substrate (cured product of the metal foil with resin) was removed was measured in the pull mode by a method according to JIS C 6481.
  • the measurement conditions are a heating rate of 10 ° C./min, the temperature range is a temperature range of less than Tg, specifically, a thermomechanical analysis (TMA) device (TMA manufactured by Hitachi High-Tech Science Corporation) at 50 to 100 ° C. / SS7000) was used for measurement.
  • TMA thermomechanical analysis
  • a cured product having a residual copper ratio of 50%, a copper wire thickness of 12 ⁇ m, a copper wire wiring width of 2 ⁇ m, and a copper pattern on a lattice of 250 mm ⁇ 250 mm was prepared.
  • a metal leaf with a resin of 250 mm ⁇ 250 mm was laminated on both sides thereof so that the resin surface was in contact with the cured product. These were sandwiched between metal plates having a thickness of about 3 mm, and heated and pressed with a press for laminating molding under the conditions shown below. As a heating condition, the temperature was raised at 6 degrees per minute from 30 degrees to 200 degrees.
  • the pressure applied to the metal leaf with resin is set to 1 MPa at the start of heating, and then when the temperature reaches 80 ° C., the pressure applied to the metal leaf with resin is 4 MPa. The metal leaf with resin was cured.
  • the present invention has a wide range of industrial applicability in the technical field of electronic materials and various devices using the same.

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PCT/JP2021/033408 2020-09-18 2021-09-10 樹脂組成物、並びに、それを用いたプリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板及び配線基板 Ceased WO2022059625A1 (ja)

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WO2024095742A1 (ja) * 2022-11-02 2024-05-10 Ａｇｃ株式会社 硬化性組成物、樹脂シート、積層体、金属張積層板および配線基板
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