WO2013069479A1 - 樹脂組成物、これを用いたプリプレグ及び積層板 - Google Patents
樹脂組成物、これを用いたプリプレグ及び積層板 Download PDFInfo
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- WO2013069479A1 WO2013069479A1 PCT/JP2012/077738 JP2012077738W WO2013069479A1 WO 2013069479 A1 WO2013069479 A1 WO 2013069479A1 JP 2012077738 W JP2012077738 W JP 2012077738W WO 2013069479 A1 WO2013069479 A1 WO 2013069479A1
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- resin composition
- inorganic filler
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- cyanate ester
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- 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
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- 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
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2475—Coating or impregnation is electrical insulation-providing, -improving, or -increasing, or conductivity-reducing
Definitions
- the present invention relates to a resin composition, a prepreg, and a laminated board, and more particularly to a resin composition for a printed wiring board having high thermal conductivity.
- thermosetting resin itself such as an epoxy resin used for an insulating layer of a printed wiring board itself has a low thermal conductivity. Therefore, in order to improve the thermal conductivity of the printed wiring board, 80 to 95% by weight of a mixed filler (inorganic filler) having a predetermined particle size distribution is blended in the thermosetting resin to increase the thermal conductivity of the cured product.
- a thermally conductive resin composition having a concentration of 3 to 10 W / mK has been proposed (see Patent Document 1).
- thermosetting resin composition is highly filled with an inorganic filler as in Patent Document 1, the thermal conductivity can be improved, but the volume ratio of the thermosetting resin is reduced, so that the moldability is deteriorated.
- cracks and voids are likely to occur between the resin and the inorganic filler.
- the moisture absorption heat resistance is deteriorated and the elastic modulus is lowered, and further, the adhesiveness between the resin and the inorganic filler becomes insufficient, so that the metal foil peel strength is lowered.
- the present invention has been made in view of the above problems, and its purpose is not only to have a high thermal conductivity, but also to a laminated board, a printed wiring board, etc., which have good moldability and suppress generation of cracks and voids. Is to provide a resin composition that can be easily and reproducibly realized. Another object of the present invention is not only thermal conductivity and moldability, but also laminates and printed wiring boards that are excellent in metal foil peel strength, moisture absorption heat resistance, bending strength, elastic modulus, and glass transition temperature. It is an object of the present invention to provide a resin composition that can be easily realized with good reproducibility, and a prepreg, a laminate, and a metal foil-clad laminate using the same.
- the present inventors have found that the cyanate ester compound (A), the epoxy resin (B), the first inorganic filler (C), and the second inorganic filler (D ) At least the ratio of the average particle diameter of the first inorganic filler (C) and the second inorganic filler (D) is 1: 0.02 to 1: 0.2.
- the present invention provides the following ⁇ 1> to ⁇ 23>.
- ⁇ 1> At least a cyanate ester compound (A), an epoxy resin (B), a first inorganic filler (C), and a second inorganic filler (D), and the first inorganic filler (C )
- the average particle size ratio of the second inorganic filler (D) is 1: 0.02 to 1: 0.2.
- ⁇ 2> The content ratio of the first inorganic filler (C) and the second inorganic filler (D) is 1: 0.03 to 1: 0.5.
- the total content of the first inorganic filler (C) and the second inorganic filler (D) is 100 parts by mass of the cyanate ester compound (A) and the epoxy resin (B). 351 to 900 parts by mass with respect to The resin composition as described in ⁇ 1> or ⁇ 2> above.
- the total content of the first inorganic filler (C) and the second inorganic filler (D) is a total of 100 parts by mass of the cyanate ester compound (A) and the epoxy resin (B). 701 to 900 parts by mass with respect to The resin composition as described in ⁇ 1> or ⁇ 2> above.
- the first inorganic filler (C) has an average particle diameter of 0.5 to 10 ⁇ m.
- the second inorganic filler (D) has an average particle diameter of 0.01 to 2 ⁇ m.
- the second inorganic filler (D) is spherical. The resin composition according to any one of ⁇ 1> to ⁇ 6> above.
- the second inorganic filler (D) is selected from the group consisting of alumina, magnesium oxide, aluminum hydroxide, boron nitride, aggregated boron nitride, silicon nitride, molybdenum compound, zinc borate, and aluminum nitride. At least one, The resin composition according to any one of ⁇ 1> to ⁇ 7> above. ⁇ 9> The second inorganic filler (D) is at least one selected from the group consisting of alumina, magnesium oxide, boron nitride, and aluminum nitride. The resin composition as described in ⁇ 8> above.
- the first inorganic filler (C) and the second inorganic filler (D) are included in a total volume of 50% by volume to 80% by volume with respect to the total volume of the resin composition.
- the first inorganic filler (C) is selected from the group consisting of alumina, magnesium oxide, aluminum hydroxide, boron nitride, aggregated boron nitride, silicon nitride, molybdenum compound, zinc borate, and aluminum nitride.
- One kind The resin composition according to any one of ⁇ 1> to ⁇ 10> above.
- the first inorganic filler (C) is one selected from the group consisting of alumina, magnesium oxide, boron nitride, and aluminum nitride.
- the cyanate ester compound (A) is a naphthol aralkyl-type cyanate ester compound represented by the following general formula (1), a novolac-type cyanate ester compound represented by the following general formula (2), and It is at least one selected from the group consisting of a biphenylaralkyl type cyanate ester compound represented by the following general formula (3).
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- the cyanate ester compound is a naphthol aralkyl-type cyanate ester compound represented by the general formula (1).
- the cyanate ester compound (A) is included in an amount of 10 to 90 parts by mass with respect to a total of 100 parts by mass of the cyanate ester compound (A) and the epoxy resin (B).
- ⁇ 16> Further including a silane coupling agent (E), The resin composition according to any one of ⁇ 1> to ⁇ 15> above.
- the silane coupling agent is contained in an amount of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the cyanate ester compound (A) and the epoxy resin (B).
- ⁇ 18> Further including a maleimide compound (F), The resin composition according to any one of ⁇ 1> to ⁇ 17> above. ⁇ 19> The maleimide compound (F) is included in an amount of 5 to 75 parts by mass with respect to a total of 100 parts by mass of the cyanate ester compound (A) and the maleimide compound (F). The resin composition as described in ⁇ 18> above.
- ⁇ 20> The substrate is impregnated or coated with the resin composition according to any one of ⁇ 1> to ⁇ 19> above, Preprig. ⁇ 21> obtained by curing the prepreg according to the above ⁇ 20>.
- Laminated board. ⁇ 22> The prepreg according to the above ⁇ 20> and a metal foil are laminated and cured.
- Metal foil-clad laminate. ⁇ 23> A printed wiring board including an insulating layer and a conductor layer formed on a surface of the insulating layer, A printed wiring board, wherein the insulating layer includes the resin composition according to any one of ⁇ 1> to ⁇ 19>.
- a laminated board, a printed wiring board, etc. that have not only high thermal conductivity but also good moldability and suppressed generation of cracks and voids with good reproducibility. Further, according to a preferred embodiment of the present invention, not only in thermal conductivity and formability, but also in glass transition temperature, metal foil peel strength, solder heat resistance, moisture absorption heat resistance, water absorption rate, bending strength, elastic modulus, etc.
- a printed wiring board or a metal foil-clad laminate having high performance can be realized.
- the resin composition of this embodiment contains at least a cyanate ester compound (A), an epoxy resin (B), a first inorganic filler (C), and a second inorganic filler (D), and the first
- the ratio of the average particle diameter of the inorganic filler (C) and the second inorganic filler (D) is 1: 0.02 to 1: 0.2.
- any compound represented by the general formula R—O—CN (wherein R is an organic group) is known.
- R is an organic group
- Biphenylaralkyl cyanate ester 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl4-cyanatophenyl) methane, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1, 3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2'-bis (4 Cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2′-bis (4-cyanatophenyl) propane , Bis (3,
- a naphthol aralkyl type cyanate ester compound represented by the following general formula (1) A novolak cyanate ester compound represented by the formula (2) and a biphenylaralkyl cyanate ester compound represented by the following general formula (3) are preferred, and a naphthol aralkyl cyanate represented by the following general formula (1) An ester compound is more preferable.
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50.
- the ⁇ -naphthol aralkyl cyanate ester compound in which the substituent R is hydrogen is not only excellent in heat resistance but also absorbs water. And is excellent in properties such as moisture absorption heat resistance and can be used particularly suitably.
- a cyanate ester compound (A) can be used individually by 1 type or in combination of 2 or more types according to the objective.
- two or more of the different general formulas (1) to (3) having different n may be used by appropriately mixing them. You can also.
- the content of the cyanate ester compound (A) in the resin composition can be appropriately set according to the intended use and performance, and is not particularly limited.
- the content of the cyanate ester compound (A) is the amount of the cyanate ester compound (A) and the epoxy resin (B).
- the total amount is preferably 10 to 90 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass.
- epoxy resin (B) used in the resin composition of the present embodiment a known one can be used as long as it is a compound having two or more epoxy groups in one molecule, and the kind thereof is not particularly limited.
- Non-halogen-based epoxy resins are preferred because of recent interest in environmental issues. Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, anthracene type epoxy resin, bisphenol.
- a novolac type epoxy resin trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, naphthalene type epoxy resin, biphenyl Type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy Examples include resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamines, glycidyl esters, compounds obtained by epoxidizing double bonds such as butadiene, compounds obtained by the reaction of hydroxyl group-containing silicone resins and epichlorohydrin, and the like.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin are preferable, more preferably phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type It is an epoxy resin.
- these epoxy resins (B) can be used individually by 1 type or in combination of 2 or more types according to the objective.
- the content of the epoxy resin (B) in the resin composition can be appropriately set according to the intended use and performance, and is not particularly limited. From the viewpoint of heat resistance, thermal conductivity and water absorption of the resin composition and its cured product, the content of the epoxy resin (B) is 100 parts by mass in total of the cyanate ester compound (A) and the epoxy resin (B). On the other hand, it is preferably 10 to 90 parts by mass, more preferably 30 to 70 parts by mass.
- the resin composition of this embodiment includes two or more types of inorganic fillers having different average particle diameters, that is, a first inorganic filler (C) having a large average particle diameter, and a second having a small average particle diameter. And at least an inorganic filler (D).
- the first inorganic filler (C) and the second inorganic filler are used from the viewpoint of improving the filling rate of the inorganic filler and enhancing the moldability of the resin composition.
- the average particle size ratio of (D) is required to be 1: 0.02 to 1: 0.2.
- the volume fraction of the inorganic filler in the resin composition (hereinafter also simply referred to as “filling ratio”) by entering the gap between the particles of the inorganic filler having the smaller average particle diameter and the larger inorganic filler.
- the ratio of the average particle diameter of the first inorganic filler (C) and the second inorganic filler (D) is more preferably 1: 0.025 to 1: 0.18, and still more preferably. 1: 0.05 to 1: 0.14.
- the average particle diameter means the median diameter (D50), and is a value in which the larger side and the smaller side are equivalent when the particle size distribution of the measured powder is divided into two.
- the average particle size (D50) in the present specification is measured by measuring the particle size distribution of powder dispersed in methyl ethyl ketone using a laser diffraction scattering type particle size distribution measuring device under the conditions of the examples described later. It means the value when the volume is accumulated from small particles and reaches 50% of the total volume.
- the first inorganic filler (C) used in the resin composition of the present embodiment has an average particle size larger than that of the second inorganic filler (D).
- the type can be appropriately selected from those generally used for insulating resins for printed wiring boards and laminates, and is not particularly limited.
- Specific examples include, for example, natural silica, fused silica, synthetic silica, amorphous silica, hollow silica and other silicas, white carbon, titanium white, aerosil, silicone composite powder, silicone resin powder, alumina, zinc oxide, magnesium oxide, Zirconium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, molybdenum oxide, zinc molybdate and other molybdenum compounds, zinc borate, aluminum nitride, barium sulfate, aluminum hydroxide heat-treated products ( Heat treatment of aluminum hydroxide to reduce part of crystal water), metal hydrates such as magnesium hydroxide, zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, natural mica , Synthetic mica, -Glass, A-glass, NE-glass,
- the first inorganic filler (C) is alumina, magnesium oxide, aluminum hydroxide, boron nitride, aggregated boron nitride, silicon nitride, molybdenum compound, boric acid. Zinc and aluminum nitride are preferable, and alumina, magnesium oxide, boron nitride, and aluminum nitride are more preferable. As long as the ratio of the average particle diameter with the second inorganic filler (D) is 1: 0.02 to 1: 0.2, the first inorganic filler (C) is one kind. Can be used alone or in appropriate combination of two or more.
- the average particle diameter of the first inorganic filler (C) is not particularly limited, but is preferably 0.5 to 10 ⁇ m, more preferably 1.5 to 7 ⁇ m from the viewpoint of dispersibility and filling rate.
- the shape of the first inorganic filler (C) is not particularly limited, but is preferably spherical from the viewpoint of reducing the specific surface area.
- the second inorganic filler (D) used in the resin composition of the present embodiment has an average particle size smaller than that of the first inorganic filler (C).
- the type can be appropriately selected from those generally used for insulating resins for printed wiring boards and laminates, and is not particularly limited.
- Specific examples include, for example, natural silica, fused silica, synthetic silica, amorphous silica, hollow silica and other silicas, white carbon, titanium white, aerosil, silicone composite powder, silicone resin powder, alumina, zinc oxide, magnesium oxide, Zirconium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, molybdenum oxide, zinc molybdate and other molybdenum compounds, zinc borate, aluminum nitride, barium sulfate, aluminum hydroxide heat-treated products ( Heat treatment of aluminum hydroxide to reduce part of crystal water), metal hydrates such as magnesium hydroxide, zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, natural mica , Synthetic mica, -Glass, A-glass, NE-glass,
- alumina, magnesium oxide, aluminum hydroxide, boron nitride, agglomerated boron nitride, silicon nitride, molybdenum compound, zinc borate, and aluminum nitride are preferable from the viewpoint of thermal conductivity and filling rate, more preferably alumina.
- Magnesium oxide, boron nitride, and aluminum nitride are preferable from the viewpoint of thermal conductivity and filling rate, more preferably alumina.
- Magnesium oxide, boron nitride, and aluminum nitride is one kind. Can be used alone or in appropriate combination of two or more.
- the average particle diameter of the second inorganic filler (D) is not particularly limited, but is preferably 0.01 to 2 ⁇ m, more preferably 0.1 to 1.0 ⁇ m from the viewpoint of dispersibility and filling rate. It is.
- the shape of the second inorganic filler (D) is not particularly limited, but is preferably spherical from the viewpoint of increasing the filling rate.
- the contents of the first inorganic filler (C) and the second inorganic filler (D) can be appropriately set and are not particularly limited, but the thermal conductivity and moldability
- the total content of the first inorganic filler (C) and the second inorganic filler (D) is 100 parts by mass in total of the cyanate ester compound (A) and the epoxy resin (B).
- it is preferably 351 to 900 parts by mass, more preferably 701 to 900 parts by mass.
- the total volume of the first inorganic filler (C) and the second inorganic filler (D) is preferably 50% by volume or more and 80% by volume or less with respect to the total volume of the resin composition. . This is because the thermal conductivity can be drastically improved by adding the first inorganic filler (C) and the second inorganic filler (D) with such a content.
- the content ratio of the first inorganic filler (C) and the second inorganic filler (D) can be set as appropriate and is not particularly limited. From the viewpoint of increasing, it is preferably 1: 0.03 to 1: 0.5.
- liquidity of a resin composition improves and it exists in the tendency for molding defects, such as the void generation
- the resin composition of the present embodiment may further contain a silane coupling agent (E) as necessary.
- the silanol group possessed by the silane coupling agent (E) is excellent in affinity and reactivity with a material having a hydroxyl group on the surface, and therefore has an effect on the organic-inorganic bond.
- the particle surface of the inorganic filler is silane.
- the adhesion between the thermosetting resin and the inorganic filler tends to be particularly remarkably enhanced. Therefore, by including the silane coupling agent (E) in the resin composition of this embodiment, the metal foil peel strength, bending strength, elastic modulus, and moisture absorption heat resistance of the obtained printed wiring board and the like tend to be increased.
- silane coupling agent (E) used here what is generally used for the surface treatment of an inorganic substance can be used conveniently, and the kind is not specifically limited. Specific examples thereof include aminosilanes such as ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane.
- Vinylsilanes such as ⁇ -methacryloxypropyltrimethoxysilane, cationic silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride, phenylsilanes, etc. Although it is mentioned, it is not specifically limited to these.
- a silane coupling agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the content of the silane coupling agent (E) can be appropriately set and is not particularly limited.
- the cyanate ester compound (A) and The amount is preferably 3 to 30 parts by mass with respect to 100 parts by mass in total of the epoxy resin (B).
- the resin composition of the present embodiment may further contain a wetting and dispersing agent as necessary.
- a wetting and dispersing agent By including the wetting and dispersing agent, the dispersibility of the inorganic filler tends to be improved.
- the wetting and dispersing agent those generally used for paints can be suitably used, and the kind thereof is not particularly limited. Specific examples thereof include Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W161, BYK-W940 and the like manufactured by Big Chemie Japan Co., Ltd. However, it is not particularly limited to these. Wet dispersants can be used alone or in combination of two or more.
- the content of the wetting and dispersing agent can be appropriately set and is not particularly limited.
- the cyanate ester compound (A) and the epoxy resin (B) The total content is preferably 1 to 10 parts by mass with respect to 100 parts by mass in total.
- the resin composition of the present embodiment may further contain a maleimide compound (F) as necessary.
- a maleimide compound (F) By including the maleimide compound (F), the cyanate ester compound (A) reacts with the maleimide group, the crosslinking density is increased, and the heat resistance and elastic modulus of the obtained printed wiring board and the like tend to be increased. is there.
- the maleimide compound (F) a known compound can be appropriately used as long as it is a compound having one or more maleimide groups in one molecule, and the kind thereof is not particularly limited.
- N-phenylmaleimide N-hydroxyphenylmaleimide
- bis (4-maleimidophenyl) methane 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane
- bis (3 , 5-dimethyl-4-maleimidophenyl) methane bis (3-ethyl-5-methyl-4-maleimidophenyl) methane
- bis (3,5-diethyl-4-maleimidophenyl) methane tris (4-maleimidophenyl) ) Methane
- maleimide compounds represented by the following general formula (4), and the like, but are not particularly limited thereto.
- the maleimide compound (F) is not limited to a monomer form, and may be a prepolymer form or a prepolymer form of a bismaleimide compound and an amine compound.
- bis (4-maleimidophenyl) methane a maleimide compound represented by the following general formula (4), 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ Propane and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane are preferred.
- each R 4 independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.
- the content of the maleimide compound (F) can be appropriately set and is not particularly limited.
- the content of the cyanate ester compound (A) and the maleimide compound The amount is preferably 5 to 75 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass in total.
- the resin composition of this embodiment may contain components other than the above-described components as necessary within a range in which desired properties are not impaired.
- arbitrary blends include various other high molecular compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, elastomers other than those described above, curing accelerators for appropriately adjusting the curing rate, difficulty Examples include flammable compounds and various additives. These can be used without particular limitation as long as they are generally used.
- a hardening accelerator if it is generally used as a hardening accelerator of a cyanate ester compound (A) or an epoxy resin (B), it can be used without a restriction
- a hardening accelerator can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the amount of the curing accelerator used can be appropriately adjusted from the viewpoint of the degree of curing of the resin, the viscosity of the resin composition, and the like, and is not particularly limited. About mass parts.
- the flame retardant compound examples include bromine compounds such as 4,4′-dibromobiphenyl, phosphorus compounds such as phosphate esters, melamine phosphate and phosphorus-containing epoxy resins, nitrogen-containing compounds such as melamine and benzoguanamine, and oxazines. Although a ring containing compound, a silicon-type compound, etc. are mentioned, it does not specifically limit to these.
- a flame-retardant compound can be used individually by 1 type or in combination of 2 or more types as appropriate.
- additives include, for example, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, dyes, pigments, thickeners, lubricants, antifoaming agents.
- examples thereof include, but are not particularly limited to, dispersants other than the above-mentioned wetting and dispersing agents, leveling agents, brighteners, polymerization inhibitors and the like.
- the resin composition of the present embodiment may contain an organic solvent as necessary. That is, the resin composition of this embodiment is used as an aspect (resin varnish) in which at least a part, preferably all, of the cyanate ester compound (A) and the epoxy resin (B) described above are dissolved or compatible with an organic solvent. be able to. Since the viscosity of the resin composition can be lowered by using an organic solvent, the handling property is improved and the impregnation property to the glass cloth tends to be improved.
- the kind of the organic solvent is not particularly limited as long as at least a part of the above-described cyanate ester compound (A) and epoxy resin (B) can be dissolved or compatible.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
- aromatic hydrocarbons such as benzene, toluene, and xylene
- amides such as dimethylformamide and dimethylacetamide, and the like. It is not limited to these.
- These organic solvents can be used individually by 1 type or in combination of 2 or more types as appropriate.
- the cyanate ester compound (A), the epoxy resin (B), the first inorganic filler (C), and the second inorganic filler (D) described above are stirred according to a conventional method.
- -It can prepare by mixing,
- the preparation method is not specifically limited.
- the first inorganic filler (C) and the second inorganic filler (D) are blended with the epoxy resin (B), dispersed with a homomixer or the like, and the cyanate ester compound (A) is blended therein.
- the method etc. are mentioned.
- known processes for uniformly mixing the components can be performed.
- the above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known apparatus such as a ball mill or a bead mill for mixing, or a revolution / spinning mixing apparatus.
- the prepreg of the present embodiment is a combination of the resin composition of the present embodiment and a substrate. Specifically, the prepreg is impregnated or coated on the substrate.
- the base material used in the prepreg of the present embodiment is not particularly limited, and is appropriately selected from, for example, known materials used for various printed wiring board materials depending on the intended use and performance. can do. Specific examples thereof include, for example, glass fibers such as E glass, T glass, L glass, D glass, S glass, NE glass, Q glass, UN glass and spherical glass, inorganic fibers other than glass such as quartz, polyimide, Examples thereof include organic fibers such as polyamide and polyester, and woven fabrics such as liquid crystal polyester, but are not particularly limited thereto.
- a base material can be used individually by 1 type or in combination of 2 or more types as appropriate.
- As the shape of the base material woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat and the like are known, and as the weaving method of the woven fabric, plain weave, Nanako weave, twill weave, etc. are known. However, either one is acceptable.
- the thickness of the substrate is not particularly limited, but is usually about 0.01 to 0.3 mm. For example, in the case of a laminate, a range of 0.01 to 0.2 mm is preferable.
- the above-mentioned base material is preferably subjected to a surface treatment from the viewpoint of adhesion to the resin and moisture absorption heat resistance.
- the surface of the substrate can be surface treated with a silane coupling agent or the like.
- the woven fabric is physically opened from a viewpoint of adhesiveness with resin.
- a film as a base material what was surface-treated by plasma treatment etc. from an adhesive viewpoint with resin is preferable.
- the prepreg of the present embodiment can be produced according to a conventional method, and the production method is not particularly limited.
- a method for producing a prepreg a method of impregnating or applying the above resin composition to a substrate is generally known. More specifically, for example, after impregnating or coating a resin varnish obtained by adding an organic solvent to the above resin composition, the substrate is heated in a dryer at 100 to 200 ° C. for 1 to 60 minutes.
- the prepreg of this embodiment can be produced by semi-curing (B-stage).
- the adhesion amount of the resin composition to the substrate that is, the resin composition amount (including the first inorganic filler (C) and the second inorganic filler (D)) with respect to the total amount of the prepreg after semi-curing.
- the range of 40 to 95% by mass is preferable.
- the laminated board of this embodiment is formed by lamination using the above-described prepreg.
- the metal foil-clad laminate of this embodiment is obtained by laminating the above-described prepreg and metal foil.
- the metal foil-clad laminate of the present embodiment is formed by laminating one or a plurality of the above-described prepregs, and placing a metal foil such as copper or aluminum on one or both sides as desired. It can be produced by molding.
- the metal foil used here will not be specifically limited if it is used for printed wiring board material, Copper foil, such as a rolled copper foil and an electrolytic copper foil, is preferable.
- an electrolytic copper foil having a small mat surface roughness is more suitable.
- the thickness of the metal foil is not particularly limited, but is preferably 2 to 70 ⁇ m, more preferably 2 to 35 ⁇ m.
- the molding conditions are not particularly limited, and can be an ordinary laminate method for printed wiring boards and multilayer boards. For example, using a multi-stage press, multi-stage vacuum press, continuous molding machine, autoclave molding machine, etc., temperature is 100 to 300 ° C., pressure is surface pressure 2 to 100 kgf / cm 2 , and heating time is 0.05 to 5 hours. It is common to carry out in the range of.
- a multilayer board by laminating and molding the above prepreg and a separately produced wiring board for the inner layer.
- copper foil is disposed on both surfaces of the above prepreg, and after laminating and forming under the above conditions, an inner layer circuit is formed, and blackening treatment is performed on this circuit to form an inner layer circuit board.
- the inner circuit board and the prepreg are alternately arranged one by one, and the copper foil is further arranged on the outermost layer, and multilayer molding is preferably performed under the above conditions, preferably under vacuum.
- a plate can be made.
- the metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern.
- the metal foil-clad laminate of this embodiment is high not only in thermal conductivity and moldability, but also in glass transition temperature, metal foil peel strength, solder heat resistance, moisture absorption heat resistance, water absorption rate, bending strength, elastic modulus, etc. Since it has performance, it can be used particularly effectively as a printed wiring board for a semiconductor package that requires such performance.
- the above printed wiring board can be manufactured, for example, by the following method. First, a metal foil-clad laminate such as the copper clad laminate described above is prepared. Next, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is stacked on the outer surface. Then, it is integrally molded by heating and pressing.
- a metal foil-clad laminate such as the copper clad laminate described above is prepared.
- an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate.
- the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the prepregs are stacked
- a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit.
- a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit and the metal foil for the outer layer circuit. Etching is performed on the metal foil for forming an outer layer circuit, and a printed wiring board is manufactured.
- the insulating layer can include the above-described resin composition of the present embodiment.
- the prepreg of the present embodiment described above the base material and the resin composition of the present embodiment impregnated or applied thereto
- the layer of the resin composition of the metal foil-clad laminate of the embodiment is composed of an insulating layer containing the resin composition of this embodiment.
- the resin composition of this embodiment is not limited to what was mentioned above,
- an electrically insulating material, a sealing material, an adhesive agent Also, it can be effectively used in resist materials and the like, and its use is not particularly limited.
- part means “part by mass” unless otherwise specified.
- Example 1 40 parts by mass of the ⁇ -naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1 and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, manufactured by KAI Kasei Co., Ltd.) 20 parts by mass, 40 parts by mass of a biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.), 15 parts by mass of a silane coupling agent (Z6040, manufactured by Toray Dow Corning Co., Ltd.), 5 parts by mass of a wetting and dispersing agent containing acid groups (BYK-W903, manufactured by Big Chemie Japan Co., Ltd.) is dissolved and mixed in methyl ethyl ketone, and this is a true spherical alumina (trade name: AX3- 15, 500 parts by mass of Nippon Steel & Sumikin Materials Co., Ltd.
- Non-spherical alumina (Micron) and non-spherical alumina (trade name: Advanced Alumina AA) with an average particle diameter of 3 ⁇ m 3. 100 parts by mass of Sumitomo Chemical Co., Ltd.), 150 parts by mass of spherical alumina (trade name: ASFP-20, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an average particle size of 0.3 ⁇ m, Nikka Octix Manganese ( Mn 8%) (Nippon Chemical Industry Co., Ltd.) 0.01 parts by mass and 2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) 0.5 parts by mass are mixed to obtain a resin varnish. Prepared.
- the average particle size is determined by dispersing each inorganic filler with methyl ethyl ketone, followed by dispersing for 3 minutes with an ultrasonic homogenizer, and using a laser diffraction scattering type particle size distribution measuring device (manufactured by Shimadzu Corporation). Measured value.
- the obtained resin varnish is further diluted with methyl ethyl ketone to obtain a resin varnish having a solid content concentration of 65 wt%, and this resin varnish is impregnated with 0.05 mm thick E glass cloth (Asahi Kasei E-Materials Co., Ltd.). Then, a prepreg of 0.1 mmmt was produced by heating and drying at 160 ° C. for 3 minutes.
- a metal foil-clad laminate double-sided copper-clad laminate having a thickness of 0.8 mm was produced by performing vacuum pressing at a temperature of 220 ° C. for 120 minutes to perform lamination molding.
- Example 2 Change the blending amount of true spherical alumina (AX3-15) to 630 parts by mass and the blending amount of spherical alumina (ASFP-20) to 20 parts by mass, and omit blending of non-spherical alumina (AA-3). Except for this, the same procedure as in Example 1 was performed.
- Example 3 Changed the amount of silane coupling agent (Z6040) to 5 parts by mass, the amount of true spherical alumina (AX3-15) to 630 parts by mass, and the amount of spherical alumina (ASFP-20) to 20 parts by mass. Then, the same procedure as in Example 1 was performed except that the blending of non-spherical alumina (AA-3) was omitted.
- Example 2 Except for changing the blending amount of true spherical alumina (AX3-15) to 650 parts by mass and omitting blending of non-spherical alumina (AA-3) and spherical alumina (ASFP-20), the same as in Example 1. went.
- Example 3 Except for changing the blending amount of true spherical alumina (AX3-15) to 750 parts by mass and omitting blending of non-spherical alumina (AA-3) and spherical alumina (ASFP-20), the same as in Example 1. went.
- Example 4 Except omitting the blending of true spherical alumina (AX3-15) and non-spherical alumina (AA-3) and changing the blending amount of spherical alumina (ASFP-20) to 750 parts by mass, it is the same as in Example 1. went.
- the metal foil-clad laminates of Examples 1 to 3 had higher thermal conductivity than the metal foil-clad laminate of Comparative Example 1. Further, it was confirmed that the metal foil-clad laminates of Examples 1 to 3 were excellent in formability (appearance evaluation) as compared with the metal foil-clad laminates of Comparative Examples 2 to 4. On the other hand, it was confirmed that the metal foil-clad laminate of Comparative Example 1 has a significantly low thermal conductivity and an inferior elastic modulus. Further, in the metal foil-clad laminates of Comparative Examples 2 to 4, voids were generated and it was confirmed that the moldability was inferior.
- the resin composition of the present invention is excellent in thermal conductivity and moldability, in various applications such as electrical / electronic materials, machine tool materials, and aviation materials, for example, electrical insulating materials, semiconductor plastic packages, Widely and effectively usable as sealing materials, adhesives, laminated materials, resists, build-up laminated board materials, etc., and particularly effectively used as printed wiring board materials for high integration and high density. It is.
- the laminate and metal foil-clad laminate of the present invention have excellent performance not only in thermal conductivity and moldability, but also in metal foil peel strength, moisture absorption heat resistance, bending strength, elastic modulus, and glass transition temperature. Therefore, its industrial practicality is extremely high.
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Abstract
Description
また、本発明の他の目的は、熱伝導率及び成形性のみならず、金属箔ピール強度、吸湿耐熱性、曲げ強度、弾性率、及びガラス転移温度にも優れる積層板やプリント配線板等を簡易に且つ再現性よく実現可能な樹脂組成物、並びに、これを用いたプリプレグ、積層板及び金属箔張り積層板を提供することにある。
<1> シアン酸エステル化合物(A)、エポキシ樹脂(B)、第一の無機充填材(C)及び第二の無機充填材(D)を少なくとも含有し、前記第一の無機充填材(C)と前記第二の無機充填材(D)の平均粒子径の比が1:0.02~1:0.2である、
樹脂組成物。
<2> 前記第一の無機充填材(C)と前記第二の無機充填材(D)の含有割合が、1:0.03~1:0.5である、
上記<1>に記載の樹脂組成物。
<3> 前記第一の無機充填材(C)と前記第二の無機充填材(D)の合計含有量が、前記シアン酸エステル化合物(A)と前記エポキシ樹脂(B)の合計100質量部に対して、351~900質量部である、
上記<1>又は<2>に記載の樹脂組成物。
<4> 前記第一の無機充填材(C)と前記第二の無機充填材(D)の合計含有量が、前記シアン酸エステル化合物(A)と前記エポキシ樹脂(B)の合計100質量部に対して、701~900質量部である、
上記<1>又は<2>に記載の樹脂組成物。
上記<1>~<4>のいずれか一項に記載の樹脂組成物。
<6> 前記第二の無機充填材(D)は、0.01~2μmの平均粒子径を有する、
上記<1>~<5>のいずれか一項に記載の樹脂組成物。
<7> 前記第二の無機充填材(D)は、球状である、
上記<1>~<6>のいずれか一項に記載の樹脂組成物。
<8> 前記第二の無機充填材(D)が、アルミナ、酸化マグネシウム、水酸化アルミニウム、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、モリブデン化合物、ホウ酸亜鉛及び窒化アルミニウムよりなる群から選択される少なくとも1種である、
上記<1>~<7>のいずれか一項に記載の樹脂組成物。
<9> 前記第二の無機充填材(D)が、アルミナ、酸化マグネシウム、窒化ホウ素及び窒化アルミニウムよりなる群から選択される少なくとも1種である、
上記<8>に記載の樹脂組成物。
<10> 前記第一の無機充填材(C)及び第二の無機充填材(D)が、樹脂組成物の全体積に対して、合計で50体積%以上80体積%以下含まれる、
上記<1>~<9>のいずれか一項に記載の樹脂組成物。
<11> 前記第一の無機充填材(C)が、アルミナ、酸化マグネシウム、水酸化アルミニウム、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、モリブデン化合物、ホウ酸亜鉛及び窒化アルミニウムよりなる群から選択される1種である、
上記<1>~<10>のいずれか一項に記載の樹脂組成物。
<12> 前記第一の無機充填材(C)が、アルミナ、酸化マグネシウム、窒化ホウ素及び窒化アルミニウムよりなる群から選択される1種である、
上記<11>に記載の樹脂組成物。
上記<1>~<12>のいずれか一項に記載の樹脂組成物。
<14> 前記シアン酸エステル化合物が、上記一般式(1)で表されるナフトールアラルキル型シアン酸エステル化合物である、
上記<13>に記載の樹脂組成物。
<15> 前記シアン酸エステル化合物(A)が、前記シアン酸エステル化合物(A)及び前記エポキシ樹脂(B)の合計100質量部に対して、10~90質量部含まれる、
上記<1>~<14>のいずれか一項に記載の樹脂組成物。
<16> さらにシランカップリング剤(E)を含む、
上記<1>~<15>のいずれか一項に記載の樹脂組成物。
<17> 前記シランカップリング剤が、前記シアン酸エステル化合物(A)及び前記エポキシ樹脂(B)の合計100質量部に対して、3~20質量部含まれる、
上記<16>に記載の樹脂組成物。
<18> さらにマレイミド化合物(F)を含む、
上記<1>~<17>のいずれか一項に記載の樹脂組成物。
<19> 前記マレイミド化合物(F)が、前記シアン酸エステル化合物(A)及び前記マレイミド化合物(F)の合計100質量部に対して、5~75質量部含まれる、
上記<18>に記載の樹脂組成物。
プレプリグ。
<21> 上記<20>に記載のプリプレグを硬化して得られる、
積層板。
<22> 上記<20>に記載のプリプレグと金属箔とを積層し硬化してなる、
金属箔張り積層板。
<23> 絶縁層と、前記絶縁層の表面に形成された導体層とを含むプリント配線板であって、
前記絶縁層が、上記<1>~<19>のいずれか一項に記載の樹脂組成物を含む
プリント配線板。
なお、シアン酸エステル化合物(A)は、目的に応じて1種を単独で或いは2種以上を適宜組み合わせて使用することができる。また、上記一般式(1)~(3)で表されるシアン酸エステル化合物として、各一般式(1)~(3)中のnが異なる2種以上のものを適宜混合して使用することもできる。
ここで、本実施形態の樹脂組成物においては、無機充填材の充填率を向上させるとともに樹脂組成物の成形性を高める観点から、第一の無機充填材(C)と第二の無機充填材(D)の平均粒子径の比が1:0.02~1:0.2であることが必要とされる。その理由は、平均粒子径が小さい方の無機充填材が大きい無機充填材の粒子の隙間に入り込むことにより、樹脂組成物中の無機充填材の体積含有率(以下、単に「充填率」ともいう。)を高めることができて熱伝導率を向上させることができるからである。ここで、第一の無機充填材(C)と第二の無機充填材(D)の平均粒子径の比は、より好ましくは1:0.025~1:0.18であり、さらに好ましくは1:0.05~1:0.14である。
なお、本明細書において、平均粒子径とは、メジアン径(D50)を意味し、測定した粉体の粒度分布を2つに分けたときの大きい側と小さい側が等量となる値である。より具体的には、本明細書中における平均粒子径(D50)は、後述する実施例の条件下でレーザ回折散乱式の粒度分布測定装置によりメチルエチルケトン中に分散させた粉体の粒度分布を測定したときの、小さい粒子から体積積算して全体積の50%に達したときの値を意味する。
なお、第二の無機充填材(D)との平均粒子径の比が1:0.02~1:0.2であることを満たす限り、第一の無機充填材(C)は、1種を単独で或いは2種以上を適宜組み合わせて使用することができる。
なお、第一の無機充填材(C)との平均粒子径の比が1:0.02~1:0.2であることを満たす限り、第二の無機充填材(D)は、1種を単独で或いは2種以上を適宜組み合わせて使用することができる。
また、第一の無機充填材(C)及び第二の無機充填材(D)の合計の体積が、樹脂組成物の全体積に対して、50体積%以上80体積%以下であることが好ましい。このような含有量で第一の無機充填材(C)と第二の無機充填材(D)を添加することにより、熱伝導率が飛躍的に向上することができるからである。
ここで使用されるシランカップリング剤(E)としては、一般に無機物の表面処理に使用されているものを好適に用いることができ、その種類は特に限定されない。その具体例としては、例えば、γ-アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルトリメトキシシランなどのアミノシラン系、γ-グリシドキシプロピルトリメトキシシランなどのエポキシシラン系、γ-メタアクリロキシプロピルトリメトキシシランなどのビニルシラン系、N-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリメトキシシラン塩酸塩などのカチオニックシラン系、フェニルシラン系などが挙げられるが、これらに特に限定されない。シランカップリング剤は、1種を単独で或いは2種以上を適宜組み合わせて使用することができる。
また、難燃性化合物としては、例えば、4,4’-ジブロモビフェニル等の臭素化合物、リン酸エステル、リン酸メラミン、リン含有エポキシ樹脂などのリン化合物、メラミンやベンゾグアナミンなどの窒素含有化合物、オキサジン環含有化合物、シリコン系化合物などが挙げられるが、これらに特に限定されない。難燃性化合物は、1種を単独で或いは2種以上を適宜組み合わせて使用することができる。
一方、各種添加剤の具体例としては、例えば、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、光増感剤、染料、染料、顔料、増粘剤、滑剤、消泡剤、上記湿潤分散剤以外の分散剤、レベリング剤、光沢剤、重合禁止剤等が挙げられるが、これらに特に限定されない。これら任意の配合物は、1種を単独で或いは2種以上を組み合わせて使用することができる。
基材の形状としては、織布、不織布、ロービング、チョップドストランドマット、サーフェシングマット等が知られており、また、織布の織り方としては、平織り、ななこ織り、綾織り等が知られているが、いずれであっても構わない。また、基材の厚みは、特に制限はされないが、通常は0.01~0.3mm程度であり、例えば積層板用途であれば0.01~0.2mmの範囲が好適である。これらの基材のなかでも、積層板用途においては面方向の膨張率と加工性とのバランスから、特にEガラスのガラス繊維を使用することが好ましい。
反応器内で、α-ナフトールアラルキル樹脂(SN495V、OH基当量:236g/eq.、新日鐵化学(株)製:ナフトールアラルキルの繰り返し単位数nは1~5のものが含まれる。)0.47モル(OH基換算)を、クロロホルム500mlに溶解させ、この溶液にトリエチルアミン0.7モルを添加した。温度を-10℃に保ちながら反応器内に0.93モルの塩化シアンのクロロホルム溶液300gを1.5時間かけて滴下し、滴下終了後、30分撹拌した。その後さらに、0.1モルのトリエチルアミンとクロロホルム30gの混合溶液を反応器内に滴下し、30分撹拌して反応を完結させた。副生したトリエチルアミンの塩酸塩を反応液から濾別した後、得られた濾液を0.1N塩酸500mlで洗浄した後、水500mlでの洗浄を4回繰り返した。これを硫酸ナトリウムにより乾燥した後、75℃でエバポレートし、さらに90℃で減圧脱気することにより、褐色固形の上記一般式(I)で表されるα-ナフトールアラルキル型シアン酸エステル化合物(式中のRはすべて水素原子である)を得た。得られたα-ナフトールアラルキル型シアン酸エステル化合物を赤外吸収スペクトルにより分析したところ、2264cm-1付近のシアン酸エステル基の吸収が確認された。
合成例1で得たα-ナフトールアラルキル型シアン酸エステル化合物40質量部と、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)20質量部と、ビフェニルアラルキル型エポキシ樹脂(NC-3000-FH,日本化薬(株)製)40質量部と、シランカップリング剤(Z6040、東レダウコーニング(株)製)15質量部と、酸基を含む湿潤分散剤(BYK-W903、ビッグケミー・ジャパン(株)製)5質量部とをメチルエチルケトン中で溶解混合し、これに、平均粒子径が3μmの真球状アルミナ(商品名:AX3-15、新日鉄住金マテリアルズ(株)マイクロン社製)500質量部と、平均粒子径が3μmの非球状アルミナ(商品名:アドバンストアルミナAA-3、住友化学(株)製)100質量部と、平均粒子径が0.3μmの球状アルミナ(商品名:ASFP-20、電気化学工業(株)製)150質量部と、ニッカオクチックスマンガン(Mn8%)(日本化学産業(株)製)0.01質量部と、2,4,5-トリフェニルイミダゾール(東京化成工業(株)製)0.5質量部とを混合して樹脂ワニスを調製した。
なお、平均粒子径は、各々の無機充填材をメチルエチルケトンで分散させ、その後超音波ホモジナイザーにて3分間分散処置を行ない、レーザ回折散乱式の粒度分布測定装置((株)島津製作所製)を用いて測定した値である。
得られた樹脂ワニスをさらにメチルエチルケトンで希釈して固形分濃度が65wt%の樹脂ワニスとし、この樹脂ワニスを厚さ0.05mmのEガラスクロス(旭化成イーマテリアルズ(株)製)に含浸塗工し、160℃で3分間加熱乾燥することにより0.1mmmtのプリプレグを作製した。
次に、得られたプリプレグを8枚重ね合わせ、得られた積層体の上下面に12μm厚の電解銅箔(3EC-III、三井金属鉱業(株)製)を配置し、圧力30kgf/cm2、温度220℃、120分間の真空プレスを行い積層成形することで、厚さ0.8mmの金属箔張り積層板(両面銅張積層板)を作製した。
1)熱伝導率:得られた金属張り積層板の密度を測定し、また、比熱をDSC(TA Instrumen Q100型)により測定し、さらに、キセノンフラッシュアナライザ(Bruker:LFA447 Nanoflash)により熱拡散率を測定した。そして、熱伝導率を以下の式から算出した。
熱伝導率(W/m・K)=密度(kg/m3)×比熱(kJ/kg・K)×熱拡散率(m2/S)×1000
2)ピール強度:JIS C6481のプリント配線板用銅張積層板試験方法(5.7引き剥がし強さ参照。)に準拠して測定した。
3)吸湿耐熱性:金属箔張り積層板をダイシングソーで50mm×50mm×0.8mmのサイズに切断後、片面の半分以外の銅箔をすべてエッチング除去して、片面にのみ銅箔が半分残された試験片を得た。この試験片を用い、プレシッヤークッカー試験機(平山製作所製、PC-3型)で121℃、2気圧で3時間処理後、260℃の半田槽の中に60秒浸漬した後の外観変化を目視で観察した(フクレ発生数/試験数)
4)曲げ強度:JIS K6911に準拠して、オートグラフ試験機で測定した。
5)弾性率:JIS K6911に準拠して、オートグラフ試験機で測定した。
6)外観評価:得られた金属張り積層板を520mm×340mm×0.8mmのサイズに切断後、両面の銅箔をすべてエッチング除去して、表面の銅箔がすべて除去されたサンプル(積層板)を得た。この積層板を目視で観察し、ボイドが発生してないものを「○」、ボイドが発生したものを「×」と評価した。
7)ガラス転移温度:得られた金属箔張り積層板をダイシングソーで40mm×20mm×0.8mmのサイズに切断して得たサンプルを用い、JIS C6481に準拠して、動的粘弾性分析装置(TAインスツルメント製)で測定した。
真球状アルミナ(AX3-15)の配合量を630質量部に、球状アルミナ(ASFP-20)の配合量を20質量部にそれぞれ変更し、非球状アルミナ(AA-3)の配合を省略すること以外は、実施例1と同様に行った。
シランカップリング剤(Z6040)の配合量を5質量部に、真球状アルミナ(AX3-15)の配合量を630質量部に、球状アルミナ(ASFP-20)の配合量を20質量部にそれぞれ変更し、非球状アルミナ(AA-3)の配合を省略すること以外は、実施例1と同様に行った。
シランカップリング剤(Z6040)の配合量を5質量部に、真球状アルミナ(AX3-15)の配合量を500質量部にそれぞれ変更し、非球状アルミナ(AA-3)及び球状アルミナ(ASFP-20)の配合を省略すること以外は、実施例1と同様に行った。
真球状アルミナ(AX3-15)の配合量を650質量部に変更し、非球状アルミナ(AA-3)及び球状アルミナ(ASFP-20)の配合を省略すること以外は、実施例1と同様に行った。
真球状アルミナ(AX3-15)の配合量を750質量部に変更し、非球状アルミナ(AA-3)及び球状アルミナ(ASFP-20)の配合を省略すること以外は、実施例1と同様に行った。
真球状アルミナ(AX3-15)及び非球状アルミナ(AA-3)の配合を省略し、球状アルミナ(ASFP-20)の配合量を750質量部に変更すること以外は、実施例1と同様に行った。
Claims (23)
- シアン酸エステル化合物(A)、エポキシ樹脂(B)、第一の無機充填材(C)及び第二の無機充填材(D)を少なくとも含有し、前記第一の無機充填材(C)と前記第二の無機充填材(D)の平均粒子径の比が1:0.02~1:0.2である、
樹脂組成物。 - 前記第一の無機充填材(C)と前記第二の無機充填材(D)の含有割合が、1:0.03~1:0.5である、
請求項1に記載の樹脂組成物。 - 前記第一の無機充填材(C)と前記第二の無機充填材(D)の合計含有量が、前記シアン酸エステル化合物(A)と前記エポキシ樹脂(B)の合計100質量部に対して、351~900質量部である、
請求項1又は2に記載の樹脂組成物。 - 前記第一の無機充填材(C)と前記第二の無機充填材(D)の合計含有量が、前記シアン酸エステル化合物(A)と前記エポキシ樹脂(B)の合計100質量部に対して、701~900質量部である、
請求項1又は2に記載の樹脂組成物。 - 前記第一の無機充填材(C)は、0.5~10μmの平均粒子径を有する、
請求項1~4のいずれか一項に記載の樹脂組成物。 - 前記第二の無機充填材(D)は、0.01~2μmの平均粒子径を有する、
請求項1~5のいずれか一項に記載の樹脂組成物。 - 前記第二の無機充填材(D)は、球状である、
請求項1~6のいずれか一項に記載の樹脂組成物。 - 前記第二の無機充填材(D)が、アルミナ、酸化マグネシウム、水酸化アルミニウム、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、モリブデン化合物、ホウ酸亜鉛及び窒化アルミニウムよりなる群から選択される少なくとも1種である、
請求項1~7のいずれか一項に記載の樹脂組成物。 - 前記第二の無機充填材(D)が、アルミナ、酸化マグネシウム、窒化ホウ素及び窒化アルミニウムよりなる群から選択される少なくとも1種である、
請求項8に記載の樹脂組成物。 - 前記第一の無機充填材(C)及び第二の無機充填材(D)が、樹脂組成物の全体積に対して、合計で50体積%以上80体積%以下含まれる、
請求項1~9のいずれか一項に記載の樹脂組成物。 - 前記第一の無機充填材(C)が、アルミナ、酸化マグネシウム、水酸化アルミニウム、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、モリブデン化合物、ホウ酸亜鉛及び窒化アルミニウムよりなる群から選択される1種である、
請求項1~10のいずれか一項に記載の樹脂組成物。 - 前記第一の無機充填材(C)が、アルミナ、酸化マグネシウム、窒化ホウ素及び窒化アルミニウムよりなる群から選択される1種である、
請求項11に記載の樹脂組成物。 - 前記シアン酸エステル化合物(A)が、下記一般式(1)で表されるナフトールアラルキル型シアン酸エステル化合物、下記一般式(2)で表されるノボラック型シアン酸エステル化合物、及び、下記一般式(3)で表されるビフェニルアラルキル型シアン酸エステル化合物よりなる群から選択される少なくとも1種である、
請求項1~12のいずれか一項に記載の樹脂組成物。 - 前記シアン酸エステル化合物が、上記一般式(1)で表されるナフトールアラルキル型シアン酸エステル化合物である、
請求項13に記載の樹脂組成物。 - 前記シアン酸エステル化合物(A)が、前記シアン酸エステル化合物(A)及び前記エポキシ樹脂(B)の合計100質量部に対して、10~90質量部含まれる、
請求項1~14のいずれか一項に記載の樹脂組成物。 - さらにシランカップリング剤(E)を含む、
請求項1~15のいずれか一項に記載の樹脂組成物。 - 前記シランカップリング剤が、前記シアン酸エステル化合物(A)及び前記エポキシ樹脂(B)の合計100質量部に対して、3~20質量部含まれる、
請求項16に記載の樹脂組成物。 - さらにマレイミド化合物(F)を含む、
請求項1~17のいずれか一項に記載の樹脂組成物。 - 前記マレイミド化合物(F)が、前記シアン酸エステル化合物(A)及び前記マレイミド化合物(F)の合計100質量部に対して、5~75質量部含まれる、
請求項18に記載の樹脂組成物。 - 請求項1~19のいずれか一項に記載の樹脂組成物を基材に含浸又は塗布してなる、
プレプリグ。 - 請求項20に記載のプリプレグを硬化して得られる、
積層板。 - 請求項20に記載のプリプレグと金属箔とを積層し硬化してなる、
金属箔張り積層板。 - 絶縁層と、前記絶縁層の表面に形成された導体層とを含むプリント配線板であって、
前記絶縁層が、請求項1~19のいずれか一項に記載の樹脂組成物を含む
プリント配線板。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12847461.6A EP2778198B1 (en) | 2011-11-07 | 2012-10-26 | Resin composition, and prepreg and laminated sheet each produced using same |
CN201280054753.XA CN103917596A (zh) | 2011-11-07 | 2012-10-26 | 树脂组合物、使用了其的预浸料和层压板 |
SG11201401906SA SG11201401906SA (en) | 2011-11-07 | 2012-10-26 | Resin composition, and prepreg and laminate using the same |
JP2013542924A JP6103486B2 (ja) | 2011-11-07 | 2012-10-26 | 樹脂組成物、これを用いたプリプレグ及び積層板 |
KR1020147011976A KR101945076B1 (ko) | 2011-11-07 | 2012-10-26 | 수지 조성물, 이것을 사용한 프리프레그 및 적층판 |
US14/356,266 US9775238B2 (en) | 2011-11-07 | 2012-10-26 | Resin composition, and prepreg and laminate using the same |
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JP (1) | JP6103486B2 (ja) |
KR (1) | KR101945076B1 (ja) |
CN (1) | CN103917596A (ja) |
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WO2013187536A1 (ja) * | 2012-06-14 | 2013-12-19 | 日本ゼオン株式会社 | 架橋性樹脂成形体、架橋樹脂成形体、および積層体 |
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KR101668855B1 (ko) * | 2013-09-30 | 2016-10-28 | 주식회사 엘지화학 | 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판 |
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JP2017014445A (ja) * | 2015-07-06 | 2017-01-19 | 株式会社トクヤマ | 窒化アルミニウム複合フィラーおよびこれを含む樹脂組成物 |
WO2018038179A1 (ja) | 2016-08-24 | 2018-03-01 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 |
US10689496B2 (en) | 2016-08-24 | 2020-06-23 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed circuit board |
KR20190038689A (ko) | 2016-08-24 | 2019-04-08 | 미츠비시 가스 가가쿠 가부시키가이샤 | 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트 및 프린트 배선판 |
KR20190099117A (ko) | 2017-02-07 | 2019-08-26 | 미츠비시 가스 가가쿠 가부시키가이샤 | 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트 및 프린트 배선판 |
US11098195B2 (en) | 2017-02-07 | 2021-08-24 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed circuit board |
WO2018147053A1 (ja) | 2017-02-07 | 2018-08-16 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 |
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Publication number | Publication date |
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KR20140090991A (ko) | 2014-07-18 |
JPWO2013069479A1 (ja) | 2015-04-02 |
TW201326276A (zh) | 2013-07-01 |
EP2778198A1 (en) | 2014-09-17 |
CN103917596A (zh) | 2014-07-09 |
KR101945076B1 (ko) | 2019-02-01 |
SG11201401906SA (en) | 2014-10-30 |
JP6103486B2 (ja) | 2017-03-29 |
EP2778198A4 (en) | 2015-06-24 |
US9775238B2 (en) | 2017-09-26 |
TWI605078B (zh) | 2017-11-11 |
EP2778198B1 (en) | 2018-02-14 |
US20140349089A1 (en) | 2014-11-27 |
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