WO2009113596A1 - Prepreg and laminate using the prepreg - Google Patents

Prepreg and laminate using the prepreg Download PDF

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Publication number
WO2009113596A1
WO2009113596A1 PCT/JP2009/054699 JP2009054699W WO2009113596A1 WO 2009113596 A1 WO2009113596 A1 WO 2009113596A1 JP 2009054699 W JP2009054699 W JP 2009054699W WO 2009113596 A1 WO2009113596 A1 WO 2009113596A1
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Prior art keywords
prepreg
conjugated diene
amino group
laminate
weight
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PCT/JP2009/054699
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French (fr)
Japanese (ja)
Inventor
有信 堅田
孝司 木内
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日本ゼオン株式会社
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Publication of WO2009113596A1 publication Critical patent/WO2009113596A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material

Definitions

  • the present invention relates to a prepreg suitably used for manufacturing a multilayer wiring board including an electric circuit board and a laminate using the prepreg.
  • a circuit board is generally composed of a dielectric layer and a conductor layer.
  • information transmission has begun to increase in speed and frequency, and microwave communication and millimeter wave communication have become a reality.
  • microwave communication and millimeter wave communication have become a reality.
  • Patent Document 1 discloses 1,2-polybutadiene having a molecular weight of less than 5,000 at room temperature, a thermoplastic block copolymer such as styrene-butadiene-styrene triblock copolymer which is a solid polymer, dicumyl peroxide and t-butyl.
  • a laminated body is disclosed in which a solvent is removed after impregnating to prepreg to prepare a prepreg, and then a plurality of prepregs are laminated between two copper foils and cured.
  • the laminate obtained by this method has a problem that the heat resistance is not sufficient, and when held at a high temperature, the dielectric loss tangent is increased and the mechanical properties are greatly deteriorated.
  • Patent Document 2 an ethylene-propylene polymer having a weight average molecular weight of less than 50,000 is added to a circuit board material containing a polybutadiene or polyisoprene polymer, a flame retardant, a knitted fabric, a particulate filler, and an organic peroxide. It is disclosed that by containing 6 to 12% by weight in the total polymer, deterioration due to heat is small and stability such as dielectric constant is improved. However, this method has a problem that sufficient heat resistance cannot be obtained.
  • An object of the present invention is to provide a prepreg that can be used as a high-frequency circuit board material that has high heat resistance and has stable dielectric loss tangent and mechanical strength even when used over a wide temperature range for a long time. And providing a laminate using the prepreg.
  • the present inventors have added an amino group-containing antioxidant to a curable composition containing a conjugated diene polymer such as 1,2-polybutadiene or a styrene-butadiene block copolymer and a radical generator. It has been found that the heat resistance can be improved while the dielectric loss tangent is low in the resulting laminate without blending the activity of the radical generator. Moreover, it discovered that these effects were remarkably improved by using a secondary amino group-containing anti-aging agent, particularly a diphenylamino group-containing anti-aging agent, as an amino group-containing anti-aging agent.
  • a secondary amino group-containing anti-aging agent particularly a diphenylamino group-containing anti-aging agent
  • the present inventors also inhibit the curing (crosslinking) reaction of the conjugated diene polymer by blending a specific amount of an amino group-containing antioxidant with the conjugated diene polymer or with the radical generator. It was found that the heat resistance of the resulting laminate was further improved. The present inventors have completed the invention based on these findings.
  • a prepreg obtained by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generator, and an amino group-containing antioxidant.
  • a laminate obtained by laminating the above prepreg or by laminating the prepreg and another material.
  • the prepreg of the present invention is formed by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generator, and an amino group-containing antioxidant.
  • the laminate of the present invention is cured after the prepreg is laminated or after the prepreg and other materials are laminated.
  • the conjugated diene polymer used in the present invention is a polymer containing at least a conjugated diene monomer unit.
  • the conjugated diene polymer is not particularly limited, but at least one selected from the group consisting of a conjugated diene homopolymer and a conjugated diene copolymer is preferably used.
  • the polymerization mode of these polymers is appropriately selected according to the purpose of use, and the polymerization of monomers can be carried out according to a conventional method.
  • conjugated diene monomer examples include butadiene, isoprene, chloroprene, pentadiene and the like, preferably butadiene and isoprene, and more preferably butadiene.
  • the conjugated diene homopolymer is a conjugated diene polymer composed only of conjugated diene monomer units, and there is no particular limitation as long as it is obtained by polymerizing a conjugated diene monomer.
  • Examples of the conjugated diene homopolymer include polybutadiene, polyisoprene, polychloroprene, polycyanobutadiene, polypentadiene, and the like, preferably polybutadiene, polyisoprene, and more preferably polybutadiene.
  • a conjugated diene copolymer is a copolymer containing at least conjugated diene monomer units.
  • the conjugated diene copolymer There is no particular limitation on the conjugated diene copolymer, and for example, a random copolymer or a block copolymer can be used.
  • a copolymerized monomer there is no particular limitation on the monomer that can be copolymerized with the conjugated diene monomer (hereinafter sometimes referred to as a copolymerized monomer).
  • cyano group-containing vinyl and aromatic vinyl are preferable, and aromatic vinyl is particularly preferable.
  • aromatic vinyl examples include styrene, ⁇ -methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2,4-diisopropyl styrene, 2,4-dimethyl styrene, and 4-t-butyl styrene. , 5-t-butyl-2-methylstyrene, N, N-dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, etc. Among them, styrene and ⁇ -methylstyrene are particularly preferable.
  • the ratio of the conjugated diene monomer unit to the copolymerized monomer unit in the conjugated diene copolymer is appropriately selected according to the purpose of use, and is usually 95/5 to 5 / in weight ratio of conjugated diene monomer unit / copolymerized monomer unit.
  • 95 preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and within this range, the resulting laminate has high properties such as heat resistance, mechanical strength and toughness. It is preferable to be balanced.
  • a block copolymer When a block copolymer is used as the conjugated diene copolymer, there is no particular limitation on the bonding mode of the block copolymer, and it is usually appropriately selected from 2-block copolymer, 3-block copolymer, 4-block copolymer, 5-block copolymer, etc. according to the purpose of use. However, diblock copolymers and triblock copolymers are preferred, and triblock copolymers are more preferred. If such a suitable block copolymer is used, the balance of the laminate property, heat resistance, and mechanical strength of the resulting laminate can be maintained at a high level, which is particularly preferred.
  • triblock copolymer examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, ⁇ -methylstyrene-butadiene- ⁇ -methylstyrene block copolymer, and preferably styrene-butadiene-styrene. It is a block copolymer.
  • the amount of 1,2-vinyl bond in the conjugated diene monomer unit portion of the conjugated diene polymer used in the present invention is appropriately selected according to the purpose of use, but is usually 5 mol% or more, preferably 40 mol% or more, More preferably, it is 60 mol% or more, and most preferably 80 mol% or more. When the amount of 1,2-vinyl bonds is within this range, it is preferable because the mechanical strength and heat resistance of the resulting laminate can be improved to a high degree.
  • the amount of 1,2-vinyl bonds in the conjugated diene polymer can be determined, for example, in the presence of a microstructure modifier composed of an organolithium compound as a polymerization initiator and a Lewis base compound such as an ether or tertiary amine in a hydrocarbon solvent. It can be adjusted by polymerization. The amount of 1,2-vinyl bond can be measured by infrared analysis.
  • the molecular weight of the conjugated diene polymer when the conjugated diene homopolymer or conjugated diene copolymer is used alone can be appropriately selected according to the purpose of use, but the weight measured by gel permeation chromatography (polystyrene conversion, toluene eluent).
  • the average molecular weight is usually in the range of 500 to 5,000,000, preferably 1,000 to 1,000,000.
  • the conjugated diene polymers may be used alone or in combination of two or more.
  • the prepreg laminating property and the heat resistance of the resulting laminate can be obtained. It is preferable because properties such as property and mechanical strength can be highly balanced.
  • the molecular weight of the conjugated diene homopolymer is a weight average molecular weight measured by gel permeation chromatography (polystyrene conversion, toluene eluent). Usually, it is in the range of 500 to 500,000, preferably 1,000 to 10,000, more preferably 1,000 to 5,000. The molecular weight of one conjugated diene copolymer is determined by gel permeation chromatography (polystyrene conversion).
  • the weight average molecular weight measured with a toluene eluent is usually in the range of 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 300,000. .
  • the molecular weights of the conjugated diene homopolymer and the conjugated diene copolymer are within this range, the relationship between the laminate property and mechanical strength of the obtained laminate can be highly balanced, which is preferable.
  • the use ratio in the case of combining the conjugated diene homopolymer and the conjugated diene copolymer is appropriately selected depending on the purpose of use, but is usually 10/90 to 95/5 in terms of the weight ratio of the conjugated diene homopolymer / conjugated diene copolymer.
  • the range is preferably 30/70 to 90/10, more preferably 50/50 to 85/15. When the ratio between the two is in this range, characteristics such as heat resistance, mechanical strength, dielectric loss tangent and the like of the obtained laminate are highly balanced.
  • the radical generator used in the present invention is not particularly limited as long as it can induce a curing reaction in the conjugated diene polymer.
  • organic peroxides, diazo compounds, nonpolar radical generators, and the like are used.
  • Organic peroxides and nonpolar radical generators are particularly preferable from the viewpoint of reducing the dielectric loss tangent of the obtained laminate.
  • crosslinking can occur in the conjugated diene polymer, for example, at a carbon-carbon double bond moiety.
  • organic peroxide examples include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy)
  • dialkyl peroxides and peroxyketals are preferable.
  • diazo compound examples include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4′-azidobenzal) cyclohexanone, and the like.
  • Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.
  • the 1-minute half-life temperature of the radical generator used in the present invention is appropriately selected depending on the type and use conditions of the radical generator, but is usually 50 to 350 ° C, preferably 100 to 250 ° C, more preferably 150. It is in the range of ⁇ 230 ° C.
  • radical generators can be used alone or in combination of two or more.
  • the amount of radical generator used is usually in the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the conjugated diene polymer. It is.
  • amino group-containing anti-aging agent In the present invention, one major feature is the use of an amino group-containing anti-aging agent as an anti-aging agent.
  • An amino group-containing anti-aging agent is an antioxidant having an amino group.
  • the amino group-containing anti-aging agent is not particularly limited, and usually a primary amino group-containing anti-aging agent or a secondary amino group-containing anti-aging agent is used, preferably a secondary amino group-containing anti-aging agent. An agent is used.
  • Examples of the primary amino group-containing antioxidant include aldol- ⁇ -naphthylamine, acetaldehyde aniline, p, p′-diaminodiphenylmethane, and the like.
  • Examples of secondary amino group-containing antioxidants include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and the like.
  • diphenylamino group-containing antioxidants having a high volatility point are preferable, and in particular, N-phenyl-1-naphthylamine, 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p- Toluenesulfonylamido) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, and the like, and a diphenylamino group-containing antioxidant containing three or more aromatic rings Is preferred.
  • These amino group-containing antioxidants can be used alone or in combination of two or more.
  • the amount of the amino group-containing antioxidant is appropriately selected according to the purpose of use, but from the viewpoint of improving the heat resistance of the resulting laminate without inhibiting the crosslinking reaction of the conjugated diene polymer.
  • the use ratio of the amino group-containing anti-aging agent and the radical generator is appropriately selected according to the purpose of use, and is usually 1/99 to 90/90 by weight ratio of the amino group-containing anti-aging agent / radical generator.
  • the range is 10, preferably 2/98 to 70/30, more preferably 3/97 to 50/50.
  • the use ratio of the amino group-containing antioxidant and the radical generator is within this range, the heat resistance of the resulting laminate can be improved without inhibiting the crosslinking reaction of the conjugated diene polymer. .
  • the curable composition used in the present invention contains the conjugated diene polymer, radical generator, and amino group-containing anti-aging agent as essential components, and optionally contains a filler, a crosslinking aid, a flame retardant, and other ingredients. An agent or the like can be added.
  • a filler to the curable composition because the heat resistance can be further improved in the obtained laminate.
  • the filler to be used is not particularly limited as long as it is generally used industrially, and either an inorganic filler or an organic filler can be used, but an inorganic filler is preferred.
  • the inorganic filler examples include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, and oxidation.
  • Inorganic oxide particles such as titanium, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, beryllium oxide, barium ferrite, and strontium ferrite; inorganic hydroxide particles such as aluminum hydroxide and magnesium hydroxide; calcium carbonate, Inorganic carbonate particles such as magnesium carbonate and sodium hydrogen carbonate; inorganic sulfate particles such as calcium sulfate; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass and glass balloon ; Calcium titanate And titanate particles such as lead zirconate titanate, aluminum nitride, silicon carbide particles and whiskers.
  • inorganic hydroxide particles such as aluminum hydroxide and magnesium hydroxide
  • calcium carbonate, Inorganic carbonate particles such as magnesium carbonate and sodium hydrogen carbonate
  • inorganic sulfate particles such as calcium sulfate
  • inorganic silicate particles such as talc, clay,
  • metal particles, inorganic oxide particles, inorganic hydroxide particles, inorganic silicate particles, titanate particles, and the like are preferable for highly balancing the dielectric loss tangent and heat resistance of the laminate.
  • Oxide particles and titanates are more preferred.
  • organic filler examples include compound particles such as wood powder, starch, organic pigment, polystyrene, nylon, polyolefin such as polyethylene and polypropylene, vinyl chloride, various elastomers, and waste plastic. These fillers can be used alone or in combination of two or more, and the addition amount is usually 10 to 1,000 parts by weight, preferably 50 parts per 100 parts by weight of the conjugated diene polymer. The range is from ⁇ 750 parts by weight, more preferably from 100 to 500 parts by weight.
  • the impregnation property of the curable composition into the reinforcing fibers can be highly improved in the production of the prepreg, and a laminate obtained by curing. It is preferable because the mechanical strength and heat resistance of the resin can be highly balanced.
  • the crosslinking aid used in the present invention is a bifunctional or higher functional compound capable of forming a crosslinked structure.
  • the crosslinking aid industrially used ones can be used without any particular limitation.
  • bifunctional compounds such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene, etc.
  • Trifunctional compounds such as triisopropenylbenzene and trimethallyl isocyanate.
  • the amount of the crosslinking aid is appropriately selected according to the purpose of use, but is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight of the conjugated diene polymer. Is in the range of 1 to 20 parts by weight.
  • a flame retardant used in the present invention, sufficient flame retardancy is imparted to the resulting laminate, which is preferable.
  • the flame retardant used those used industrially can be used without any particular limitation.
  • any of the following halogen flame retardants and non-halo flame retardants can be used.
  • Halogen flame retardant is a flame retardant containing halogen atoms.
  • the halogen-based flame retardant include hexabromobenzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3,5-dibromophenylpropane), pentabromotoluene, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneo Low molecular halogen-containing organic compounds such as pentyl phosphate and halogen-containing condensed phosphates; halogenated paraffins having a halogen content of 40 to 70% by weight; halogenated
  • Non-halogen flame retardants are flame retardants that do not contain halogen atoms, including, for example, metal hydroxide flame retardants, metal oxide flame retardants, phosphorus flame retardants, nitrogen flame retardants, both phosphorus and nitrogen And flame retardant.
  • metal hydroxide flame retardants include aluminum hydroxide and magnesium hydroxide.
  • metal oxide flame retardant include magnesium oxide and aluminum oxide.
  • phosphorus flame retardants include red phosphorus and phosphate esters.
  • phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, and the like.
  • a tertiary phosphate ester having a relatively high molecular weight such as tricresyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, and the like is preferable.
  • the nitrogen-based flame retardant is not particularly limited as long as it is a flame retardant containing nitrogen, and examples thereof include melamine derivatives, guanidines, isocyanuric acid, and preferably melamine derivatives.
  • examples of the melamine derivatives include melamine, melamine resin, melam, melem, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, melamine sulfate, guanylmelamine sulfate, melam sulfate, melem sulfate, Melamine sulfate is preferred.
  • guanidines examples include guanidine nitrate, guanidine carbonate, guanidine sulfamate, aminoguanidine nitrate, aminoguanidine bicarbonate, and preferably guanidine nitrate.
  • Examples of the flame retardant containing both phosphorus and nitrogen include ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, guanidine phosphate, phosphazenes, etc., preferably ammonium polyphosphate, melamine polyphosphate , Melam polyphosphate.
  • the flame retardants can be used alone or in combination of two or more.
  • the amount of the flame retardant added is usually in the range of 10 to 300 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the conjugated diene polymer.
  • Examples of other compounding agents include other polymer components, other anti-aging agents, colorants, dyes, and pigments. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.
  • the curable composition used in the present invention can be obtained by mixing the above components. Mixing can be performed according to a conventional method.
  • the reinforcing fiber used in the present invention is not particularly limited.
  • organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber;
  • inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, and the like.
  • organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable.
  • the glass fiber fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used.
  • reinforcing fibers can be used alone or in combination of two or more.
  • the amount of reinforcing fibers used is appropriately selected according to the purpose of use, but is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight in the prepreg or laminate. When the thickness is within this range, the dielectric loss tangent and heat resistance of the laminate are highly balanced and suitable.
  • the prepreg of the present invention can be produced by impregnating the curable composition into the reinforcing fiber.
  • the impregnation method conventional methods may be used.
  • a conjugated diene polymer, a radical generator, an amino group-containing anti-aging agent, and, if desired, a filler, a crosslinking aid, a flame retardant, and other compounding agents are used as solvents.
  • Wet method in which the reinforcing fiber is impregnated with a curable composition having a reduced viscosity by dissolving it in a solvent, and then the solvent is removed.
  • the curable composition is coated on a release paper, and the reinforcing fiber is aligned and heated to dissolve.
  • a hot melt method dry method in which the curable composition is impregnated with pressure using a roll or a doctor blade and then allowed to cool is used, but the wet method is usually used.
  • the drying temperature after impregnation by the wet method is usually in the range of 50 to 250 ° C., preferably 100 to 200 ° C., more preferably 120 to 170 ° C., and usually below the 1 minute half-life temperature of the radical generator,
  • the temperature is preferably 10 ° C. or more lower than the 1 minute half-life temperature, more preferably 20 ° C. or more lower than the 1 minute half-life temperature.
  • the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C.
  • the drying time may be appropriately selected, but is usually in the range of 0.1 to 120 minutes, preferably 0.5 to 60 minutes, more preferably 1 to 30 minutes.
  • the thickness of the prepreg of the present invention is appropriately selected depending on the purpose of use, but is usually in the range of 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably 0.05 to 0.5 mm. When the thickness of the prepreg is within this range, the operability of the prepreg and the mechanical strength and toughness of the laminate obtained by curing are sufficiently exhibited, which is preferable.
  • the laminate of the present invention can be produced by laminating the prepreg, or laminating the prepreg and other materials other than the prepreg, shaping them as desired, and then curing.
  • the other material that may be laminated is appropriately selected according to the purpose of use, and examples thereof include a thermoplastic resin material and a metal material, and preferably a metal material.
  • the metal material those generally used for circuit boards can be used without particular limitation, and usually metal foil, preferably copper foil is used.
  • the thickness of the metal material is appropriately selected according to the purpose of use, but is usually in the range of 1 to 50 ⁇ m, preferably 3 to 30 ⁇ m, more preferably 5 to 20 ⁇ m, and most preferably 5 to 15 ⁇ m.
  • the surface of the metal material is treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, and the like.
  • a silane coupling agent a silane coupling agent
  • a thiol coupling agent a titanate coupling agent
  • various adhesives and the like.
  • those treated with a silane coupling agent are more preferred.
  • the roughness (Rz) of the surface of the layer made of the metal material at the adhesion interface between the prepreg of the present invention and the metal material is not particularly limited, but is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, Preferably it is 2 micrometers or less.
  • the lower limit of the roughness is not particularly limited, but is usually 10 nm or more, preferably 5 nm or more, more preferably 1 nm or more. If the roughness of the surface of the layer made of a metal material is in the above range, the occurrence of noise, delay, transmission loss, etc. in high frequency transmission is preferably suppressed.
  • the adjustment of the roughness of the surface of the layer made of a metal material can be easily performed by selecting and using one having a roughness of the surface of the metal material to be laminated in a desired range. A metal material having such a surface roughness is available as a commercial product. The roughness (Rz) can be measured with an AFM (atomic force microscope).
  • the method for laminating and curing the prepreg may be in accordance with a conventional method, for example, a known press having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).
  • a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).
  • SMC sheet mold compound
  • BMC bulk mold compound
  • the heating temperature is a temperature at which crosslinking by the radical generator occurs, and is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. High temperature. Usually, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C.
  • the heating time is usually in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes.
  • the pressing pressure is usually 0.1 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 1 to 5 MPa. Further, the hot pressing may be performed in a vacuum or a reduced pressure atmosphere.
  • the laminate of the present invention thus obtained has little transmission loss in the high frequency region and is excellent in heat resistance. Therefore, it can be used for a long time in a wide temperature range and can be suitably used as a high frequency substrate material.
  • Dielectric loss tangent The dielectric loss tangent (tan ⁇ ) at 1 GHz of the laminate was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A). Judged by criteria. ⁇ : 100 or less ⁇ : More than 100
  • Heat resistance (dielectric loss tangent): After the obtained laminate was held at 230 ° C. for 30 days, an impedance analyzer (manufactured by Agilent Technologies, model number E4991A) was used. The dielectric loss tangent (tan ⁇ ) at 1 GHz of the laminate was measured by the capacitance method.
  • Example 1 "B3000” (polybutadiene homopolymer; manufactured by Nippon Soda Co., Ltd .; molecular weight 3000, 1,2-vinyl bond content 95 mol%) 100 parts, "Tufprene A (registered trademark)” (styrene-butadiene-styrene block copolymer; manufactured by Asahi Kasei Corporation Number average molecular weight 50000, bound styrene content 40%) 20 parts, bisphenol A bis (dicresyl) phosphate 80 parts as flame retardant, silica (manufactured by Admafine; particle size 0.5 ⁇ m) 150 parts, di-t as radical generator -1.2 parts of butyl peroxide and 1 part of 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline as an amino group-containing antioxidant were mixed in xylene to obtain a curable composition. Next, a glass cloth (E glass) was impregnated with the obtained cur
  • Example 2 A prepreg and a laminate were produced in the same manner as in Example 1 except that the amino group-containing antioxidant was changed to 0.8 part of 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, and each characteristic was evaluated. . The results are shown in Table 1.
  • Comparative Example 1 A prepreg and a laminate were prepared in the same manner as in Example 1 except that no anti-aging agent was used, and each characteristic was evaluated. The results are shown in Table 1.
  • Comparative Example 3 In the same manner as in Comparative Example 2, except that 1 part of 2,2-oxalylamidobis [ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) proprionate] was added as an antioxidant, A laminate was prepared and each characteristic was evaluated. The results are shown in Table 1.
  • Example 2 From Table 1, it can be seen that the laminates obtained in Examples 1 and 2 have excellent heat resistance and small changes in dielectric loss tangent and mechanical strength even when kept at high temperature for a long time. Moreover, it turns out that the effect is high when a diphenylamino group containing anti-aging agent is used (Example 2). On the other hand, when an amino group-containing anti-aging agent is not used, the heat resistance is inferior (Comparative Example 1), a polymer having an alicyclic structure is added (Comparative Example 2), and other anti-aging agents are added. (Comparative Example 3) Only a slight improvement in heat resistance was observed with respect to mechanical strength.

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Abstract

Disclosed is a prepreg which is obtained by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generating agent and an amino group-containing antioxidant. Also disclosed is a laminate obtained by laminating and then curing a plurality of the prepregs or laminating and then curing the prepreg(s) and another material.

Description

プリプレグ、及びそのプリプレグを用いた積層体Prepreg and laminate using the prepreg
  本発明は、電気回路基板を含む多層配線基板等の製造に好適に用いられるプリプレグ及びそのプリプレグを用いた積層体に関する。 The present invention relates to a prepreg suitably used for manufacturing a multilayer wiring board including an electric circuit board and a laminate using the prepreg.
  回路基板は、一般に誘電体層と導体層とから構成される。近年、高度情報化時代を迎え、情報伝送は高速化・高周波化に動き出し、マイクロ波通信やミリ波通信が現実になってきている。これらの高周波化時代の回路基板は、高周波におけるノイズや伝送ロスを極限まで軽減する必要があり、誘電正接（ｔａｎδ）が低い誘電体材料の選定が重要な課題となってきている。 A circuit board is generally composed of a dielectric layer and a conductor layer. In recent years, with the advent of advanced information technology, information transmission has begun to increase in speed and frequency, and microwave communication and millimeter wave communication have become a reality. In circuit boards in these high frequency eras, it is necessary to reduce noise and transmission loss at high frequencies as much as possible, and selection of a dielectric material having a low dielectric loss tangent (tan δ) has become an important issue.
  誘電正接の低い誘電材料としては、ポリブタジエンやポリイソプレン等の共役ジエンポリマーが注目されている。たとえば、特許文献１には、室温液状の分子量５，０００未満である１，２－ポリブタジエン、固体ポリマーであるスチレン－ブタジエン－スチレントリブロックコポリマー等の熱可塑性ブロックコポリマー、ジクミルペルオキシドやｔ－ブチルペルオキシヘキシン－３などの有機過酸化物及びエチレンビステトラブロモフタルイミド、テトラデカブロモジフェノキシベンゼン、デカブロモジフェノキシルオキシドなどの臭素含有難燃剤などを溶媒中で混合し、スラリーとして繊維強化材に含浸させた後に溶媒除去してプリプレグを作製し、次いで２枚の銅箔間に複数枚のプリプレグを積層し、硬化してなる積層体が開示されている。しかしながら、本法で得られる積層体では、耐熱性が十分ではなく、高温で保持した場合、誘電正接の増加、及び機械的特性の劣化が大きいという問題があった。 As a dielectric material having a low dielectric loss tangent, conjugated diene polymers such as polybutadiene and polyisoprene are attracting attention. For example, Patent Document 1 discloses 1,2-polybutadiene having a molecular weight of less than 5,000 at room temperature, a thermoplastic block copolymer such as styrene-butadiene-styrene triblock copolymer which is a solid polymer, dicumyl peroxide and t-butyl. Mixing organic peroxides such as peroxyhexine-3 and bromine-containing flame retardants such as ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenoxyloxide, etc. in a solvent, and as a fiber reinforcing material as a slurry A laminated body is disclosed in which a solvent is removed after impregnating to prepreg to prepare a prepreg, and then a plurality of prepregs are laminated between two copper foils and cured. However, the laminate obtained by this method has a problem that the heat resistance is not sufficient, and when held at a high temperature, the dielectric loss tangent is increased and the mechanical properties are greatly deteriorated.
  一方、特許文献２には、ポリブタジエンまたはポリイソプレンポリマー、引火遅延剤、編織物、粒状充填剤、有機過酸化物とを含む回路基板材料に重量平均分子量が５０，０００未満のエチレン－プロピレンポリマーを全ポリマー中の６～１２重量％含有させることで、熱による劣化が少なく誘電率等の安定性が改良されることが開示されている。しかしながら、本法でも十分な耐熱性が得られない問題があった。本法においては、また、２１０℃の熱劣化試験で老化防止剤としてＮａｕｇａｒｄ ＸＬ－１（登録商標）（２，２－オキサリルジアミドビス［エチル３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロプリオネート］）を添加しても改善効果が見られなかったことが記載されている。 On the other hand, in Patent Document 2, an ethylene-propylene polymer having a weight average molecular weight of less than 50,000 is added to a circuit board material containing a polybutadiene or polyisoprene polymer, a flame retardant, a knitted fabric, a particulate filler, and an organic peroxide. It is disclosed that by containing 6 to 12% by weight in the total polymer, deterioration due to heat is small and stability such as dielectric constant is improved. However, this method has a problem that sufficient heat resistance cannot be obtained. In this method, Nagard® XL-1® (2,2-oxalyldiamidobis [ethyl 3- (3,5-di-t-butyl-4) is used as an anti-aging agent in a heat deterioration test at 210 ° C. -Hydroxyphenyl) proprionate]) was added, no improvement effect was noted.
特開平８－２０８８５６号公報JP-A-8-208856 特表２００３－５２８４５０号公報Special table 2003-528450 gazette
  本発明の目的は、耐熱性が高く、広い温度範囲で長時間に渡って使用しても誘電正接及び機械的強度が安定な、高周波回路基板材料として好適に使用できる積層体を製造可能なプリプレグ、及びこのプリプレグを用いた積層体を提供することにある。 An object of the present invention is to provide a prepreg that can be used as a high-frequency circuit board material that has high heat resistance and has stable dielectric loss tangent and mechanical strength even when used over a wide temperature range for a long time. And providing a laminate using the prepreg.
  本発明者らは、上記課題に鑑み鋭意検討の結果、１，２－ポリブタジエンやスチレン－ブタジエンブロックコポリマーなどの共役ジエンポリマーとラジカル発生剤とを含む硬化性組成物にアミノ基含有老化防止剤を配合することでラジカル発生剤の活性を阻害せず、得られる積層体において誘電正接が低いまま耐熱性を向上させることができることを見出した。また、これらの効果は、アミノ基含有老化防止剤として、第２級アミノ基含有老化防止剤、特にジフェニルアミノ基含有老化防止剤を使用することで格段と向上することを見出した。本発明者らは、また、共役ジエンポリマーに対して、あるいはラジカル発生剤に対して、特定量のアミノ基含有老化防止剤を配合することで、共役ジエンポリマーの硬化（架橋）反応を阻害することなく、得られる積層体の耐熱性がいっそう向上することを見出した。本発明者らは、これらの知見に基づいて発明を完成するに至ったものである。 As a result of intensive studies in view of the above problems, the present inventors have added an amino group-containing antioxidant to a curable composition containing a conjugated diene polymer such as 1,2-polybutadiene or a styrene-butadiene block copolymer and a radical generator. It has been found that the heat resistance can be improved while the dielectric loss tangent is low in the resulting laminate without blending the activity of the radical generator. Moreover, it discovered that these effects were remarkably improved by using a secondary amino group-containing anti-aging agent, particularly a diphenylamino group-containing anti-aging agent, as an amino group-containing anti-aging agent. The present inventors also inhibit the curing (crosslinking) reaction of the conjugated diene polymer by blending a specific amount of an amino group-containing antioxidant with the conjugated diene polymer or with the radical generator. It was found that the heat resistance of the resulting laminate was further improved. The present inventors have completed the invention based on these findings.
  かくして本発明によれば、共役ジエンポリマー、ラジカル発生剤、及びアミノ基含有老化防止剤を含む硬化性組成物を強化繊維に含浸してなるプリプレグが提供される。
  本発明によれば、また、上記のプリプレグを積層した後、または前記プリプレグと他材料とを積層した後に硬化してなる積層体が提供される。 Thus, according to the present invention, there is provided a prepreg obtained by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generator, and an amino group-containing antioxidant.
According to the present invention, there is also provided a laminate obtained by laminating the above prepreg or by laminating the prepreg and another material.
  本発明によれば、耐熱性が高く、広い温度範囲で長時間に渡って使用しても誘電正接及び機械的強度が安定な、高周波回路基板材料として好適に使用できる積層体及びそれを与えるプリプレグを容易に製造することができる。また、本発明の積層体は、誘電正接が低く、耐熱性に優れるので、通信機器用途等のマイクロ波またはミリ波等の高周波回路基板に好適に使用することができる。 According to the present invention, a laminate that has high heat resistance and has stable dielectric loss tangent and mechanical strength even when used for a long time in a wide temperature range and can be suitably used as a high-frequency circuit board material, and a prepreg that provides the same Can be easily manufactured. Further, since the laminate of the present invention has a low dielectric loss tangent and excellent heat resistance, it can be suitably used for a high-frequency circuit board such as a microwave or millimeter wave for use in communication equipment.
　本発明のプリプレグは、共役ジエンポリマー、ラジカル発生剤、及びアミノ基含有老化防止剤を含む硬化性組成物を強化繊維に含浸してなる。また、本発明の積層体は、前記プリプレグを積層した後、又は前記プリプレグと他材料とを積層した後に硬化してなる。
（共役ジエンポリマー）
  本発明に使用される共役ジエンポリマーとは、共役ジエンモノマー単位を少なくとも含むポリマーである。かかる共役ジエンポリマーは格別に限定はされないが、共役ジエンホモポリマーと共役ジエンコポリマーとからなる群から選ばれる少なくとも１種が好適に用いられる。これらのポリマーの重合様式は、使用目的に応じて適宜選択され、モノマーの重合は常法に従って行なうことができる。 The prepreg of the present invention is formed by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generator, and an amino group-containing antioxidant. The laminate of the present invention is cured after the prepreg is laminated or after the prepreg and other materials are laminated.
(Conjugated diene polymer)
The conjugated diene polymer used in the present invention is a polymer containing at least a conjugated diene monomer unit. The conjugated diene polymer is not particularly limited, but at least one selected from the group consisting of a conjugated diene homopolymer and a conjugated diene copolymer is preferably used. The polymerization mode of these polymers is appropriately selected according to the purpose of use, and the polymerization of monomers can be carried out according to a conventional method.
  共役ジエンモノマーとしては、例えば、ブタジエン、イソプレン、クロロプレン、ペンタジエンなどが挙げられ、好ましくはブタジエンやイソプレン、より好ましくはブタジエンである。 Examples of the conjugated diene monomer include butadiene, isoprene, chloroprene, pentadiene and the like, preferably butadiene and isoprene, and more preferably butadiene.
  共役ジエンホモポリマーとは、共役ジエンモノマー単位のみからなる共役ジエンポリマーであり、共役ジエンモノマーを重合してなるものであれば格別の限定はない。共役ジエンホモポリマーとしては、例えば、ポリブタジエン、ポリイソプレン、ポリクロロプレン、ポリシアノブタジエン、ポリペンタジエンなどが挙げられ、好ましくはポリブタジエン、ポリイソプレン、より好ましくはポリブタジエンである。 The conjugated diene homopolymer is a conjugated diene polymer composed only of conjugated diene monomer units, and there is no particular limitation as long as it is obtained by polymerizing a conjugated diene monomer. Examples of the conjugated diene homopolymer include polybutadiene, polyisoprene, polychloroprene, polycyanobutadiene, polypentadiene, and the like, preferably polybutadiene, polyisoprene, and more preferably polybutadiene.
  共役ジエンコポリマーとは、共役ジエンモノマー単位を少なくとも含むコポリマーである。共役ジエンコポリマーに格別な限定はなく、例えば、ランダムコポリマーやブロックコポリマーを用いることができる。 A conjugated diene copolymer is a copolymer containing at least conjugated diene monomer units. There is no particular limitation on the conjugated diene copolymer, and for example, a random copolymer or a block copolymer can be used.
  共役ジエンモノマーと共重合し得るモノマー（以下、共重合モノマーという場合がある。）としては格別の限定はなく、例えば、シアノ基含有ビニル、アミノ基含有ビニル、ピリジル基含有ビニル、アルコキシル基含有ビニル、芳香族ビニルなどが挙げられ、これらの中でもシアノ基含有ビニルや芳香族ビニルが好ましく、特に芳香族ビニルが好ましい。芳香族ビニルとしては、例えば、スチレン、α－メチルスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、２，４－ジイソプロピルスチレン、２，４－ジメチルスチレン、４－ｔ－ブチルスチレン、５－ｔ－ブチル－２－メチルスチレン、Ｎ，Ｎ－ジメチルアミノエチルスチレン、Ｎ，Ｎ－ジエチルアミノエチルスチレンなどを挙げることができ、これらの中でも、スチレン、及びα－メチルスチレンが特に好ましい。 There is no particular limitation on the monomer that can be copolymerized with the conjugated diene monomer (hereinafter sometimes referred to as a copolymerized monomer). For example, cyano group-containing vinyl, amino group-containing vinyl, pyridyl group-containing vinyl, alkoxyl group-containing vinyl. , Aromatic vinyl, and the like. Among these, cyano group-containing vinyl and aromatic vinyl are preferable, and aromatic vinyl is particularly preferable. Examples of the aromatic vinyl include styrene, α-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2,4-diisopropyl styrene, 2,4-dimethyl styrene, and 4-t-butyl styrene. , 5-t-butyl-2-methylstyrene, N, N-dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, etc. Among them, styrene and α-methylstyrene are particularly preferable.
  共役ジエンコポリマー中の共役ジエンモノマー単位と共重合モノマー単位との割合は、使用目的に応じて適宜選択され、共役ジエンモノマー単位／共重合モノマー単位の重量比で、通常、９５／５～５／９５、好ましくは９０／１０～１０／９０、より好ましくは８０／２０～２０／８０の範囲であり、この範囲の時に、得られる積層体の耐熱性、機械的強度及び靭性等の特性が高度にバランスされ好適である。 The ratio of the conjugated diene monomer unit to the copolymerized monomer unit in the conjugated diene copolymer is appropriately selected according to the purpose of use, and is usually 95/5 to 5 / in weight ratio of conjugated diene monomer unit / copolymerized monomer unit. 95, preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and within this range, the resulting laminate has high properties such as heat resistance, mechanical strength and toughness. It is preferable to be balanced.
  共役ジエンコポリマーとしてブロックコポリマーを用いる場合、該ブロックコポリマーの結合様式に特に限定はなく、通常、２ブロックコポリマー、３ブロックコポリマー、４ブロックコポリマー、及び５ブロックコポリマー等から、使用目的に応じて適宜選択されるが、２ブロックコポリマーと３ブロックコポリマーが好適であり、３ブロックコポリマーがより好適である。かかる好適なブロックコポリマーを用いれば、得られる積層体の積層性、耐熱性及び機械的強度のバランスを高度に保つことができ特に好適である。３ブロックコポリマーの具体例としては、スチレン－ブタジエン－スチレンブロックコポリマー、スチレン－イソプレン－スチレンブロックコポリマー、α－メチルスチレン－ブタジエン－α－メチルスチレンブロックコポリマーなどが挙げられ、好ましくはスチレン－ブタジエン－スチレンブロックコポリマーである。 When a block copolymer is used as the conjugated diene copolymer, there is no particular limitation on the bonding mode of the block copolymer, and it is usually appropriately selected from 2-block copolymer, 3-block copolymer, 4-block copolymer, 5-block copolymer, etc. according to the purpose of use. However, diblock copolymers and triblock copolymers are preferred, and triblock copolymers are more preferred. If such a suitable block copolymer is used, the balance of the laminate property, heat resistance, and mechanical strength of the resulting laminate can be maintained at a high level, which is particularly preferred. Specific examples of the triblock copolymer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, α-methylstyrene-butadiene-α-methylstyrene block copolymer, and preferably styrene-butadiene-styrene. It is a block copolymer.
  本発明に使用される共役ジエンポリマーの共役ジエンモノマー単位部分の１，２－ビニル結合量は、使用目的に応じて適宜選択されるが、通常、５モル％以上、好ましくは４０モル％以上、より好ましくは６０モル％以上、最も好ましくは８０モル％以上である。１，２－ビニル結合量がこの範囲である時に、得られる積層体の機械的強度や耐熱性を高度に向上させることができ好適である。共役ジエンポリマーの１，２－ビニル結合量は、例えば、炭化水素溶媒中、有機リチウム化合物を重合開始剤とし、エーテル又は第三級アミンのようなルイス塩基化合物からなるミクロ構造調節剤の存在下、重合することにより調整可能である。当該１，２－ビニル結合量は赤外分析法により測定可能である。 The amount of 1,2-vinyl bond in the conjugated diene monomer unit portion of the conjugated diene polymer used in the present invention is appropriately selected according to the purpose of use, but is usually 5 mol% or more, preferably 40 mol% or more, More preferably, it is 60 mol% or more, and most preferably 80 mol% or more. When the amount of 1,2-vinyl bonds is within this range, it is preferable because the mechanical strength and heat resistance of the resulting laminate can be improved to a high degree. The amount of 1,2-vinyl bonds in the conjugated diene polymer can be determined, for example, in the presence of a microstructure modifier composed of an organolithium compound as a polymerization initiator and a Lewis base compound such as an ether or tertiary amine in a hydrocarbon solvent. It can be adjusted by polymerization. The amount of 1,2-vinyl bond can be measured by infrared analysis.
  共役ジエンホモポリマーまたは共役ジエンコポリマーをそれぞれ単独で用いる場合の共役ジエンポリマーの分子量は、使用目的に応じて適宜選択できるが、ゲルパーミエーションクロマトグラフィー（ポリスチレン換算、トルエン溶離液）で測定される重量平均分子量で、通常、５００～５，０００，０００、好ましくは１，０００～１，０００，０００の範囲である。 The molecular weight of the conjugated diene polymer when the conjugated diene homopolymer or conjugated diene copolymer is used alone can be appropriately selected according to the purpose of use, but the weight measured by gel permeation chromatography (polystyrene conversion, toluene eluent). The average molecular weight is usually in the range of 500 to 5,000,000, preferably 1,000 to 1,000,000.
  本発明において、上記共役ジエンポリマーは、それぞれ単独で、あるいは２種以上を組み合わせて用いることができるが、共役ジエンホモポリマーと共役ジエンコポリマーを組み合わせることでプリプレグの積層性並びに得られる積層体の耐熱性及び機械的強度等の特性を高度にバランスさせることができ好適である。 In the present invention, the conjugated diene polymers may be used alone or in combination of two or more. However, by combining a conjugated diene homopolymer and a conjugated diene copolymer, the prepreg laminating property and the heat resistance of the resulting laminate can be obtained. It is preferable because properties such as property and mechanical strength can be highly balanced.
  共役ジエンポリマーとして共役ジエンホモポリマーと共役ジエンコポリマーとを組み合わせて用いる場合の、共役ジエンホモポリマーの分子量は、ゲルパーミエーションクロマトグラフィー（ポリスチレン換算、トルエン溶離液）で測定される重量平均分子量で、通常、５００～５００，０００、好ましくは１，０００～１０，０００、より好ましくは１，０００～５，０００の範囲であり、一方の共役ジエンコポリマーの分子量は、ゲルパーミエーションクロマトグラフィー（ポリスチレン換算、トルエン溶離液）で測定される重量平均分子量で、通常、１，０００～１，０００，０００、好ましくは５，０００～５００，０００、より好ましくは１０，０００～３００，０００の範囲である。共役ジエンホモポリマーと共役ジエンコポリマーの分子量がこの範囲である時に、得られる積層体の積層性と機械的強度との関係を高度にバランスさせることができ好適である。 When a conjugated diene homopolymer and a conjugated diene copolymer are used in combination as the conjugated diene polymer, the molecular weight of the conjugated diene homopolymer is a weight average molecular weight measured by gel permeation chromatography (polystyrene conversion, toluene eluent). Usually, it is in the range of 500 to 500,000, preferably 1,000 to 10,000, more preferably 1,000 to 5,000. The molecular weight of one conjugated diene copolymer is determined by gel permeation chromatography (polystyrene conversion). The weight average molecular weight measured with a toluene eluent) is usually in the range of 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 300,000. . When the molecular weights of the conjugated diene homopolymer and the conjugated diene copolymer are within this range, the relationship between the laminate property and mechanical strength of the obtained laminate can be highly balanced, which is preferable.
  共役ジエンホモポリマーと共役ジエンコポリマーを組み合わせる場合の使用割合は、使用目的に応じて適宜選択されるが、共役ジエンホモポリマー／共役ジエンコポリマーの重量比で、通常、１０／９０～９５／５、好ましくは３０／７０～９０／１０、より好ましくは５０／５０～８５／１５の範囲である。両者の割合がこの範囲にあるときに、得られる積層体の耐熱性、機械的強度及び誘電正接等の特性が高度にバランスされ好適である。 The use ratio in the case of combining the conjugated diene homopolymer and the conjugated diene copolymer is appropriately selected depending on the purpose of use, but is usually 10/90 to 95/5 in terms of the weight ratio of the conjugated diene homopolymer / conjugated diene copolymer. The range is preferably 30/70 to 90/10, more preferably 50/50 to 85/15. When the ratio between the two is in this range, characteristics such as heat resistance, mechanical strength, dielectric loss tangent and the like of the obtained laminate are highly balanced.
（ラジカル発生剤）
  本発明に使用されるラジカル発生剤は、上記共役ジエンポリマーにおいて硬化反応を誘起し得るものであれば格別な限定はないが、通常、有機過酸化物、ジアゾ化合物および非極性ラジカル発生剤などが挙げられ、有機過酸化物や非極性ラジカル発生剤が、得られる積層体の誘電正接を低下させる観点から特に好適である。ラジカル発生剤によれば、共役ジエンポリマー中、例えば、炭素－炭素二重結合部分で架橋が生じ得る。 (Radical generator)
The radical generator used in the present invention is not particularly limited as long as it can induce a curing reaction in the conjugated diene polymer. Usually, organic peroxides, diazo compounds, nonpolar radical generators, and the like are used. Organic peroxides and nonpolar radical generators are particularly preferable from the viewpoint of reducing the dielectric loss tangent of the obtained laminate. According to the radical generator, crosslinking can occur in the conjugated diene polymer, for example, at a carbon-carbon double bond moiety.
  有機過酸化物としては、例えば、ｔ－ブチルヒドロペルオキシド、ｐ－メンタンヒドロペルオキシド、クメンヒドロペルオキシドなどのヒドロペルオキシド類；ジクミルペルオキシド、ｔ－ブチルクミルペルオキシド、α，α’－ビス（ｔ－ブチルペルオキシ－ｍ－イソプロピル）ベンゼン、ジ－ｔ－ブチルペルオキシド、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）－３－ヘキシン、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）ヘキサンなどのジアルキルペルオキシド類；ジプロピオニルペルオキシド、ベンゾイルペルオキシドなどのジアシルペルオキシド類；２，２－ジ（ｔ－ブチルペルオキシ）ブタン、１，１－ジ（ｔ－ヘキシルペルオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルペルオキシ）－２－メチルシクロヘキサン、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサンなどのペルオキシケタール類；ｔ－ブチルペルオキシアセテート、ｔ－ブチルペルオキシベンゾエートなどのペルオキシエステル類；ｔ－ブチルペルオキシイソプロピルカルボナート、ジ（イソプロピルペルオキシ）ジカルボナートなどのペルオキシカルボナート類；ｔ－ブチルトリメチルシリルペルオキシドなどのアルキルシリルペルオキシド類；などが挙げられる。中でも、ジアルキルペルオキシド類およびペルオキシケタール類が好ましい。
　ジアゾ化合物としては、例えば、４，４’－ビスアジドベンザル（４－メチル）シクロヘキサノン、２，６－ビス（４’－アジドベンザル）シクロヘキサノンなどが挙げられる。
  非極性ラジカル発生剤としては、２，３－ジメチル－２，３－ジフェニルブタン、３，４－ジメチル－３，４－ジフェニルヘキサン、１，１，２－トリフェニルエタン、１，１，１－トリフェニル－２－フェニルエタンなどが挙げられる。 Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α'-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) And peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides and peroxyketals are preferable.
Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4′-azidobenzal) cyclohexanone, and the like.
Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.
  本発明に使用されるラジカル発生剤の１分間半減期温度は、ラジカル発生剤の種類及び使用条件により適宜選択されるが、通常、５０～３５０℃、好ましくは１００～２５０℃、より好ましくは１５０～２３０℃の範囲である。 The 1-minute half-life temperature of the radical generator used in the present invention is appropriately selected depending on the type and use conditions of the radical generator, but is usually 50 to 350 ° C, preferably 100 to 250 ° C, more preferably 150. It is in the range of ~ 230 ° C.
  これらのラジカル発生剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。ラジカル発生剤の使用量は、共役ジエンポリマー１００重量部に対して、通常、０．０１～１０重量部、好ましくは０．１～１０重量部、より好ましくは０．５～５重量部の範囲である。 These radical generators can be used alone or in combination of two or more. The amount of radical generator used is usually in the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the conjugated diene polymer. It is.
（アミノ基含有老化防止剤）
  本発明においては、老化防止剤としてアミノ基含有老化防止剤を使用することを１つの大きな特徴とする。
  アミノ基含有老化防止剤とは、アミノ基を有する抗酸化物質である。アミノ基含有老化防止剤には格別な限定はなく、通常、第１級アミノ基含有老化防止剤や第２級アミノ基含有老化防止剤が用いられ、好ましくは、第２級アミノ基含有老化防止剤が用いられる。 (Amino group-containing anti-aging agent)
In the present invention, one major feature is the use of an amino group-containing anti-aging agent as an anti-aging agent.
An amino group-containing anti-aging agent is an antioxidant having an amino group. The amino group-containing anti-aging agent is not particularly limited, and usually a primary amino group-containing anti-aging agent or a secondary amino group-containing anti-aging agent is used, preferably a secondary amino group-containing anti-aging agent. An agent is used.
  第１級アミノ基含有老化防止剤としては、例えば、アルドール－α－ナフチルアミン、アセトアルデヒドアニリン、ｐ，ｐ’－ジアミノジフェニルメタンなどが挙げられる。
  第２級アミノ基含有老化防止剤としては、例えば、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、６－エトキシ－１，２－ジヒドロ－２，２，４－トリメチルキノリンなどの第２級アミノ基・ケトン基含有老化防止剤；Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－イソプロピル－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミンなどの、分子中にジフェニルアミン構造を有する化合物であるジフェニルアミノ基含有老化防止剤；などが挙げられる。これらの中でも、高揮発点を有するジフェニルアミノ基含有老化防止剤が好ましく、特に、Ｎ－フェニル－１－ナフチルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミンなどの、芳香環を３つ以上有するジフェニルアミノ基含有老化防止剤が好適である。
  これらのアミノ基含有老化防止剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。 Examples of the primary amino group-containing antioxidant include aldol-α-naphthylamine, acetaldehyde aniline, p, p′-diaminodiphenylmethane, and the like.
Examples of secondary amino group-containing antioxidants include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and the like. Secondary amino group / ketone group-containing antioxidants: N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamide) ) Diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N '-(1,3-Dimethylbutyl) -p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxy And a diphenylamino group-containing anti-aging agent which is a compound having a diphenylamine structure in the molecule, such as propyl) -p-phenylenediamine. Among these, diphenylamino group-containing antioxidants having a high volatility point are preferable, and in particular, N-phenyl-1-naphthylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p- Toluenesulfonylamido) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, and the like, and a diphenylamino group-containing antioxidant containing three or more aromatic rings Is preferred.
These amino group-containing antioxidants can be used alone or in combination of two or more.
  アミノ基含有老化防止剤の使用量は、使用目的に応じて適宜選択されるが、共役ジエンポリマーの架橋反応を阻害することなく、得られる積層体の耐熱性を向上させる観点から、共役ジエンポリマー１００重量部に対して、通常、０．０００１～１０重量部、好ましくは０．００１～５重量部、より好ましくは０．０１～３重量部、特に好ましくは０．０２～１重量部の範囲である。 The amount of the amino group-containing antioxidant is appropriately selected according to the purpose of use, but from the viewpoint of improving the heat resistance of the resulting laminate without inhibiting the crosslinking reaction of the conjugated diene polymer. Usually in the range of 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, and particularly preferably 0.02 to 1 part by weight with respect to 100 parts by weight. It is.
  アミノ基含有老化防止剤とラジカル発生剤との使用割合は、使用目的に応じて適宜選択されるが、アミノ基含有老化防止剤／ラジカル発生剤の重量比で、通常、１／９９～９０／１０、好ましくは２／９８～７０／３０、より好ましくは３／９７～５０／５０の範囲である。アミノ基含有老化防止剤とラジカル発生剤との使用割合がこの範囲にあるときに、共役ジエンポリマーの架橋反応を阻害することなく、得られる積層体の耐熱性を向上することができ好適である。 The use ratio of the amino group-containing anti-aging agent and the radical generator is appropriately selected according to the purpose of use, and is usually 1/99 to 90/90 by weight ratio of the amino group-containing anti-aging agent / radical generator. The range is 10, preferably 2/98 to 70/30, more preferably 3/97 to 50/50. When the use ratio of the amino group-containing antioxidant and the radical generator is within this range, the heat resistance of the resulting laminate can be improved without inhibiting the crosslinking reaction of the conjugated diene polymer. .
（硬化性組成物）
  本発明に使用される硬化性組成物には、上記共役ジエンポリマー、ラジカル発生剤、及びアミノ基含有老化防止剤を必須成分として、所望により、充填剤、架橋助剤、難燃剤及びその他の配合剤などを添加することができる。 (Curable composition)
The curable composition used in the present invention contains the conjugated diene polymer, radical generator, and amino group-containing anti-aging agent as essential components, and optionally contains a filler, a crosslinking aid, a flame retardant, and other ingredients. An agent or the like can be added.
  本発明においては、硬化性組成物に充填剤を添加することで、得られる積層体においてより耐熱性を向上させることができ好適である。使用される充填剤は、工業的に一般に使用されるものであれば格別な限定はなく無機充填剤や有機充填剤のいずれも用いることができるが、好適には無機充填剤である。 に お い て In the present invention, it is preferable to add a filler to the curable composition because the heat resistance can be further improved in the obtained laminate. The filler to be used is not particularly limited as long as it is generally used industrially, and either an inorganic filler or an organic filler can be used, but an inorganic filler is preferred.
  無機充填剤としては、例えば、鉄、銅、ニッケル、金、銀、アルミニウム、鉛、タングステン等の金属粒子；カーボンブラック、グラファイト、活性炭、炭素バルーン等の炭素粒子；シリカ、シリカバルーン、アルミナ、酸化チタン、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化すず、酸化アンチモン、酸化ベリリウム、バリウムフェライト、ストロンチウムフェライト等の無機酸化物粒子；水酸化アルミニウム、水酸化マグネシウム等の無機水酸化物粒子；炭酸カルシウム、炭酸マグネシウム、炭酸水素ナトリウム等の無機炭酸塩粒子；硫酸カルシウム等の無機硫酸塩粒子；タルク、クレー、マイカ、カオリン、フライアッシュ、モンモリロナイト、ケイ酸カルシウム、ガラス、ガラスバルーン等の無機ケイ酸塩粒子；チタン酸カルシウム、チタン酸ジルコン酸鉛等のチタン酸塩粒子、窒化アルミニウム、炭化ケイ素粒子やウィスカー等が挙げられる。これらの中でも、積層体の誘電正接と耐熱性を高度にバランスさせるためには、金属粒子、無機酸化物粒子、無機水酸化物粒子、無機ケイ酸塩粒子及びチタン酸塩粒子などが好ましく、無機酸化物粒子やチタン酸塩などがより好ましい。 Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, and oxidation. Inorganic oxide particles such as titanium, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, beryllium oxide, barium ferrite, and strontium ferrite; inorganic hydroxide particles such as aluminum hydroxide and magnesium hydroxide; calcium carbonate, Inorganic carbonate particles such as magnesium carbonate and sodium hydrogen carbonate; inorganic sulfate particles such as calcium sulfate; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass and glass balloon ; Calcium titanate And titanate particles such as lead zirconate titanate, aluminum nitride, silicon carbide particles and whiskers. Among these, metal particles, inorganic oxide particles, inorganic hydroxide particles, inorganic silicate particles, titanate particles, and the like are preferable for highly balancing the dielectric loss tangent and heat resistance of the laminate. Oxide particles and titanates are more preferred.
  有機充填剤としては、例えば、木粉、デンプン、有機顔料、ポリスチレン、ナイロン、ポリエチレンやポリプロピレンのようなポリオレフィン、塩化ビニル、各種エラストマー、廃プラスチック等の化合物粒子が挙げられる。
  これらの充填剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その添加量は、共役ジエンポリマー１００重量部に対して、通常、１０～１，０００重量部、好ましくは５０～７５０重量部、より好ましくは１００～５００重量部の範囲である。 Examples of the organic filler include compound particles such as wood powder, starch, organic pigment, polystyrene, nylon, polyolefin such as polyethylene and polypropylene, vinyl chloride, various elastomers, and waste plastic.
These fillers can be used alone or in combination of two or more, and the addition amount is usually 10 to 1,000 parts by weight, preferably 50 parts per 100 parts by weight of the conjugated diene polymer. The range is from ˜750 parts by weight, more preferably from 100 to 500 parts by weight.
  本発明においては、硬化性組成物に架橋助剤を添加することにより、プリプレグの製造に際しては硬化性組成物の強化繊維への含浸性を高度に向上でき、また、硬化して得られる積層体の機械的強度と耐熱性を高度にバランスさせることができ好適である。 In the present invention, by adding a crosslinking aid to the curable composition, the impregnation property of the curable composition into the reinforcing fibers can be highly improved in the production of the prepreg, and a laminate obtained by curing. It is preferable because the mechanical strength and heat resistance of the resin can be highly balanced.
  本発明に用いる架橋助剤は、架橋構造を形成し得る２官能性以上の化合物である。架橋助剤としては、工業的に用いられるものを格別な限定なく用いることができ、例えば、ｐ－ジイソプロペニルベンゼン、ｍ－ジイソプロペニルベンゼン、ｏ－ジイソプロペニルベンゼンなどの２官能性化合物、トリイソプロペニルベンゼン、トリメタアリルイソシアネートなどの３官能性化合物等が挙げられる。
  これらの架橋助剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。架橋助剤の使用量は、使用目的に応じて適宜選択されるが、共役ジエンポリマー１００重量部に対し、通常、０．１～５０重量部、好ましくは０．５～３０重量部、より好ましくは１～２０重量部の範囲である。 The crosslinking aid used in the present invention is a bifunctional or higher functional compound capable of forming a crosslinked structure. As the crosslinking aid, industrially used ones can be used without any particular limitation. For example, bifunctional compounds such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene, etc. , Trifunctional compounds such as triisopropenylbenzene and trimethallyl isocyanate.
These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is appropriately selected according to the purpose of use, but is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight of the conjugated diene polymer. Is in the range of 1 to 20 parts by weight.
  本発明においては、硬化性組成物に難燃剤を添加することにより、得られる積層体に充分な難燃性が付与され好適である。
  使用される難燃剤は、工業的に用いられるものを格別な限定はなく用いることができ、例えば、以下のようなハロゲン系難燃剤やノンハロ系難燃剤のいずれをも用いることができる。 In the present invention, by adding a flame retardant to the curable composition, sufficient flame retardancy is imparted to the resulting laminate, which is preferable.
As the flame retardant used, those used industrially can be used without any particular limitation. For example, any of the following halogen flame retardants and non-halo flame retardants can be used.
  ハロゲン系難燃剤は、ハロゲン原子を含む難燃剤である。ハロゲン系難燃剤としては、例えば、ヘキサブロモベンゼン、デカブロモジフェニルオキシド、ビス（トリブロモフェノキシ）エタン、１，２－ビス（ペンタブロモフェニル）エタン、テトラブロモビスフェノールＳ、テトラデカブロモジフェノキシベンゼン、２，２－ビス（４－ヒドロキシ－３，５－ジブロモフェニルプロパン）、ペンタブロモトルエン、トリス（２－クロロエチル）ホスフェート、トリス（クロロプロピル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、トリス（トリブロモネオペンチル）ホスフェート、含ハロゲン縮合燐酸エステルなどの低分子ハロゲン含有有機化合物；ハロゲン含有量が４０～７０重量％のハロゲン化パラフィン類；ハロゲン化エラストマー；塩素化ポリスチレン、ヨウ化ポリスチレンなどのハロゲン化ポリスチレン；ハロゲン含有量が５０重量％以上の高塩素化ポリエチレン、高塩素化ポリプロピレン、クロロスルホン化ポリエチレンなどのハロゲン化ポリオレフィン；塩素化ポリ塩化ビニルなどのハロゲン化ポリ塩化ビニル；などの高分子量のものが挙げられる。 Halogen flame retardant is a flame retardant containing halogen atoms. Examples of the halogen-based flame retardant include hexabromobenzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3,5-dibromophenylpropane), pentabromotoluene, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneo Low molecular halogen-containing organic compounds such as pentyl phosphate and halogen-containing condensed phosphates; halogenated paraffins having a halogen content of 40 to 70% by weight; halogenated elastomers; chlorinated polystyrene, iodinated polystyrene Halogenated polystyrene such as high chlorinated polyethylene, high chlorinated polypropylene, chlorosulfonated polyethylene and the like having a halogen content of 50% by weight or more; Halogenated polyvinyl chloride such as chlorinated polyvinyl chloride; The thing of high molecular weight is mentioned.
  ノンハロ系難燃剤としては、ハロゲン原子を含まない難燃剤であり、例えば、金属水酸化物系難燃剤、金属酸化物系難燃剤、燐系難燃剤、窒素系難燃剤、燐及び窒素双方を含有する難燃剤などを挙げることができる。 Non-halogen flame retardants are flame retardants that do not contain halogen atoms, including, for example, metal hydroxide flame retardants, metal oxide flame retardants, phosphorus flame retardants, nitrogen flame retardants, both phosphorus and nitrogen And flame retardant.
  金属水酸化物系難燃剤としては、水酸化アルミニウム、水酸化マグネシウム等が挙げられる。金属酸化物系難燃剤としては、酸化マグネシウム、酸化アルミニウム等が挙げられる。燐系難燃剤としては、赤燐、燐酸エステル等が挙げられる。燐酸エステルとしては、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、レゾルシノールビス（ジフェニル）ホスフェート、ビスフェノールＡビス（ジフェニル）ホスフェート、ビスフェノールＡビス（ジクレジル）ホスフェートなどが挙げられるが、好ましくは、トリクレジルホスフェート、レゾルシノールビス（ジフェニル）ホスフェート、ビスフェノールＡビス（ジフェニル）ホスフェート、ビスフェノールＡビス（ジクレジル）ホスフェートなどの比較的分子量の大きい３級燐酸エステルが挙げられる。 Examples of metal hydroxide flame retardants include aluminum hydroxide and magnesium hydroxide. Examples of the metal oxide flame retardant include magnesium oxide and aluminum oxide. Examples of phosphorus flame retardants include red phosphorus and phosphate esters. Examples of phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, and the like. However, a tertiary phosphate ester having a relatively high molecular weight such as tricresyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, and the like is preferable.
  窒素系難燃剤としては、窒素を含む難燃剤であれば格別の限定はなく、たとえば、メラミン誘導体類、グアニジン類、イソシアヌル酸などが挙げられるが、好ましくはメラミン誘導体類が挙げられる。メラミン誘導体類としては、たとえば、メラミン、メラミン樹脂、メラム、メレム、メラミンシアヌレート、サクシノグアナミン、エチレンジメラミン、トリグアナミン、硫酸メラミン、硫酸グアニルメラミン、硫酸メラム、硫酸メレムなどが挙げられるが、好ましくは硫酸メラミンである。グアニジン類としては、たとえば、硝酸グアニジン、炭酸グアニジン、スルファミン酸グアニジン、硝酸アミノグアニジン、重炭酸アミノグアニジンなどが挙げられるが、好ましくは硝酸グアニジンが挙げられる。 The nitrogen-based flame retardant is not particularly limited as long as it is a flame retardant containing nitrogen, and examples thereof include melamine derivatives, guanidines, isocyanuric acid, and preferably melamine derivatives. Examples of the melamine derivatives include melamine, melamine resin, melam, melem, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, melamine sulfate, guanylmelamine sulfate, melam sulfate, melem sulfate, Melamine sulfate is preferred. Examples of guanidines include guanidine nitrate, guanidine carbonate, guanidine sulfamate, aminoguanidine nitrate, aminoguanidine bicarbonate, and preferably guanidine nitrate.
  燐及び窒素の双方を含有する難燃剤としては、たとえば、ポリ燐酸アンモニウム、燐酸メラミン、ポリ燐酸メラミン、ポリ燐酸メラム、燐酸グアニジン、フォスファゼン類などが挙げられるが、好ましくはポリ燐酸アンモニウム、ポリ燐酸メラミン、ポリ燐酸メラムである。 Examples of the flame retardant containing both phosphorus and nitrogen include ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, guanidine phosphate, phosphazenes, etc., preferably ammonium polyphosphate, melamine polyphosphate , Melam polyphosphate.
  これらの難燃剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。難燃剤の添加量は、共役ジエンポリマー１００重量部に対して、通常、１０～３００重量部、好ましくは２０～２００重量部、より好ましくは３０～１５０重量部の範囲である。 These flame retardants can be used alone or in combination of two or more. The amount of the flame retardant added is usually in the range of 10 to 300 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the conjugated diene polymer.
  その他の配合剤としては、その他のポリマー成分、その他の老化防止剤、着色剤、染料、顔料などが挙げられる。これらのその他の配合剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その使用量は、本発明の効果を損ねない範囲で適宜選択される。 Examples of other compounding agents include other polymer components, other anti-aging agents, colorants, dyes, and pigments. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.
  本発明に使用される硬化性組成物は、上記成分を混合して得ることができる。混合は、常法に従って行なうことができる。 硬化 The curable composition used in the present invention can be obtained by mixing the above components. Mixing can be performed according to a conventional method.
（強化繊維）
  本発明に使用される強化繊維としては、格別な制限はないが、例えば、ＰＥＴ（ポリエチレンテレフタレート）繊維、アラミド繊維、超高分子ポリエチレン繊維、ポリアミド（ナイロン）繊維、液晶ポリエステル繊維などの有機繊維；ガラス繊維、炭素繊維、アルミナ繊維、タングステン繊維、モリブデン繊維、ブデン繊維、チタン繊維、スチール繊維、ボロン繊維、シリコンカーバイド繊維、シリカ繊維などの無機繊維；などを挙げることができる。これらの中でも、有機繊維やガラス繊維が好ましく、特にアラミド繊維、液晶ポリエステル繊維、ガラス繊維が好ましい。ガラス繊維としては、Ｅガラス、ＮＥガラス、Ｓガラス、Ｄガラス、Ｈガラス等の繊維を好適に用いることができる。 (Reinforced fiber)
The reinforcing fiber used in the present invention is not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; And inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, and the like. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used.
  これらの強化繊維は、それぞれ単独であるいは２種以上を組み合わせて用いることができる。強化繊維の使用量は、使用目的に応じて適宜選択されるが、プリプレグあるいは積層体中の、通常、１０～９０重量％、好ましくは２０～８０重量％、より好ましくは３０～７０重量％の範囲であり、この範囲にあるときに積層体の誘電正接と耐熱性が高度にバランスされ好適である。 These reinforcing fibers can be used alone or in combination of two or more. The amount of reinforcing fibers used is appropriately selected according to the purpose of use, but is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight in the prepreg or laminate. When the thickness is within this range, the dielectric loss tangent and heat resistance of the laminate are highly balanced and suitable.
（プリプレグ）
  本発明のプリプレグは、前記硬化性組成物を上記強化繊維に含浸して製造することができる。
  含浸方法としては、常法に従えばよく、例えば、共役ジエンポリマー、ラジカル発生剤、アミノ基含有老化防止剤、及び所望により、充填剤、架橋助剤、難燃剤、及びその他の配合剤を溶媒に溶解して低粘度化した硬化性組成物を強化繊維に含浸させた後に脱溶媒させるウェット法、リリースペーパー上に硬化性組成物をコーティングし、その上に強化繊維を引き揃え、加熱溶解した硬化性組成物をロールあるいはドクターブレード等で加圧含浸させ、その後、放冷するホットメルト法（ドライ法）などが挙げられるが、通常はウェット法で行なわれる。 (Prepreg)
The prepreg of the present invention can be produced by impregnating the curable composition into the reinforcing fiber.
As the impregnation method, conventional methods may be used. For example, a conjugated diene polymer, a radical generator, an amino group-containing anti-aging agent, and, if desired, a filler, a crosslinking aid, a flame retardant, and other compounding agents are used as solvents. Wet method in which the reinforcing fiber is impregnated with a curable composition having a reduced viscosity by dissolving it in a solvent, and then the solvent is removed. The curable composition is coated on a release paper, and the reinforcing fiber is aligned and heated to dissolve. A hot melt method (dry method) in which the curable composition is impregnated with pressure using a roll or a doctor blade and then allowed to cool is used, but the wet method is usually used.
  ウェット法で含浸した後の乾燥温度は、通常、５０～２５０℃、好ましくは１００～２００℃、より好ましくは１２０～１７０℃の範囲であり、通常、ラジカル発生剤の１分間半減期温度以下、好ましくは１分間半減期温度より１０℃以上低い温度、より好ましくは１分間半減期温度より２０℃以上低い温度である。ここで１分間半減期温度は、ラジカル発生剤の半量が１分間で分解する温度である。例えば、ジ－ｔ－ブチルペルオキシドでは１８６℃、２，５－ジメチル－２，５－ビス（ｔ－ブチルペルオキシ）－３－ヘキシンでは１９４℃である。乾燥時間は適宜選択すればよいが、通常、０．１～１２０分間、好ましくは０．５～６０分間、より好ましくは１～３０分間の範囲である。 The drying temperature after impregnation by the wet method is usually in the range of 50 to 250 ° C., preferably 100 to 200 ° C., more preferably 120 to 170 ° C., and usually below the 1 minute half-life temperature of the radical generator, The temperature is preferably 10 ° C. or more lower than the 1 minute half-life temperature, more preferably 20 ° C. or more lower than the 1 minute half-life temperature. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C. for 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne. The drying time may be appropriately selected, but is usually in the range of 0.1 to 120 minutes, preferably 0.5 to 60 minutes, more preferably 1 to 30 minutes.
  本発明のプリプレグの厚みは、使用目的に応じて適宜選択されるが、通常、０．００１～１０ｍｍ、好ましくは０．０１～１ｍｍ、より好ましくは０．０５～０．５ｍｍの範囲である。プリプレグの厚みがこの範囲であるときに、プリプレグの操作性、及び硬化して得られる積層体の機械的強度や靭性が充分に発揮され好適である。 厚 み The thickness of the prepreg of the present invention is appropriately selected depending on the purpose of use, but is usually in the range of 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably 0.05 to 0.5 mm. When the thickness of the prepreg is within this range, the operability of the prepreg and the mechanical strength and toughness of the laminate obtained by curing are sufficiently exhibited, which is preferable.
（積層体）
  本発明の積層体は、上記プリプレグを積層するか、または前記プリプレグと前記プリプレグ以外の他材料とを積層して、所望により賦形した後に、硬化することで製造することができる。
  積層してもよい他材料としては、使用目的に応じて適宜選択されるが、例えば、熱可塑性樹脂材料、金属材料などが挙げられ、好ましくは金属材料が挙げられる。金属材料としては、回路基板で一般に用いられるものを格別な限定なく用いることができ、通常金属箔、好ましくは銅箔が用いられる。金属材料の厚みは、使用目的に応じて適宜選択されるが、通常、１～５０μｍ、好ましくは３～３０μｍ、より好ましくは５～２０μｍ、最も好ましくは５～１５μｍの範囲である。また、積層時のプリプレグと金属材料との接着を向上させる観点から、金属材料は、その表面が、シランカップリング剤、チオール系カップリング剤、チタネート系カップリング剤、各種接着剤などで処理されているものが好ましい。中でもシランカップリング剤で処理されているものがより好ましい。
　本発明のプリプレグと、金属材料との接着界面における、金属材料からなる層表面の粗度（Ｒｚ）は、特に限定されないが、通常、１０μｍ以下、好ましくは５μｍ以下、より好ましくは３μｍ以下、さらに好ましくは２μｍ以下である。一方、粗度の下限は、格別な限定はないが、通常、１０ｎｍ以上、好ましくは５ｎｍ以上、より好ましくは１ｎｍ以上である。金属材料からなる層表面の粗度が上記範囲にあれば、高周波伝送に於けるノイズ、遅延、伝送ロス等の発生が抑えられ好ましい。金属材料からなる層表面の粗度の調整は、積層する金属材料表面の粗度が所望の範囲にあるものを選択して使用することにより容易に行うことができる。かかる表面粗度を有する金属材料は市販品として入手可能である。なお、粗度（Ｒｚ）は、ＡＦＭ（原子間力顕微鏡）により測定可能である。 (Laminate)
The laminate of the present invention can be produced by laminating the prepreg, or laminating the prepreg and other materials other than the prepreg, shaping them as desired, and then curing.
The other material that may be laminated is appropriately selected according to the purpose of use, and examples thereof include a thermoplastic resin material and a metal material, and preferably a metal material. As the metal material, those generally used for circuit boards can be used without particular limitation, and usually metal foil, preferably copper foil is used. The thickness of the metal material is appropriately selected according to the purpose of use, but is usually in the range of 1 to 50 μm, preferably 3 to 30 μm, more preferably 5 to 20 μm, and most preferably 5 to 15 μm. Also, from the viewpoint of improving the adhesion between the prepreg and the metal material during lamination, the surface of the metal material is treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, and the like. Are preferred. Of these, those treated with a silane coupling agent are more preferred.
The roughness (Rz) of the surface of the layer made of the metal material at the adhesion interface between the prepreg of the present invention and the metal material is not particularly limited, but is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, Preferably it is 2 micrometers or less. On the other hand, the lower limit of the roughness is not particularly limited, but is usually 10 nm or more, preferably 5 nm or more, more preferably 1 nm or more. If the roughness of the surface of the layer made of a metal material is in the above range, the occurrence of noise, delay, transmission loss, etc. in high frequency transmission is preferably suppressed. The adjustment of the roughness of the surface of the layer made of a metal material can be easily performed by selecting and using one having a roughness of the surface of the metal material to be laminated in a desired range. A metal material having such a surface roughness is available as a commercial product. The roughness (Rz) can be measured with an AFM (atomic force microscope).
  プリプレグを積層及び硬化させる方法は、常法に従えばよく、例えば、平板成形用のプレス枠型を有する公知のプレス機、シートモールドコンパウンド（ＳＭＣ）やバルクモールドコンパウンド（ＢＭＣ）などのプレス成形機を用いた熱プレスによって行なうことができる。加熱温度は、ラジカル発生剤による架橋が起こる温度であり、通常、１分間半減期温度以上、好ましくは１分間半減期温度より５℃以上高い温度、より好ましくは１分間半減期温度より１０℃以上高い温度である。通常は、１００～３００℃、好ましくは１５０～２５０℃の範囲である。加熱時間は、通常、０．１～１８０分間、好ましくは１～１２０分間、より好ましくは２～２０分間の範囲である。プレス圧力は、通常、０．１～２０ＭＰａ、好ましくは０．１～１０ＭＰａ、より好ましくは１～５ＭＰａである。また、熱プレスは、真空または減圧雰囲気下で行ってもよい。 The method for laminating and curing the prepreg may be in accordance with a conventional method, for example, a known press having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC). Can be carried out by hot pressing using The heating temperature is a temperature at which crosslinking by the radical generator occurs, and is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. High temperature. Usually, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is usually in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes. The pressing pressure is usually 0.1 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 1 to 5 MPa. Further, the hot pressing may be performed in a vacuum or a reduced pressure atmosphere.
  かくして得られる本発明の積層体は、高周波領域での伝送ロスが少なく且つ耐熱性に優れるため、広い温度範囲で長時間利用可能であり、高周波基板材料として好適に用いることができる。 The laminate of the present invention thus obtained has little transmission loss in the high frequency region and is excellent in heat resistance. Therefore, it can be used for a long time in a wide temperature range and can be suitably used as a high frequency substrate material.
  以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例における部および％は、特に断りのない限り重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.
  実施例および比較例における各特性は、下記の方法に従い測定、評価した。
（１） 誘電正接：インピダンスアナライザー（アジレントテクノロジー社製、型番号Ｅ４９９１Ａ）を用いて積層体の１ＧＨｚにおける誘電正接（ｔａｎδ）を、容量法で測定し、比較例１の誘電正接を１００として、下記基準で判断した。
　　○：１００以下
　　×：１００を超える
（２） 耐熱性（誘電正接）：得られた積層体を、２３０℃で３０日間保持した後、インピダンスアナライザー（アジレントテクノロジー社製、型番号Ｅ４９９１Ａ）を用いて積層体の１ＧＨｚにおける誘電正接（ｔａｎδ）を容量法で測定した。（保持後のｔａｎδ）／（保持前のｔａｎδ）を算出し、下記基準で判断した。
　　○：２未満
　　△：２以上４未満
　　×：４以上
（３） 耐熱性（機械的強度）：得られた積層体を、２３０℃で３０日間保持した後、引っ張り試験機を用いて、ＡＳＴＭ  Ｄ６３８に従って、積層体の引っ張り強度を測定した。同様にして、保持前にも積層体の引っ張り強度を測定しておき、（保持後の引っ張り強度）／（保持前の引っ張り強度）を算出し、下記基準で判断した。
　　○：０．７５以上
　　△：０．５以上０．７５未満
　　×：０．５未満 Each characteristic in an Example and a comparative example was measured and evaluated according to the following method.
(1) Dielectric loss tangent: The dielectric loss tangent (tan δ) at 1 GHz of the laminate was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A). Judged by criteria.
○: 100 or less ×: More than 100 (2) Heat resistance (dielectric loss tangent): After the obtained laminate was held at 230 ° C. for 30 days, an impedance analyzer (manufactured by Agilent Technologies, model number E4991A) was used. The dielectric loss tangent (tan δ) at 1 GHz of the laminate was measured by the capacitance method. (Tan δ after holding) / (tan δ before holding) was calculated and judged according to the following criteria.
○: Less than 2 Δ: 2 or more and less than 4 ×: 4 or more (3) Heat resistance (mechanical strength): After the obtained laminate was held at 230 ° C. for 30 days, ASTM D638 was used using a tensile tester. Thus, the tensile strength of the laminate was measured. Similarly, the tensile strength of the laminate was measured before holding, (Tensile strength after holding) / (Tensile strength before holding) was calculated, and judged according to the following criteria.
○: 0.75 or more △: 0.5 or more and less than 0.75 ×: Less than 0.5
実施例１
  「Ｂ３０００」（ポリブタジエンホモポリマー；日本曹達社製；分子量３０００、１，２－ビニル結合量９５モル％）１００部、「タフプレンＡ（登録商標）」（スチレン－ブタジエン－スチレンブロックコポリマー；旭化成社製；数平均分子量５００００、結合スチレン量４０％）２０部、難燃剤としてビスフェノールＡビス（ジクレジル）ホスフェート  ８０部、シリカ（アドマファイン製；粒径０．５μｍ）１５０部、ラジカル発生剤としてジ－ｔ－ブチルペルオキシド１．２部及びアミノ基含有老化防止剤として６－エトキシ－１，２－ジヒドロ－２，２，４－トリメチルキノリン１部をキシレン中で混合し、硬化性組成物を得た。次いで、得られた硬化性組成物をガラスクロス（Ｅガラス）に含浸させ、加熱により溶媒を除去してプリプレグを作製した。プリプレグの厚さは１２０μｍ、強化繊維含有量は４１％であった。 Example 1
"B3000" (polybutadiene homopolymer; manufactured by Nippon Soda Co., Ltd .; molecular weight 3000, 1,2-vinyl bond content 95 mol%) 100 parts, "Tufprene A (registered trademark)" (styrene-butadiene-styrene block copolymer; manufactured by Asahi Kasei Corporation Number average molecular weight 50000, bound styrene content 40%) 20 parts, bisphenol A bis (dicresyl) phosphate 80 parts as flame retardant, silica (manufactured by Admafine; particle size 0.5 μm) 150 parts, di-t as radical generator -1.2 parts of butyl peroxide and 1 part of 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline as an amino group-containing antioxidant were mixed in xylene to obtain a curable composition. Next, a glass cloth (E glass) was impregnated with the obtained curable composition, and the solvent was removed by heating to prepare a prepreg. The thickness of the prepreg was 120 μm, and the reinforcing fiber content was 41%.
  次に、作製したプリプレグ５枚を重ね、２００℃で１０分間、３ＭＰａにて加熱プレスを行い厚さ０．５ｃｍの積層体を得た。得られた積層体の誘電正接と耐熱性を評価した。その結果を表１に示す。 Next, 5 produced prepregs were stacked and heated at 200 ° C. for 10 minutes at 3 MPa to obtain a laminate having a thickness of 0.5 cm. The dielectric loss tangent and heat resistance of the obtained laminate were evaluated. The results are shown in Table 1.
実施例２
  アミノ基含有老化防止剤を４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン０．８部に変える以外は実施例１と同様にしてプリプレグ及び積層体を作製し、各特性を評価した。その結果を表１に示す。 Example 2
A prepreg and a laminate were produced in the same manner as in Example 1 except that the amino group-containing antioxidant was changed to 0.8 part of 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, and each characteristic was evaluated. . The results are shown in Table 1.
比較例１
  老化防止剤を用いないこと以外は実施例１と同様にしてプリプレグ及び積層体を作製し、各特性を評価した。その結果を表１に示す。 Comparative Example 1
A prepreg and a laminate were prepared in the same manner as in Example 1 except that no anti-aging agent was used, and each characteristic was evaluated. The results are shown in Table 1.
比較例２
  「トリレン５４」（エチレン－プロピレン－ジシクロペンタジエンランダムコポリマー；ユニロイヤル社製；重量平均分子量：３００００、エチレン／プロピレン比率＝４８／５２、ＤＣＰ含有量＝９．５％、ブルックフィールズ粘度：２２００ポイズ）１０部を加える以外は比較例１と同様にしてプリプレグ及び積層体を作製し、各特性を評価した。その結果を表１に示す。 Comparative Example 2
"Tolylene 54" (ethylene-propylene-dicyclopentadiene random copolymer; manufactured by Uniroyal Corporation; weight average molecular weight: 30000, ethylene / propylene ratio = 48/52, DCP content = 9.5%, Brookfields viscosity: 2200 poise ) A prepreg and a laminate were prepared in the same manner as in Comparative Example 1 except that 10 parts were added, and each characteristic was evaluated. The results are shown in Table 1.
比較例３
  老化防止剤として２，２－オキサリルジアミドビス［エチル３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロプリオネート］１部を加える以外は比較例２と同様にしてプリプレグ及び積層体を作製し、各特性を評価した。その結果を表１に示す。 Comparative Example 3
In the same manner as in Comparative Example 2, except that 1 part of 2,2-oxalylamidobis [ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) proprionate] was added as an antioxidant, A laminate was prepared and each characteristic was evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、実施例１と２で得られた積層体は耐熱性に優れ、高温で長時間保持された場合でも誘電正接と機械的強度の変化が小さいことが分かる。また、その効果は、ジフェニルアミノ基含有老化防止剤を用いた場合に高いことが分かる（実施例２）。一方、アミノ基含有老化防止剤を用いない場合は耐熱性に劣り（比較例１）、脂環構造を有するポリマーを配合したり（比較例２）、更に他の老化防止剤を配合しても（比較例３）、機械的強度に関し若干の耐熱性改善が見られたのみであった。 From Table 1, it can be seen that the laminates obtained in Examples 1 and 2 have excellent heat resistance and small changes in dielectric loss tangent and mechanical strength even when kept at high temperature for a long time. Moreover, it turns out that the effect is high when a diphenylamino group containing anti-aging agent is used (Example 2). On the other hand, when an amino group-containing anti-aging agent is not used, the heat resistance is inferior (Comparative Example 1), a polymer having an alicyclic structure is added (Comparative Example 2), and other anti-aging agents are added. (Comparative Example 3) Only a slight improvement in heat resistance was observed with respect to mechanical strength.

Claims (7)

  1. 　共役ジエンポリマー、ラジカル発生剤、及びアミノ基含有老化防止剤を含む硬化性組成物を強化繊維に含浸してなるプリプレグ。 A prepreg obtained by impregnating reinforcing fibers with a curable composition containing a conjugated diene polymer, a radical generator, and an amino group-containing anti-aging agent.
  2. 　共役ジエンポリマー１００重量部に対して、アミノ基含有老化防止剤を０．００１～１０重量部配合してなる請求項１記載のプリプレグ。 The prepreg according to claim 1, wherein 0.001 to 10 parts by weight of an amino group-containing antioxidant is blended with 100 parts by weight of the conjugated diene polymer.
  3. 　アミノ基含有老化防止剤／ラジカル発生剤の重量比が１／９９～９０／１０の範囲である請求項１または２記載のプリプレグ。 The prepreg according to claim 1 or 2, wherein the weight ratio of the amino group-containing antioxidant / radical generator is in the range of 1/99 to 90/10.
  4. 　アミノ基含有老化防止剤が第２級アミノ基含有老化防止剤である請求項１乃至３のいずれかに記載のプリプレグ。 The prepreg according to any one of claims 1 to 3, wherein the amino group-containing antioxidant is a secondary amino group-containing antioxidant.
  5. 　第２級アミノ基含有老化防止剤が、ジフェニルアミノ基含有老化防止剤である請求項４記載のプリプレグ。 The prepreg according to claim 4, wherein the secondary amino group-containing antioxidant is a diphenylamino group-containing antioxidant.
  6. 　硬化性組成物が、難燃剤をさらに含んでなる請求項１乃至５のいずれかに記載のプリプレグ。 The prepreg according to any one of claims 1 to 5, wherein the curable composition further comprises a flame retardant.
  7. 　請求項１乃至６のいずれかに記載のプリプレグを積層した後、または前記プリプレグと他材料とを積層した後に硬化してなる積層体。 A laminate obtained by curing after laminating the prepreg according to claim 1 or laminating the prepreg and another material.
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JP2003528450A (en) * 2000-03-21 2003-09-24 ワールド・プロパティーズ・インコーポレイテッド Thermosetting composition based on polybutadiene and polyisoprene and production method thereof
JP2005292279A (en) * 2004-03-31 2005-10-20 Nippon Zeon Co Ltd Radiation sensitive composition, laminate and method for manufacturing same, and electronic component

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JPS63241046A (en) * 1987-03-27 1988-10-06 Nippon Zeon Co Ltd Rubber composition
JPH01167346A (en) * 1987-12-23 1989-07-03 Nippon Zeon Co Ltd Rubber vibration insulator composition
JPH08208856A (en) * 1994-10-13 1996-08-13 Rogers Corp Thermosetting composition based on polybutadiene and polyisoprene and its production
JP2003528450A (en) * 2000-03-21 2003-09-24 ワールド・プロパティーズ・インコーポレイテッド Thermosetting composition based on polybutadiene and polyisoprene and production method thereof
WO2003046072A1 (en) * 2001-11-30 2003-06-05 Zeon Corporation Rubber composition, vulcanizable rubber composition and damping rubber vulcanizate
JP2005292279A (en) * 2004-03-31 2005-10-20 Nippon Zeon Co Ltd Radiation sensitive composition, laminate and method for manufacturing same, and electronic component

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