Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4028—Isocyanates; Thioisocyanates
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general

Definitions

• the present invention relates to a resin composition and a method for manufacturing a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a printed wiring board using the composition.
• Patent Document 1 discloses a black polyimide film as a flexible printed wiring board that secures a light-shielding property by containing aniline black or the like.
• the present invention has been made in view of the above problems, and a resin composition capable of obtaining a rigid substrate having excellent light-shielding properties and surface hardness, and a prepreg and a resin sheet using the resin composition. It is an object of the present invention to provide a method for manufacturing a laminated board, a metal foil-covered laminated board, a printed wiring board, and a printed wiring board.
• n2 represents an integer of 1 or more.
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.
• the cyanate ester compound (F) contains a naphthol aralkyl type cyanate ester compound represented by the following formula (VI) and / or a novolak type cyanate ester compound represented by the following formula (VII).
• R 5 independently represents a hydrogen atom or a methyl group, and n 6 represents an integer of 1 or more.
• R 6 independently represents a hydrogen atom or a methyl group, and n 7 represents an integer of 1 or more.
• G Further comprising a maleimide compound (G), The resin composition according to any one of [1] to [6]. [8]
• the maleimide compound (G) is bis (4-maleimidephenyl) methane, 2,2'-bis ⁇ 4- (4-maleimidephenoxy) -phenyl ⁇ propane, bis (3-ethyl-5-methyl-4-maleimide).
• the barcol hardness of the metal foil-clad laminate is 70 to 80, and The transmittance of the substrate from which the metal foil has been removed from the metal foil-clad laminate in the wavelength range of 400 to 2000 nm is 0.1% or less.
• the metal foil-clad laminate according to [13]. [15] It was produced by using at least one selected from the group consisting of the prepreg according to [10] and the resin sheet according to [11] as a build-up material.
• a metal foil-clad laminate according to [13] or [14] was used as a build-up material.
• Printed wiring board. Insulation layer and Including a conductor layer formed on the surface of the insulating layer, The insulating layer contains the resin composition according to any one of [1] to [9]. Printed wiring board.
• the resin composition of the first embodiment is, for example, a resin composition used for a rigid substrate using a prepreg, particularly a glass cloth, as a base material and impregnating or coating the base material with the resin composition.
• the resin composition contains an epoxy compound (A), a curing agent (B), black particles (C), and an inorganic filler (D), and if necessary, a maleimide compound (G) and other materials. Ingredients may be included.
• an epoxy compound having a structure obtained by epoxidizing a certain resin or compound is described as "-type epoxy compound" in the name of the resin or compound. May be expressed as.
• the epoxy compound (A) is selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy compound, a bisnaphthalene type epoxy compound and an anthraquinone type epoxy compound. It is preferably one kind or two or more kinds, and a biphenyl aralkyl type epoxy resin is more preferable.
• phenol compound (E) As the phenol compound (E), any known compound can be appropriately used as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and the type thereof is not particularly limited.
• the cyanate ester compound (F) is not particularly limited, and for example, naphthol aralkyl type cyanate ester compound, novolac type cyanate ester compound, aromatic hydrocarbon formaldehyde type cyanic acid ester compound, and biphenyl aralkyl type cyanate. Examples thereof include acid ester compounds.
• the cyanide ester compound (F) may be used alone or in combination of two or more.
• a naphthol aralkyl type cyanate ester compound or a novolac type cyanate ester compound is preferable from the viewpoint of moldability and surface hardness.
• the novolak-type cyanide ester compound is not particularly limited, but for example, a compound represented by the following formula (VII) is preferable.
• R 6 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable.
• n7 represents an integer of 1 or more. The upper limit of n7 is preferably 10 and more preferably 7.
• the content of the cyanate ester compound (F) is preferably 30 to 70 parts by mass, and more preferably 35 to 65 parts, based on 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B). It is parts by mass, more preferably 40 to 60 parts by mass.
• the content of the cyanide ester compound (F) is within the above range, the moldability and the surface hardness tend to be further improved.
• two or more kinds of cyanate ester compounds (F) are used in combination, it is preferable that the total content thereof satisfies the above values.
• the black particles (C) are not particularly limited, and are, for example, carbon black, graphite powder, activated carbon powder, scaly graphite powder, acetylene black, ketjen black, fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nano.
• Carbon-based particles (carbon particles) such as cones; titanium-based particles such as titanium black can be mentioned. Among these, carbon particles are preferable, and carbon black is more preferable.
• the black particles (C) one type may be used alone, or two or more types may be used in combination.
• thermosetting resin that coats the surface of the black particles (C) is not particularly limited, and examples thereof include epoxy resin, polyurethane resin, acrylic resin, polyethylene resin, polycarbonate resin, and polyamide resin.
• the content of the black particles (C) is 1 to 20 parts by mass, preferably 2 to 17 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the content of the inorganic filler (D). It is a mass part.
• the content of the black particles (C) with respect to the inorganic filler (D) is within the above range, the light-shielding property and the moldability tend to be further improved.
• the inorganic filler (D) one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the maleimide compound (G) is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total content of the epoxy compound (A) and the curing agent (B). It is more preferably 15 to 20 parts by mass.
• the content of the maleimide compound (G) is within the above range, the moldability and the surface hardness tend to be further improved.
• two or more types of maleimide compounds (G) are used in combination, it is preferable that the total content thereof satisfies the above values.
• -Aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as ⁇ -acryloxypropyltrimethoxysilane; N- ⁇ - (N-) Examples thereof include cationic silane compounds such as vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds.
• the silane coupling agent may be used alone or in combination of two or more.
• the wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPERBYK-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903 and the like.
• Organic peroxides such as benzoyl peroxide, di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine , 2-N-Ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholin, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidin and other tertiary amines; phenol , Phenols such as xylenol, cresol, resorcin, catechol; organics such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acety
• the resin composition of the second embodiment is a resin composition containing an epoxy compound (A), a curing agent (B), black particles (C), and an inorganic filler (D), and the resin composition.
• the barcol hardness of the metal foil-clad laminate obtained by using a material is 60 to 90, and the transmittance of the substrate from which the metal foil has been removed from the metal foil-clad laminate in the wavelength range of 400 to 2000 nm is 0. It is 1% or less.
• the barcol hardness of the metal foil-clad laminate obtained by using the resin composition of the second embodiment is 60 to 90, preferably 65 to 75, and more preferably 70 to 80. When the barcol hardness is within the above range, it has sufficient surface hardness.
• the barcol hardness can be adjusted by the content of the inorganic filler (D), the content ratio of the black particles (C) and the inorganic filler (D), the type of the inorganic filler (D), and the like.
• the barcol hardness can be measured by the measuring method described in Examples.
• the transmittance of the substrate from which the metal foil has been removed from the metal foil-clad laminate obtained by using the resin composition of the second embodiment in the wavelength range of 400 to 2000 nm is 0.1% or less, and the transmittance is The lower limit of is not particularly limited, but is preferably equal to or less than the detection limit. When the transmittance is 0.1% or less, it has sufficient light-shielding property.
• the transmittance can be adjusted by adjusting the content of the black particles (C), the content ratio of the black particles (C) and the inorganic filler (D), the type of the black particles (C), and the like.
• the transmittance can be measured by the measuring method described in Examples.
• the same as in the first embodiment shall be exemplified with respect to the types and contents of the epoxy compound (A), the curing agent (B), the black particles (C), and the inorganic filler (D). Can be done.
• the method for producing the resin composition of the present embodiment (the resin composition of the first embodiment and the second embodiment) described above is not particularly limited, but for example, each of the above-mentioned components is sequentially blended with a solvent and sufficiently stirred. There is a way to do it. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability.
• the above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.
• an organic solvent can be used if necessary.
• the type of organic solvent is not particularly limited as long as it can dissolve the resin in the composition.
• the resin composition of the present embodiment described above can be suitably used as a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, or a printed wiring board.
• a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, or a printed wiring board will be described.
• the prepreg of the present embodiment has a base material and the resin composition of the present embodiment impregnated or coated on the base material.
• the method for producing the prepreg can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the base material with the resin composition of the present embodiment, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. , The prepreg of the present embodiment can be produced.
• the content of the resin composition (including the filler) of the present embodiment in the prepreg is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and preferably 35 to 85% by mass, based on the total amount of the prepreg. Is 40 to 80% by mass. When the content of the resin composition is within the above range, the moldability tends to be further improved.
• the base material is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance.
• Specific examples of the fibers constituting the base material are not particularly limited, but for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; quartz and the like.
• Inorganic fibers other than glass polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene-3,4'oxydiphenylene-terephthalamide (Technora (registered trademark), Teijin Techno Products Limited) Total aromatic polyamide such as 2,6-hydroxynaphthoic acid-parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Klaray Co., Ltd.), polyester such as Zexion (registered trademark, manufactured by KB Salen); polyparaphenylene Examples thereof include organic fibers such as benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.) and polyimide. Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers is preferable from the viewpoint of low coefficient of thermal expansion. These base materials may be used alone or in combination of two or more.
• the shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats.
• the weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, a glass woven fabric obtained by opening the fibers or surface-treating with a silane coupling agent or the like is preferably used.
• the thickness and mass of the base material are not particularly limited, but those having a thickness of about 0.01 to 0.3 mm are usually preferably used.
• the base material is preferably a glass woven cloth having a thickness of 200 ⁇ m or less and a mass of 250 g / m 2 or less, and a glass woven cloth made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.
• the resin sheet of the present embodiment has a support and the resin composition arranged on the support.
• the resin sheet is used as one means for thinning leaves, and can be produced, for example, by directly coating and drying a resin composition on a support such as a copper foil or a resin film.
• the resin sheet can be used to form an insulating layer such as a metal foil-clad laminate or a printed wiring board.
• the support is not particularly limited, but known materials used for various printed wiring board materials can be used.
• polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film examples thereof include an organic film base material such as a release film in which a release agent is applied to the surface of these films, a conductor foil such as copper foil, a glass plate, a SUS plate, and a plate-like inorganic film such as FPR. .. Among them, electrolytic copper foil and PET film are preferable.
• the resin sheet is preferably one that is semi-cured (B-staged) after the above resin composition is applied to the support.
• the resin composition is applied to a support such as a copper foil and then semi-cured by heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to produce a resin sheet. How to do it.
• the amount of the resin composition adhered to the support is preferably in the range of 1 to 300 ⁇ m in terms of the resin thickness of the resin sheet.
• the single-layer resin sheet of the present embodiment is a single-layer resin sheet.
• the single-layer resin sheet contains the resin composition of the present embodiment.
• the single-layer resin sheet is formed by molding the above resin composition into a sheet shape.
• the method for producing the single-layer resin sheet can be carried out according to a conventional method, and is not particularly limited. For example, it can be obtained by peeling or etching the support from the resin sheet. Alternatively, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, so that a sheet base material is not used.
• a single layer resin sheet can also be obtained.
• the laminated board of this embodiment is made by laminating the above prepreg.
• the laminated board is not particularly limited as long as it includes one or more prepreg layers, and may have any other layer.
• a method for producing the laminated board a generally known method can be appropriately applied and is not particularly limited.
• a laminated plate can be obtained by laminating the above-mentioned prepregs or the prepregs and other layers and heat-press molding.
• the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, more preferably 120 to 270 ° C.
• the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, more preferably 2.5 to 4 MPa.
• the laminated board of the present embodiment can be suitably used as a metal foil-clad laminated board described later by further providing a layer made of a metal foil.
• the barcol hardness of the metal foil-clad laminate of the present embodiment is preferably 60 to 90, more preferably 65 to 75, and even more preferably 70 to 80. When the barcol hardness is within the above range, it has sufficient surface hardness.
• the barcol hardness can be adjusted by the content of the inorganic filler (D), the content ratio of the black particles (C) and the inorganic filler (D), the type of the inorganic filler (D), and the like.
• the barcol hardness can be measured by the measuring method described in Examples.
• the metal foil-clad laminate of the other embodiment is not particularly limited as long as it satisfies the above configuration.
• the resin composition constituting the prepreg or the resin sheet the resin composition of the first or second embodiment is described. You don't have to use anything. Among these, it is preferable to use the resin composition of the first or second embodiment. In that case, the same type and content as those of the first embodiment can be exemplified with respect to the type and content of the resin component, the filler and the like in the resin composition. Further, regarding the barcol hardness and the transmittance, the same ranges as those described above can be exemplified.
• the printed wiring board having a multi-layer structure has a plurality of laminated insulating layers and a plurality of conductor layers arranged between the plurality of insulating layers and on the outermost layer surface, and the insulating layer has a plurality of laminated insulating layers.
• the one containing the resin composition of this embodiment can be mentioned.
• such a multilayer printed wiring board may have a configuration known as a multilayer printed wiring board, such as a plating through hole penetrating a plurality of insulating layers.
• the printed wiring board of the present embodiment can be manufactured by, for example, the following method.
• the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared.
• the surface of the metal foil-clad laminate is etched to form an inner layer circuit to create an inner layer substrate.
• the inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the metal foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold.
• a multi-layer laminated board in which an insulating layer made of a base material and a cured product of the resin composition of the present embodiment is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured.
• desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. ..
• a conductor layer for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of this hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, and a printed wiring board is manufactured.
• the above-mentioned prepreg (the base material and the above-mentioned resin composition attached thereto) and the resin composition layer (the layer composed of the above-mentioned resin composition) in the metal foil-clad laminate are the resin composition of the present embodiment.
• An insulating layer containing an object will be formed.
• a conductor layer serving as a circuit may be formed on the prepreg to produce a printed wiring board.
• an electroless plating method can also be used to form the conductor layer.
• a step of applying a solder resist to the printed wiring board obtained as described above to form an insulating film that protects the circuit pattern may be performed. More specifically, the step of preparing the printed wiring board as described above, the step of forming a photosensitive composition layer cured by light having a wavelength of 350 to 420 nm on both sides of the printed wiring board, and the step of forming the photosensitive composition layer.
• a method including a step of arranging a mask pattern on the surface and exposing with light having a wavelength of 350 to 420 nm through the mask pattern can be mentioned. After the exposure, the uncured portion of the photosensitive composition layer can be developed to obtain a printed wiring board in which the circuit pattern is protected. Examples of the photosensitive composition layer include a solder resist layer.
• a coreless printed wiring board on which a circuit pattern is formed can be obtained.
• solution 2 in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. I poured it over. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.
• reaction solution was allowed to stand to separate the organic phase and the aqueous phase.
• the obtained organic phase was washed 5 times with 1300 g of water, and the electric conductivity of the wastewater in the 5th washing with water was 5 ⁇ S / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
• the organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance).
• the mass average molecular weight Mw of the obtained SNCN was 600.
• Infrared absorption spectrum of SNCN showed absorption of 2250 cm -1 (cyanic acid ester group) and no absorption of hydroxy group.
• Example 1 50 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) and 50 parts by mass of biphenyl aralkyl type phenol resin (KAYAHARD GPH-103, hydroxyl group equivalent: 231 g / eq.
• Example 2 A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coated carbon black used was 5 parts by mass.
• Example 3 A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coated carbon black used was 20 parts by mass.
• Example 4 A prepreg was obtained in the same manner as in Example 1 except that the amount of silica used was 100 parts by mass.
• Example 5 A prepreg was obtained in the same manner as in Example 1 except that the amount of silica used was 150 parts by mass.
• Example 7 A prepreg was obtained in the same manner as in Example 1 except that 50 parts by mass of SNCN was used instead of the biphenyl aralkyl type phenol resin and bis (3-ethyl-5-methyl-4-maleimidephenyl) methane was not used. It was.
• Example 1 A prepreg was obtained in the same manner as in Example 1 except that the insulating coated carbon black was not used.
• Example 5 A prepreg was obtained in the same manner as in Example 1 except that the amount of the insulating coated carbon black used was 30 parts by mass.
• a mixed resin powder was obtained by evaporating and distilling off the methyl ethyl ketone of the varnish obtained in Example 1.
• the obtained mixed resin powder was filled into a mold having a side of 100 mm and a thickness of 0.1 mm and 0.8 mm, and laminated and molded at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes. Hardened products of .1 mm and 0.8 mm were obtained.
• the cured product does not use a glass woven fabric.
• a 12 ⁇ m-thick electrolytic copper foil (3EC-LPIII, manufactured by Mitsui Metal Mining Co., Ltd.) was placed vertically on the prepreg obtained in the Example or Comparative Example, and the pressure was 30 kgf / cm 2 , and the temperature was 220 ° C. for 120 minutes.
• Lamination molding was performed to obtain a copper-clad laminate having an insulating layer thickness of 0.1 mm as a metal foil-clad laminate.
• the substrate obtained by removing the copper foil of the copper-clad laminate by etching was used as a sample, and the transmittance at a wavelength of 400 to 2000 nm was measured.
• a spectrophotometer U-4100 manufactured by Hitachi High-Technology was used for the measurement.
• the light-shielding property was evaluated according to the following evaluation criteria.
• Reference Example 1 a cured product having a thickness of 0.1 mm was used as a sample, and the transmittance at a wavelength of 400 to 2000 nm was measured.
• ⁇ Transmittance in the wavelength range of 400 to 2000 nm is 0.1% or less
• ⁇ Transmittance in the wavelength range of 400 to 2000 nm exceeds 0.1%
• the resin composition of the present invention has industrial applicability as a material used for producing a rigid substrate.

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