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WO1998005715A1 - Composition polymere de reticulation - Google Patents

Composition polymere de reticulation Download PDF

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Publication number
WO1998005715A1
WO1998005715A1 PCT/JP1997/002735 JP9702735W WO9805715A1 WO 1998005715 A1 WO1998005715 A1 WO 1998005715A1 JP 9702735 W JP9702735 W JP 9702735W WO 9805715 A1 WO9805715 A1 WO 9805715A1
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Prior art keywords
group
aromatic ring
polymer composition
ring
norbornane
Prior art date
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PCT/JP1997/002735
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English (en)
Japanese (ja)
Inventor
Junji Kodemura
Yuichiro Konishi
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Nippon Zeon Co., Ltd.
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Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1998005715A1 publication Critical patent/WO1998005715A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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 crosslinkable polymer composition containing an aromatic ring-containing norbornene-based polymer and a crosslinking agent as essential components, a sheet-shaped molded article comprising the composition, and a glass cross-linked composition.
  • TECHNICAL FIELD The present invention relates to a prepreg impregnated in a reinforcing base material such as steel, and a laminate obtained by laminating the prepreg. More specifically, the present invention has excellent electrical properties, heat resistance, hang resistance, chemical resistance, and mechanical strength, and can uniformly disperse a compounding agent such as a flame retardant. And a crosslinkable polymer composition.
  • the present invention provides a crosslinked molded article, prepreg, laminated body, which is excellent in electric properties, heat resistance, solder resistance, chemical resistance, and mechanical strength, and in which a compounding agent is uniformly dispersed. And a metal-clad laminate. Background technology>
  • Circuits installed in precision equipment such as electronic computers and communication equipment are required to have higher speed, higher reliability and higher density in arithmetic processing as technology advances.
  • High performance such as miniaturization, high precision, and miniaturization is progressing.
  • a reinforcing base material such as glass cross is impregnated with a resin varnish, and a dried semi-cured sheet (that is, a pre-preda) is produced.
  • a resin varnish for example, a resin varnish
  • a dried semi-cured sheet that is, a pre-preda
  • it is manufactured by laying out a copper clad board for outer layer, prepreg, copper clad board for inner layer, etc. in order between the mirror-finished plates, and then pressurizing and heating to completely cure the resin.
  • a resin material X-nor resin, epoxy resin, polyimide resin, fluorine resin, polybutadiene resin, and the like have been used.
  • thermosetting resins such as phenolic resins, epoxy resins, and polyimide resins generally have a high dielectric constant of 4.0 or more and a high dielectric loss tangent of 0.01 or more. Since the electrical characteristics are not sufficient, it has been difficult for circuit boards using these thermosetting resins to achieve high-speed and high-reliability arithmetic processing.
  • a circuit board using a thermoplastic resin such as a fluororesin or a polybutadiene resin has poor heat resistance, so that cracks and peeling may occur at the time of hang-up. In addition, the dimensional stability was poor, and multilayering was difficult.
  • thermoplastic norbornane resin with an organic peroxide.
  • Japanese Patent Application Laid-Open No. Sho 62-34924 describes that decalin is obtained by addition polymerization of norbornane-based cyclic olefin and ethylene.
  • a norbornane resin having an intrinsic viscosity [] of 1.15 to 2.22 was synthesized in the reactor, kneaded with the norbornane resin and a crosslinking agent, and then pulverized.
  • a method is disclosed in which a solution is impregnated, a solvent is removed, and then press molding is performed to perform crosslinking.
  • Japanese Unexamined Patent Publication No. 6-24816 discloses flame retardants such as thermoplastic hydrogenated ring-opened norpolene-based resins, organic peroxides, crosslinking aids, and brominated bisphenols.
  • a method has been disclosed in which, after uniformly dispersing in a solvent, the solvent is removed and the resin is thermally crosslinked. According to this method, it is possible to obtain a cross-linked molded article having excellent heat resistance and low dielectric constant and dielectric loss tangent. You.
  • the type and amount of the compounding agent to be dispersed are limited, so that it may not be sufficient depending on the application field. Disclosure of the invention)
  • An object of the present invention is to provide an excellent electric property, heat resistance, solder resistance, chemical resistance, and mechanical strength, and to uniformly disperse a compounding agent such as a flame retardant.
  • An object of the present invention is to provide a crosslinkable polymer composition having various properties suitable as a resin for a circuit board and a resin material for a circuit board.
  • an object of the present invention is to use a norbornene-based resin excellent in dielectric constant, dielectric loss tangent, moisture resistance (in other words, water absorption resistance) and the like, and to provide a crosslinkable material having excellent physical properties as described above.
  • An object of the present invention is to provide a polymer composition, a prepreg made of the composition, and a laminate suitable as a circuit board. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, as a norbornene resin, it has a specific number average molecular weight range and has an aromatic ring.
  • the present invention provides a crosslinkable polymer composition comprising: a benzene-containing norbornane-based polymer having a molecular weight of 0.001; and a crosslinking agent.
  • a crosslinkable polymer composition containing an aromatic ring-containing norbornene-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent is formed.
  • a sheet will be provided.
  • a crosslinkable polymer composition containing an aromatic ring-containing norbornane-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent is used as a reinforcing base material.
  • a prepreg impregnated with a prepreg is provided.
  • a laminate obtained by laminating the sheets and / or prepregs and crosslinking the crosslinkable polymer composition.
  • a metal-clad laminate in which a metal layer is further laminated on the laminate.
  • the aromatic ring-containing norbornane-based polymer used in the present invention is a thermoplastic norbornane-based polymer as long as it has at least one aromatic ring in the molecule.
  • a polymer containing an aromatic ring-containing monomer unit is preferably used.
  • the aromatic ring-containing monomer include an aromatic ring-containing norbornane-based monomer and an aromatic vinyl compound, and among these, the content of the aromatic ring and the norbornane-based monomer are included.
  • an aromatic ring-containing norbornane-based monomer is preferred.
  • Examples of the aromatic ring-containing norbornane-based polymer having an aromatic ring-containing monomer unit include (1) an aromatic ring-containing norbornene-based monomer. Ring-opening polymers, (2) ring-opening copolymers of an aromatic ring-containing norbornane-based monomer and an aromatic ring-free norbornane-based monomer, and (3) hydrogenated products thereof. .
  • Examples of the aromatic ring-containing norbornene-based polymer include: (4) an addition polymer of an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound; and (5) an aromatic ring-containing norbornene-based monomer.
  • the hydrogenated product is usually a (co) polymer having a carbon-carbon double bond formed in the main chain and / or a (co) polymer having a non-conjugated carbon-carbon double bond in a side chain. Hydrogenated carbon-carbon double bonds. This hydrogenated product may be hydrogenated up to a hydrogenation rate of 99% or more for the carbon-carbon double bond in the main chain and the non-conjugated carbon-carbon double bond in the side chain. Not all of the rings are hydrogenated.
  • the hydrogenation rate of the aromatic ring is appropriately selected depending on the content of the aromatic ring-containing monomer, but is usually 90% or less, preferably 80% or less, and more preferably 70%. Below, the most preferred is 60% or less.
  • aromatic ring-containing norbornene monomer used in the present invention.
  • JP-A-5-97719, JP-A-7-415550 And those described in JP-A-8-72210 can be used.
  • a typical example of the aromatic ring-containing monomer is a compound represented by the following formula (I). In the formula (I), the meaning of each symbol is as follows.
  • n 0 or a positive integer.
  • h 0 or a positive integer.
  • k 0, 1 or 2.
  • R ′ R 1 ′ each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, Selected from hydrocarbon groups substituted with a lilyl group and a polar group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group) It is.
  • R 12 ⁇ R 2.
  • the group is selected from hydrocarbon groups substituted with a group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group).
  • the carbon atom to which R '° and R 11 are attached, the carbon atom to which carbon atoms or R 12 R 14 is bonded is bonded have in direct carbon atoms It may be bonded through 1-3 alkylene groups.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; and 2 to 20 carbon atoms.
  • Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Can be.
  • aromatic ring-containing norbornane-based monomer represented by the formula (I) include norbornane having an aromatic substituent represented by the following formulas (1) to (23). And a norbornane-based monomer having a norbornane ring structure and an aromatic ring structure in a polycyclic structure represented by the following formulas (24) to (30). Can be mentioned.
  • a compound name of an aromatic ring-containing norbornane-based monomer having an aromatic substituent is, for example, 5—phenyl bicyclo [2.2.1] hept-2-ene [ Formula (1); 5-vinyl 2-norbornane], 5-methyl 5-vinyl bicyclo [2.2.1] hept 2-phen [formula (2)], 5 —Benzil-bicyclo [2.2.1] hept — 2 —ene [Equation (3)], 5 — Trirubicyclo [2.2.1] —Ene [Formula (4); eg, 5— (4—methylfurenyl) —2-nonorbornene], 5— (ethynolefenyl) —bicyclo [2.2.1] heptogram — 2-ene [Equation (5)], 5 — (Isopropyl phenyl) — Bicyclo [2,2,1] hept 2 —ene [Equation (6)), 8 — ENEIRUTE TRACE CYCL
  • Compound names of aromatic ring-containing norbornane-based monomers having a norbornane ring structure and an aromatic ring structure in the polycyclic structure are, for example, 1,41-metano-1, 4,4a, 4b, 5,8,8a, 9a —Octahydrofluorenes; 1,4-metanones 1,4,4a, 9a —Teto Lahydrofluorene [Equation (24)], 1.4-Methanol 8-Methyl 1, 4, 4a, 9a-Tetrahydrofrenolene, 1, 4 One methanol 8 — Black mouth 1, 4, 4a, 9 a — Tetrahydrofluorene, 1, 4 — Metano 8 — Bromo 1, 4, 4 a, 9 a — 1,4-metano-1,4,4a, 9a, such as tetrahydrofluorene, etc.
  • 1, 4, 4, 4a, 9a Tetrahydropower compounds; 1,4,4,4a, 5,10,10a — 1,4,1 meta such as hexahydroanthracene (formula (25)) Nos 1, 4, 4a, 5, 10 and 10a —hexahydranthranes; 7, 10 —Metano 6b, 7,10, 1Oa — Tetra Compounds obtained by further adding cyclopentadiene to (hydrophenolenolansane); (cyclopentagen-acenaphthylene adduct) [Formula (26)], 11, 12 - Ben zone - penta sheet click b [6, 5, 1, l 3 '6 0 2.' 7 0 9 '13.] - 4 - pentadecene [formula (2 7)], 1 1, 1 2 - base down Zope te shea click b [6, 6, 1, 1 3 '6 0 2.' 7 0 9 '14.] one 4 - to Kisa
  • aromatic ring-containing norbornane-based monomers include alkyl, alkylidene, and alkenyl-substituted derivatives, and halogen, hydroxyl, and ester groups of these substituted or unsubstituted compounds, in addition to the above compound examples.
  • polar substituents such as an alkyl ester group), an alkoxy group, a cyano group, an amide group, an imido group, and a silyl group may be used.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, ⁇ —methinorestylene, ⁇ —methylstyrene, 1,3-dimethylstyrene, vinylna Examples include phthalene.
  • aromatic ring-containing monomers can be used alone or in combination of two or more.
  • the content (bonding amount) of the aromatic ring-containing monomer in the aromatic ring-containing norbornene-based polymer is appropriately selected according to the purpose of use, but is usually 10% by weight or more, preferably 10% by weight or more. It is at least 30% by weight, more preferably at least 50% by weight.
  • the dispersibility of various compounding agents is highly improved.
  • norbornane-based monomers containing no aromatic ring include, for example, Japanese Patent Application Laid-Open Nos. 2-222744, 2-276428, and 8-88.
  • a known monomer disclosed in, for example, Japanese Patent Publication No. 722010 can be used.
  • the norbornane-based monomer containing no aromatic ring is typically a compound represented by the following formula (II).
  • n 0 or 1
  • R each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, or a silyl group.
  • a hydrocarbon group substituted with a polar group halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group.
  • R A to R B independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, and a silyl group.
  • polar groups halogen It is selected from a hydrocarbon group substituted by an atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imido group, or a silyl group.
  • R 15 ⁇ R l8 is rather good also form a monocyclic or polycyclic bonded to each other, and monocyclic or polycyclic This also have a double bond Good.
  • R 16 and R l6, or the R 17 and R ie may form a alkylene re den group. When q is 0, each bond is combined to form a 5-membered ring.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; and 2 to 20 carbon atoms.
  • the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Can be.
  • Examples of the norbornene-based monomer having no aromatic ring include norbornane, its alkyl, alkylidene, aromatic-substituted derivatives, and halogen or hydroxyl group of these substituted or unsubstituted norbornene.
  • Examples of the substituent include polar groups such as a ester group, an alkoxy group, a cyano group, an amido group, an imido group, and a silyl group.
  • norbornane-based monomers having no aromatic ring include, for example, 2-norbornane [that is, bicyclo [2.2.1]].
  • a norbornane-based monomer having no aromatic ring is a monomer having a structure in which norbornane is added with one or more cycle-opening pentangens.
  • Norbornene monomer aromatic ring-containing and / or other norbornene monomer in the aromatic ring-containing norbornene polymer
  • the amount (binding amount) is appropriately selected according to the purpose of use, but is usually at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight. If the content of norbornane-based monomer units is too small, properties such as electrical properties, heat resistance, solder resistance, chemical resistance, and mechanical strength may not be sufficient. , Not preferred.
  • vinyl compounds other than aromatic vinyl compounds include, for example, ethylene, propylene, 1-butene, 11-pentene, 11-hexene, 31-methyl-1--1 Butene, 3 — Methinole 1 — Penten, 3 — Methinole 1 Penten, 4 — Methinole 1 Penten, 4 — Methyl 1 1 — Hexen, 4,4 Chinolay 1 — hexene, 4, 4 1 dimethyltin I 1 pentene, 4 1 ethyl 1 1 hexene, 3 — echinolay 1 1 hexene, 1 octene, 1 — decene 1-decadene, 1-tetradecane, 1-hexadecene, 1-year-old octadecene, 1-eicosene, etc.
  • the ring-opening polymer or ring-opening copolymer of norbornene-based monomer can be obtained by a known polymerization method.
  • Catalyst system comprising a halide, nitrate or acetylacetonate compound of a metal selected from the group consisting of platinum, platinum, platinum, and the like, and a reducing agent; titanium, titanium dioxide, zinoleconium, tungsten
  • a catalyst system comprising a halide or acetylacetonate compound of a metal selected from benzene, and molybdenum, and an organic aluminum compound can be used.
  • the polymerization activity and the selectivity of ring-opening polymerization can be increased.
  • the third component include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, and the like.
  • examples include sulfur compounds, halogen-containing compounds, molecular iodine, and other Lewis acids.
  • the nitrogen-containing compound an aliphatic or aromatic tertiary amine is preferred, and specific examples thereof include triethylamine, dimethylethylaniline, and tri-n-butylamine. , Pyridine, ⁇ -picolin and the like.
  • the ring-opening (co) polymerization is possible without using a solvent, but is preferably carried out in an inert organic solvent.
  • the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ⁇ -pentane, hexane, heptane, and other aliphatic hydrocarbons; cyclohexane; Which alicyclic hydrocarbons; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachlorethane, chlorobenzene, dichlorobenzene and trichlorobenzene; No.
  • the polymerization temperature is usually in the range of —50 to 100, preferably —30 to 80, more preferably 120 to 60, and the polymerization pressure is Usually, 0 ⁇ 5 0 k gZ cm 2 , is preferred properly in the range of 0 ⁇ 2 0 kg / cm 2.
  • Norbornene monomer and aromatic vinyl compound and / or aromatic In order to produce an addition copolymer with a vinyl compound other than the aromatic vinyl compound, a known method can be employed. Specifically, for example, a vanadium compound and an organic aluminum compound, which are soluble in a solvent or a norbornene monomer, in a hydrocarbon solvent or in the absence of a solvent in a hydrocarbon solvent, preferably An example is a method of copolymerizing in the presence of a catalyst system comprising a halogen-containing organic aluminum compound.
  • hydrocarbon catalyst examples include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; and the like.
  • the polymerization temperature is usually in the range of —50 to 100 ° C, preferably —30 to 80 ° C, more preferably 120 to 60 ° C.
  • the polymerization pressure is usually in the range of 0 to 50 kg Z cm 2 , preferably 0 to 20 kg / cm 2 .
  • the hydrogenated product (hydrogenated polymer) of an aromatic ring-containing norbornane-based polymer is obtained by converting an aromatic ring-containing norbornane-based polymer into molecular hydrogen in the presence of a hydrogenated catalyst according to a conventional method. It can be obtained by a hydrogenation method.
  • the aromatic ring-containing norbornane-based polymer to be hydrogenated is often the aforementioned ring-opening polymer or ring-opening copolymer having a carbon-carbon double bond (unsaturated bond) in the main chain structure. is there.
  • a catalyst system composed of a combination of a transition metal compound and an alkyl metal compound, for example, cobalt triethylamine acetate, nickel acetylase toner toner triisobutyl aluminum, titanonium Sensory chloride / n — butyllithium, zircono Sensory chloride / sec — butyllithium, tetrabutyl toxititane Combinations of dimethylmagnesium and the like can be mentioned.
  • a transition metal compound and an alkyl metal compound for example, cobalt triethylamine acetate, nickel acetylase toner toner triisobutyl aluminum, titanonium Sensory chloride / n — butyllithium, zircono Sensory chloride / sec — butyllithium, tetrabutyl toxititane Combinations of dimethylmagnesium and the like can be mentioned.
  • the hydrogenation reaction is usually performed in an inert organic solvent.
  • a hydrocarbon-based solvent is preferred, and a cyclic hydrocarbon-based solvent is more preferred, because of excellent solubility of the generated hydrogenated product.
  • hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; cyclohexane, decalin and the like.
  • Alicyclic hydrocarbons ethers such as tetrahydrofuran and ethyl glycol dimethyl ether; and the like, and two or more of these can be used in combination.
  • the hydrogenation catalyst may be added to the polymerization reaction solution as it is to cause the reaction.
  • the aromatic ring-containing norbornene-based polymer used in the present invention preferably has high weather resistance and light deterioration resistance. Therefore, the ring-opened (co) polymer has an unsaturated bond in the main chain structure. Usually, it is preferably at least 95%, preferably at least 98%, more preferably at least 99% saturated. If there is a non-conjugated carbon-carbon double bond in the side chain, it is also preferably highly saturated. However, in order to achieve the object of the present invention, the aromatic ring structure is usually at least 10%, preferably at least 20%, more preferably at least 30%, particularly preferably at least 4%. It is desirable that 0% or more remain. Unsaturated bonds in the aromatic ring structure can be recognized and distinguished from unsaturated bonds in the main chain structure and non-conjugated unsaturated bonds in the side chain structure by 1H-NMR analysis.
  • hydrogenation mainly at carbon-carbon double bonds in the main chain structure it is usually — 20 to 120 ° C, preferably 0 to: 100 ° C, more preferably.
  • a temperature of 20 to 80 ° C usually 0.1 l SO kg Z cm 2 , preferably 0.5 to 30 kg / cm 2 , more preferably l to 20 kg gZcm Two It is desirable to carry out the hydrogenation reaction at this hydrogen pressure. Due to this hydrogenation reaction, when a non-conjugated carbon-carbon double bond exists in the side chain, hydrogenation is performed in the same manner.
  • the molecular weight of the aromatic ring-containing norbornane-based polymer used in the present invention is as follows.
  • the number average molecular weight (Mn) in terms of polystyrene by the (GPC) method is 50,000 to 500,000, preferably 1, 0000 to 100,000. , More preferably in the range of 2,000 to 500,000, and most preferably in the range of 5,000 to 35,000.
  • the number average molecular weight of the aromatic ring-containing norbornene-based polymer is too small, the mechanical strength is not sufficient. Conversely, if the number average molecular weight is too large, the dispersibility of the compounding agent is not sufficient, and both are favorable. Absent.
  • the molecular weight distribution (M w / n) of the aromatic ring-containing norbornane polymer used in the present invention is usually 4 or less, preferably 3 or less, more preferably 2 or less.
  • the mechanical strength can be increased by reducing the molecular weight distribution.
  • the aromatic ring-containing norbornane-based polymer can be prepared by a method known in Japanese Unexamined Patent Publication (Kokai) No. 3-92553, such as a, / S-unsaturated carboxylic acid, a derivative thereof, and a styrene-based polymer. It may be modified using a hydrocarbon, an organic gayne compound having an olefinic unsaturated bond and a hydrolyzable group, an unsaturated epoxy monomer, or the like. As the modifier, unsaturated carboxylic acids such as maleic anhydride, and derivatives of such acid anhydrides or alkyl esters of unsaturated carboxylic acids are preferred.
  • the composition of the present invention has a number average molecular weight (Mn) of 500 to 500,000.
  • Mn number average molecular weight
  • the method for crosslinking the crosslinkable polymer composition of the present invention is not particularly limited.
  • the crosslinking can be performed using heat, light, radiation, or the like. Is selected as appropriate.
  • an aromatic ring-containing norbornane-based polymer is used as the thermoplastic norbornane-based resin, its dispersibility is improved even with various crosslinking agents.
  • the crosslinkable polymer composition of the present invention may contain, in addition to a crosslinking agent, a crosslinking aid, a thermosetting resin, a flame retardant, other compounding agents, a solvent, and the like, if desired. .
  • the crosslinking agent is not particularly limited, and examples thereof include an organic peroxide, a photocrosslinking agent that generates radicals by light, and a thermosetting crosslinking agent that exerts its ability by heating. Can be mentioned.
  • Organic peroxides include, for example, ketone peroxides such as methylethyl ketone peroxide and cyclohexanone peroxide; 1,11 bis (t- Butyloxy) 3,3,5—Trimethyltincyclohexane, 2,2—Bisoxy (t-butylperoxy) butane, etc .; ,.
  • Dialkyl peroxides such as benzene: octa Diaryloxides such as ylperoxide and isobutyrylperoxide; and peroxyesters such as carboxylic dicarbonate.
  • dialkyl peroxide is preferred, and the type of the alkyl group may be changed depending on the molding temperature.
  • Examples of the photocrosslinking agent that generates a radical by light include benzoquinethyl ether, benzoinquinobutyl ether and other benzoinquinol ether-based conjugates; Benzophenone, benzophenone-based compounds such as dibenzobenzophenone; benzyl-based compounds such as dibenzyl and benzylmethyl ketone; 2, 2—Jetoxyacetphenone, 2—Hydroxy 2—Methyl propionone, 4 —Isopropyl 1 2—Hyd mouth 1—Methyl propionone, 1, 1-Cycloacetophenone, 2, 2-Jexoxyacetophenone, 4'-Phenoxy2, 2-Dichloroacetophenone, etc.
  • Tovonon-based compound Thioxanthonone 2—methylthioxanthone, 2—isopropylthioxanthone, and other thioxanthonone compounds; 2—ethylanthraquinone; Anthraquinone-based compounds such as anthraquinone and naphthoquinone; 2 — hydroxy — 2 — methylpropionoff; Non-propionic X-non-compounds such as nonan; organic acid gold salts such as cobalt octanoate, cobalt cobalt naphthenate, manganese octanoate and manganese naphthenate; Photocrosslinking agents can be mentioned.
  • Aliphatic ports such as lempentamine Li A Mi emissions; Jia Mi Bruno shea click b to hexa down, 3 (4), 8 (9) Single-bis ( ⁇ Mi Bruno methylation) Application Benefits shea click b [5, 2, 1, 0 2 '6] Decane; 1, 3 — (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine, N—aminoethylpiperazine, bis (4-amino-3-cyclohexyl) methane, bis (41-aminocyclohexyl) methane, and other aliphatic polyamines; 4, 4 '-diamino diphenyl ethereolene, 4, 4'-diamino diphenyle acetane, a, '-bis (4-diamino diphenylene 1, 3-diisopropirbe A'-bis (4-aminopropyl) 1,4-diisopropyl
  • Acid anhydrides fumaric acid, phthalic acid, maleic acid, trimellitic acid, and dicarboxylic acids such as hymic acid; phenolic boric resin, cresolnoic acid Polyvalent phenols such as boric resin; Nylon-16, Nylon-66, Nylon-610, Nylon-11, Nylon-6 11 , Nylon 1-12, Nylon 1 46, methoxymethylated polyamide, polyhexamethylene diamine terephthalamide, polyhexamethyl Polyamide, such as rain soft amide And the like; diisocyanates such as hexamethylene diisocyanate and tridenzene diisocyanate; and the like. These may be used alone or as a mixture of two or more. Among these, aliphatic polyamines and aromatic polyamines are preferred because they are easily dispersed uniformly.
  • cross-linking agents can be used alone or in combination of two or more.
  • the mixing ratio of the crosslinking agent is usually from 0.01 to 30 parts by weight, preferably from 0.001 to 15 parts by weight, based on 100 parts by weight of the aromatic ring-containing norbornene-based polymer.
  • Heavy! Part, more preferably 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight.
  • the use of a crosslinking aid is preferable because the crosslinking property and the dispersibility of the compounding agent can be further enhanced.
  • the crosslinking aid used in the present invention is not particularly limited, and for example, a polyfunctional monomer, a photosensitizer, a curing accelerator and the like can be used according to the type of each crosslinking agent. More specifically, known crosslinking aids such as those disclosed in Japanese Patent Application Laid-Open No. Sho 62-34924 may be used, such as quinone dioxime, benzoquinone dioxime, and the like.
  • p—Oxim such as dinitrophenol; dinitro-type crosslinking aid; N, N—m — Murine-mid crosslinking, such as fuirylene bismuthamide Auxiliaries; aryl cross-linking assistants such as diaryl phthalate, trilinolecinurate, and trilinoleocyanate; ethylene glycol dimethacrylate, Methacrylate-based crosslinking aids such as trimethylolpropane trimethacrylate; vinyl Vinyl-based crosslinking aids such as rutoluene, ethylvinylbenzene, divinylbenzene, and the like; and the like.
  • These crosslinking aids are mainly used in combination with an organic peroxide or a photocrosslinking agent. Of these, aryl crosslinkers and methacrylate crosslinkers are preferred because they are easily dispersed uniformly.
  • thermosetting crosslinking agent examples include, for example, pyridin, pentanoresinethylamine, triethanolanoreamin, trietinoreamin, tributylamine. , Tribenzilamine, dimethinoleformamide, imidazoles, and other amines to control the curing rate and improve the efficiency of the crosslinking reaction. It is added for the purpose of doing.
  • the amount of the crosslinking aid to be added is appropriately selected depending on the type of the crosslinking agent, but is usually 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight, per part by weight of the crosslinking agent. 5 parts by weight. If the amount of the crosslinking aid is too small, crosslinking is unlikely to occur. Conversely, if the amount is too large, the electrical properties, water resistance, moisture resistance, etc. of the crosslinked resin may be reduced.
  • thermosetting resin such as an epoxy resin because the adhesive strength of the laminate is highly improved.
  • thermosetting resin is not particularly limited, and generally used ones can be used. Examples thereof include epoxy resins, urea resins, melanin resins, phenol resins, and unsaturated polyester resins. And a tellurium resin. Of these, epoxy resins are preferred.
  • Thermosetting resins usually consist of a low molecular weight raw material and a curing agent.
  • a curing agent for example, in the case of epoxy resin, it consists of an epoxy compound and various curing agents Is done.
  • the epoxy compound is not particularly limited as long as it is a compound having an epoxy group in a molecule, and includes a bisphenol type, a novolak type, a fl cyclic type, a heterocyclic type, and a glycerol type.
  • examples include compounds used as epoxy resins such as phosphorus type and dicyclopentadiene type.
  • a halogenated bisphenol type epoxy compound represented by the formula (E1) is preferable.
  • X is a halogen atom
  • R is a divalent hydrocarbon group
  • m is an integer of 1 to 3
  • n is 0 or an integer of 1 or more.
  • a novolak type epoxy compound represented by the formula (E2) is preferably used.
  • R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p is 0 or an integer of 1 or more.
  • the average value of p is 0 to 5 and R ′ is a hydrogen atom or a methyl group.
  • These epoxy compounds can be used alone or in combination of two or more.
  • the bisphenol type epoxy compound of the formula (E1) is preferred, and when heat resistance and chemical resistance are to be improved, the formula (E2) Novolak type epoxy compounds are preferred.
  • a specific example of the epoxy compound of the formula (E1) a compound represented by the formula (E3) can be mentioned.
  • the halogenated bisphenol-type epoxy compound represented by the formula (E3) for example, those having a Br content of 20% by weight or 50% by weight are commercially available. Have been.
  • curing agent for the epoxy resin examples include, for example, an amine compound, an imidazole compound, a nitrogen-containing heterocyclic compound such as diazabicyclodecene, an organic phosphine, and an organic boron complex. And quaternary ammonium compounds, quaternary phosphoniums and the like.
  • the mixing ratio of the thermosetting resin is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 100 to 100 parts by weight of the aromatic ring-containing norbornene-based polymer.
  • the amount is 15 to 120 parts by weight.
  • flame retardant used in the present invention there is no particular limitation on the flame retardant used in the present invention, but those which do not decompose, modify or degrade with the crosslinking agent are preferred.
  • Various chlorinated and bromine-based flame retardants can be used as the lipogen-based flame retardant, but the flame retardant effect, heat resistance during molding, dispersibility in the polymer, polymer Hexabromobenzene, pentabromoethylbenzen, hexibopen mobilifnil, de Cabromo diphenyl, Hexa-sub-modulofluxide, Octapromo-modulofluxide, Dekabu-flux modifoxy-fluxide, Pentabu-flux microcyclohexane, Tetrabromo Bisphenol 8 and its derivatives [eg, tetrabromobisphenol A—bis (hydroxyxethyl ether), tetrabromobisphenol A—bis (2,3— Jib mouth mopro propyl ether), tetrabromobisphenol A—bis (promoethyl), tetrabromobisphenol A—bis (aryl ether), etc.
  • Bromobisphenol S and derivatives thereof [eg, tetrabromobisphenol S—bis (hydroxixethyl), tetrabromobis Phenol S-bis (2,3-dibromopropyl ether), etc.), tetrabromobromophthalic anhydride, and derivatives thereof [eg, tetrabromophthalimide, ethylene bis Tribromophthalimid, etc.), ethylenebis (5, 6-dibromomonobornane-1,2,3—dicarboximid), tris (2,3—dibromopropyl-1) iso Cyanurate, adduct of Diels-Alder reaction of hexacyclocyclopentagen, trib mouth ninoleregisyl ether, trib mouth morphine crelate , Ethylene bistribromophenyl ether, Ethylene bispentabromophenyl ether, Tetradecab modifoxy
  • flame retardants used in the present invention particularly preferred flame retardants will be described with reference to chemical formulas.
  • Uniform dispersibility in polymer composition, crosslinking compounds represented by the following formulas (N1) to (N9) are preferable as flame retardants that are not easily decomposed, denatured, and altered by a crosslinking agent such as an organic peroxide. It can be mentioned as a thing.
  • n is 0 or an integer of 1 or more.
  • n is an integer of 0 or 1 or more
  • ml to m 6 are integers of 1 or more
  • the halogenated bisphenol-type epoxy compound in the thermosetting resin is also a kind of flame retardant.
  • the compounding ratio of the flame retardant is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 100 to 140 parts by weight, based on 100 parts by weight of the aromatic ring-containing norbornane polymer. It is preferably 15 to 120 parts by weight.
  • a flame retardant aid for example, antimony trioxide, antimony pentoxide, sodium antimonate, Antimony flame retardant aids such as antimony chloride can be used.
  • These flame retardant auxiliaries are usually used in a proportion of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the flame retardant.
  • the crosslinkable polymer composition of the present invention may contain, if necessary, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an anti-violation agent, a lubricant, a dye, a pigment, Various compounding agents such as natural oils, synthetic oils, waxes, organic or inorganic fillers can be added in appropriate amounts.
  • the organic or inorganic filler various fillers such as powder, granules, and arrowheads can be used.
  • the filler for example, silica, gay alga earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, Dolomite, sulfated calcium, potassium titanate, barium sulfate, sulfite, talc, creed, my strength, asbestos, glass fibers, glass flakes, glass beads, Calcium gaymate, Monmorillonite, Bentonite, Graphite, Aluminum powder, Molybdenum sulfide, Boron fiber, Silicon carbide fiber, Polyethylene fiber , Polypropylene fibers, polyester fibers, and polyamide fibers.
  • the crosslinkable polymer composition is added to a polycarbonate, a polystyrene, a polyphenylene sulfone, or the like.
  • thermoplastic resins such as sulfide, polyetherimide, polyester, polyamide, polyacrylate, and polysulfone can be blended.
  • These compounding agents can be used alone or in combination of two or more.
  • the mixing ratio can be appropriately determined according to each function and purpose of use.
  • the solvent used may be, for example, an aromatic hydrocarbon such as toluene, xylene, or ethylbenzene.
  • aromatic hydrocarbon such as toluene, xylene, or ethylbenzene.
  • the solvent is used in an amount sufficient to uniformly dissolve or disperse the aromatic ring-containing norbornene-based polymer, the crosslinking agent, and, if necessary, each component.
  • the crosslinkable polymer composition is molded and then crosslinked to obtain a crosslinkable molded article.
  • the method of molding the crosslinkable polymer composition is either dissolved in a solvent or molded so as not to cause deterioration in moldability due to crosslinking in the course of molding, or a crosslinking reaction does not occur. Melting and molding at a temperature where the temperature or crosslinking rate is sufficiently slow. Specifically, the crosslinkable polymer composition dissolved in a solvent is cast on a flat support, and the solvent is removed, and then molded into a sheet or impregnated into a substrate to be molded.
  • the pre-preda which is one of the specific examples of the cross-linked molded article of the present invention, comprises a norbornene-based polymer, a cross-linking agent, and, if necessary, a solvent such as toluene, cyclohexane, or xylene. It is manufactured by uniformly dissolving or dispersing various compounding agents, then impregnating the reinforcing base material, and then drying to remove the solvent. Generally, the pre-reader is about 50 to 500 m. Thickness is preferred.
  • the proportion of the solvent used is usually 1 to 90% by weight of solid content, preferably 5 to 85% by weight, more preferably 10 to 80% by weight, and most preferably 20 to 8% by weight. Adjusted to be 0% by weight.
  • the reinforcing base material for example, a paper base material (for example, a lint paper, a craft paper), a glass base material (for example, a glass cross, a glass mat, a glass paper quartz) Fibers) and synthetic resin fiber base materials (for example, polyester fibers and aramid fibers) can be used.
  • a paper base material for example, a lint paper, a craft paper
  • a glass base material for example, a glass cross, a glass mat, a glass paper quartz) Fibers
  • synthetic resin fiber base materials for example, polyester fibers and aramid fibers
  • the impregnation ratio of the crosslinkable polymer composition to the reinforcing base material is appropriately selected according to the purpose of use, but is usually 1 to 90% by weight, preferably 10 to 80% by weight, based on the total amount of the prepreg. % By weight, more preferably in the range of 20 to 70% by weight.
  • a method for producing a sheet which is one of the specific examples of the crosslinkable molded article of the present invention, is not particularly limited, but generally, a casting method is used.
  • the crosslinkable polymer composition of the present invention is dissolved in a solvent such as toluene, xylene, or cyclohexane so as to have a solid content concentration of about 5 to 50% by weight.
  • the sheet is cast or coated on the smooth surface of the support, the solvent is removed by drying or the like, and the sheet is obtained by peeling off the smooth surface.
  • a mirror-finished metal plate, a resin carrier film, or the like can be used as the support.
  • a resin carrier film determine the solvent to be used and the drying conditions while paying attention to the solvent resistance and heat resistance of the resin material.
  • Sheets obtained by the casting method are generally 1! It has a thickness of about lmm. These sheets can be used as an interlayer insulating film, a film for forming a moisture-proof layer, etc. by crosslinking. Further, it can be used for manufacturing a laminate described below.
  • a laminate such as a laminate which is a specific example of a cross-linked molded article obtained by using the cross-linkable polymer composition of the present invention, comprises the above-described prepreg and the number of sheets of uncross-linked or uncross-linked. The required thickness is obtained by stacking, heat-compression molding, crosslinking and heat-sealing.
  • the laminate is a circuit board (for example, a printed wiring board, a multi-layer printed wiring board, a high-density wiring board, etc.), generally, a plurality of prepregs are stacked and heated and compression-molded to form an insulating layer. I do.
  • the pre-preda and the sheet may be combined and laminated, or depending on the field of use, a plurality of sheets alone may be laminated.
  • a wiring conductive layer made of gold foil or the like is further laminated, or the circuit is formed by etching the metal layer surface.
  • the wiring conductive layer may be laminated not only on the outer surface (one surface or both surfaces) of the finished laminate, but also on the inside of the laminate depending on the purpose of forming an inner layer circuit or the like. .
  • prepreg and nose or sheet are combined vertically and laminated. I prefer to do it.
  • the surface of the required number of stacked pre-predaders and sheets or sheets is heated to a heat-sealing temperature or higher corresponding to the norbornane resin used, usually 150 to 300. Heat to about 30 to 80 kgf Z cm 2 , and crosslink and heat fuse between each layer to obtain a laminate.
  • other methods of forming a metal layer on the laminate include vapor deposition, electrical plating, sputter, ion plating, spraying, and layering. No. Commonly used metals include copper, nigel, tin, silver, gold, aluminum, platinum, titanium, zinc, and chromium. Copper is most frequently used on circuit boards
  • a crosslinked molded article is obtained by heating the crosslinkable molded article alone or by laminating it at a certain temperature or higher.
  • the temperature at which the cross-linking reaction occurs is mainly determined by the combination of the organic peroxide and the crosslinking assistant, but is usually from 80 to 350 ° C, preferably 120 ° C.
  • Crosslinking is achieved by heating to a temperature of from about 300 ° C to about 300 ° C, more preferably from about 150 ° C to about 250 ° C.
  • the crosslinking time is preferably about 4 times the half-life of the organic peroxide, usually 5 to 120 minutes, more preferably 10 to 90 minutes, and more preferably. Or 20 to 60 minutes.
  • cross-linking agent When an optical cross-linking agent is used as a cross-linking agent, it can be cross-linked by light irradiation. When a thermosetting crosslinking agent is used, the crosslinking is carried out by heating to a temperature at which the crosslinking agent exerts its ability. When the crosslinkable molded articles are laminated and crosslinked, heat fusion and crosslinkage occur between each employee, and an integrated crosslinked molded article is obtained. (5) Crosslinked molded body
  • a laminated board, a circuit board, an interlayer insulating film examples include a film for forming a wet layer.
  • Crosslinked molded article of the present invention has water absorption 0.0 to 3%, 1 0 15 ⁇ 1 0 17 ⁇ , the dielectric constant and dielectric loss tangent at 1 MHz, respectively from 2.0 to 2.5, 0 .001 to 0.0007. Therefore, the crosslinked molded article of the present invention is superior in water resistance and electrical properties as compared with the conventional thermosetting resin molded article.
  • the heat resistance of the crosslinked molded article of the present invention is equivalent to that of a conventional thermosetting resin molded article. For example, even if 260.degree. Solder is brought into contact with the laminate obtained by laminating the copper foil of the present invention for 30 seconds, no abnormality such as peeling of the copper foil or occurrence of flaking is observed.
  • the crosslinked molded article of the present invention is preferably one having excellent flame retardancy, specifically, one having a flame retardancy of V-2 or better in the UL-94 standard. Those exhibiting a flame retardancy of —1 or V-0 are more preferred, and those exhibiting a flame retardancy of V-0 are particularly preferred.
  • a cross-linkable resin composition containing the above-described flame retardant may be used. Examples>
  • the glass transfer temperature was measured by the differential scanning calorimetry (DSC method).
  • the copper foil peel strength was determined by taking a test piece of width 100 mm and width 100 mm from the laminate, making a parallel cut of width 10 mm on the copper foil surface, and then applying a tensile tester. The copper foil was peeled off continuously at a speed of 5 O mmZ in the direction perpendicular to the surface, and the lowest value of stress at that time was shown.
  • Toluene resistance was measured by cutting out a 25 mm square piece of copper from which the copper foil had been removed, boiling it in toluene for 5 minutes, and visually observing the change in appearance. The evaluation was based on the following criteria.
  • the hang resistance was measured by cutting the laminate from which the copper foil had been removed into 25 mm squares, floating them in a 260 deg. Solder bath for 120 seconds, and then visually examining the change in appearance. And evaluated according to the following criteria.
  • MTF Tetrahydrofluorene
  • the obtained hydrogenated polymer (Polymer A) was determined by 1 H-NMR measurement to have a hydrogenation rate of unsaturated bonds of the main chain of at least 99% and a hydrogenation rate of the benzene ring of almost 0%. It was a white powder having a number average molecular weight (Mn) of 13,200 and a weight average molecular weight (Mw) of 21,700.
  • MTF was changed to a monomer mixture of 50% by weight of MTF and 50% by weight of tetracyclododecene (hereinafter abbreviated as “TCD”), and the amount of 1-hexene used was 5.75 mmol
  • Polymerization reaction and hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 2.30 mmol, and the hydrogenation rate of the unsaturated bond in the main chain was 99% or more.
  • the hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 27,200, the weight average molecular weight (Mw) is 49, 100, and the MTF Hydrogenated polymer (polymer) in which the copolymerization ratio of TCD and TCD is 50:50 (weight ratio) E).
  • MTF is converted to a monomer mixture of 20% by weight of MTF and 80% by weight of methyltetracyclodecene (hereinafter abbreviated as “MTD”), and the amount of used hexane is 11%.
  • Polymerization reaction and hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the hydrogenation rate of unsaturated bonds in the main chain was changed from 5.75 mmol to 2.30 mmol.
  • the hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 30,300, the weight average molecular weight (Mw) is 53,900, and thus, a hydrogenated polymer (polymer F) having a copolymerization ratio of MTF and MTD of 20:80 (weight ratio) was obtained.
  • the MTF was changed to a monomer mixture of MTF 10% by weight and] VLT D 90% by weight, and the amount of 1-hexene used was 5.75 mmol force, etc.
  • a polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the value was changed to mmo1, and the hydrogenation rate of the unsaturated bond in the main chain was 99% or more, and hydrogen in the benzene ring was obtained.
  • the addition rate is almost 0%, the number average molecular weight (Mn) is 32,400, the weight average molecular weight (Mw) is 57,900, and the copolymerization ratio of MTF and MTD As a result, a hydrogenated polymer (polymer G) having a weight ratio of 10:90 was obtained.
  • the MTF was changed to a mixed monomer of 50% by weight of 50% by weight of TCD and 50% by weight of TCD, and the amount of 1-hexene used was 5%.
  • a polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the amount was changed from 75 mmol to 2.30 mmol, and the hydrogenation rate of unsaturated bonds in the main chain was 9 9% or more
  • the hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 29,200, the weight average molecular weight (Mw) is 53,100, and both PNB and TCD
  • a hydrogenated polymer (polymer H) having a polymerization ratio of 50:50 (weight ratio) was obtained.
  • a polymerization vessel having an internal volume of 1 liter was replaced with nitrogen gas, hexane solution MTF of consequent opening, catalyst and to VO (0 C 2 H 5) hexa emissions solution C 1 2 to Shik b, and Echiruarumi Niumusesukiku mouth Lai de [a 1 (C 2 H 5 ),. 5 C 1!. 5] the hexane solution consequent opening of the polymerization vessel at concentrations respectively 6 0 g / Li Tsu Bok Honoré, 0. 5 mmo 1 / litre, 4.0 mmo 1 liter, supplied with 15 liters of ethylene ZH r and 2.5 liters of hydrogen gas The system was supplied at a rate of H r and the system was controlled at 10 ° C. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel so that the entire amount of the polymerization liquid in the flask became 1 liter and the average residence time was 0.5 hour.
  • the polymerization was stopped by adding a small amount of isopropyl alcohol to the withdrawn polymerization solution, and then using a homogenizer at a ratio of 1: 1 of an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water. Contact was made under strong stirring to transfer the catalyst residue to the aqueous phase. The mixture was allowed to stand, the aqueous phase was removed, and the mixture was further washed twice with distilled water to purify and separate the polymer solution.
  • the polymerization solution was poured into 3 liters of acetone to precipitate a polymer, which was collected by filtration. Next, the recovered polymer was dried at 100 ° C. and 1 Torr or less for 48 hours.
  • the obtained polymer (Polymer I; MTF / ethylene addition copolymer) had an ethylene content of 62 mol%, a number average molecular weight (Mn) of 10, 500, and a weight average molecular weight. (Mw) was 37,800.
  • Table 1 shows the composition, polymerization method, hydrogenation rate, molecular weight, etc. of each polymer obtained in Synthesis Examples 1 to 11 collectively.
  • This varnish is impregnated by immersing E glass cloth, and then It was dried in an air oven to produce a curable composite material (prepredder).
  • the weight of the base material in the prepreg was 40% by weight based on the total amount of the prepreg.
  • a plurality of the above prepregs are stacked as necessary so that the thickness after molding becomes 0.8 mm, and copper foil with a thickness of 35 ⁇ m is placed on both sides of the prepreg, and molded by a hot press molding machine It was cured to obtain a laminate.
  • each varnish was immersed in and impregnated with E glass cloth to prepare a prepreg, and then a resin laminate was obtained.
  • the physical properties of each of the resin laminates thus obtained were measured, they showed good dielectric properties, water absorption, heat resistance, solvent resistance, and copper foil peeling strength.
  • the flame retardancy was V-0.
  • Tables 2 and 3 show the compositions and results of Examples 1 to 32 collectively.
  • varnishes were phase-separated into two phases, and a uniform solution could not be obtained.
  • varnishes were impregnated by impregnating E-galaxros, but the impregnating components differed between the upper and lower portions of E-galaxros, and uniform impregnation was not possible.
  • a cyclic olefin addition polymer [APEL 515, manufactured by Mitsui Petrochemicals Co., Ltd .; number average molecular weight (Mn) 47, 200, weight average molecular weight (Mw) 83, 100], and various components shown in Table 4 were blended, and dissolved in toluene so that the solid content concentration became 20% by weight to prepare a varnish.
  • Each of the obtained varnishes was phase-separated into two phases, and a uniform solution could not be obtained.
  • These varnishes were impregnated with E glass cross by impregnation, but the impregnating components differed between the upper and lower portions of the E glass cross, and uniform impregnation was not possible.
  • Table 4 summarizes the compositions of these comparative examples.
  • a cyclic olefin-based addition polymer [APEL 515, manufactured by Mitsui Petrochemical Co., Ltd .; number average molecular weight (Mn) 47, 200, weight average molecular weight (Mw) 83, 1 [0 0] was performed in the same manner as in Examples 33 to 41, and the same evaluation was performed.
  • Table 5 shows the compositions and results of Examples 33 to 41 and Comparative Examples 15 to 17 collectively.
  • a crosslinkable polymer composition having excellent heat resistance, hang resistance, chemical resistance, mechanical strength, and the like, and suitable for uniformly dispersing various compounding agents such as a flame retardant, A molded article, a prepreg, a two-layer body, a metal-clad laminate, and the like using the composition are provided.

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Abstract

Cette invention se rapporte à une composition polymère de réticulation contenant un polymère de norbornène aromatique ayant un poids moléculaire moyen en nombre (Mn) compris entre 500 et 500 000 et un agent de réticulation; à des feuilles et à des pré-imprégnés produits à partir d'une telle composition; ainsi qu'à des stratifiés produits par stratification de ces feuilles et/ou de ces pré-imprégnés.
PCT/JP1997/002735 1996-08-07 1997-08-06 Composition polymere de reticulation WO1998005715A1 (fr)

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JPH11269394A (ja) * 1998-03-24 1999-10-05 Nippon Zeon Co Ltd 接着性樹脂組成物
JP2005047992A (ja) * 2003-07-30 2005-02-24 Nof Corp 架橋性樹脂組成物、架橋性樹脂成形品および難燃性架橋樹脂成形品
JP2005047991A (ja) * 2003-07-30 2005-02-24 Nof Corp めっき可能な架橋性樹脂組成物、架橋性樹脂成形品および架橋樹脂成形品
JP2005239975A (ja) * 2004-02-27 2005-09-08 Maruzen Petrochem Co Ltd 芳香族含有環状オレフィン共重合体の製造方法
JP2006503171A (ja) * 2002-10-11 2006-01-26 ユニバーシティ オブ コネチカット 架橋ポリシクロオクテン
WO2007026527A1 (fr) * 2005-08-30 2007-03-08 Zeon Corporation Polymère d'addition de cyclooléfines, composite et article moulé de celui-ci et matériau optique
US7273915B2 (en) 2003-08-13 2007-09-25 Zeon Corporation Crosslinkable resin composition and resin formed body produced therefrom
JP2008031319A (ja) * 2006-07-28 2008-02-14 Fujifilm Corp ノルボルネン系重合体、フィルム、偏光板および液晶表示装置
US7364672B2 (en) 2004-12-06 2008-04-29 Arlon, Inc. Low loss prepregs, compositions useful for the preparation thereof and uses therefor
CN100390217C (zh) * 2003-08-13 2008-05-28 日本瑞翁株式会社 聚合性组合物、以及由此得到的成型体
US7579404B2 (en) 2003-08-07 2009-08-25 Zeon Corporation Polymerizable composition and molded product thereof

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JPH02255848A (ja) * 1988-12-21 1990-10-16 Mitsui Petrochem Ind Ltd 難燃性環状オレフィン系重合体組成物
JPH0314882A (ja) * 1989-03-10 1991-01-23 Mitsui Petrochem Ind Ltd メッキ用組成物およびメッキ物
JPH04132730A (ja) * 1990-01-02 1992-05-07 General Electric Co <Ge> 硬化可能なポリフェニレンエ―テル‐ポリエポキシド組成物
JPH04356554A (ja) * 1990-11-01 1992-12-10 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂組成物
JPH04372613A (ja) * 1991-06-20 1992-12-25 Nippon Soda Co Ltd 難燃性樹脂組成物
JPH059269A (ja) * 1991-07-03 1993-01-19 Dow Chem Nippon Kk 電気積層板用エポキシ樹脂組成物
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JPH06228380A (ja) * 1993-01-29 1994-08-16 Mitsui Petrochem Ind Ltd 環状オレフィン系重合体組成物
JPH06240066A (ja) * 1993-02-12 1994-08-30 Mitsui Petrochem Ind Ltd 環状オレフィン系樹脂組成物
JPH0872210A (ja) * 1993-10-26 1996-03-19 Mitsui Petrochem Ind Ltd ポリオレフィン系多層積層体および用途
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JPH10120768A (ja) * 1996-08-28 1998-05-12 Nippon Zeon Co Ltd 環状オレフィン系重合体及び架橋性重合体組成物
JPH11269394A (ja) * 1998-03-24 1999-10-05 Nippon Zeon Co Ltd 接着性樹脂組成物
JP2006503171A (ja) * 2002-10-11 2006-01-26 ユニバーシティ オブ コネチカット 架橋ポリシクロオクテン
JP2005047992A (ja) * 2003-07-30 2005-02-24 Nof Corp 架橋性樹脂組成物、架橋性樹脂成形品および難燃性架橋樹脂成形品
JP2005047991A (ja) * 2003-07-30 2005-02-24 Nof Corp めっき可能な架橋性樹脂組成物、架橋性樹脂成形品および架橋樹脂成形品
EP1655319B1 (fr) * 2003-08-07 2012-03-28 Zeon Corporation Composition polymerisable et corps forme constitue de cette composition
US7803870B2 (en) 2003-08-07 2010-09-28 Zeon Corporation Polymerizable composition and molded product thereof
US7579404B2 (en) 2003-08-07 2009-08-25 Zeon Corporation Polymerizable composition and molded product thereof
US7381782B2 (en) 2003-08-13 2008-06-03 Zeon Corporation Polymerizable composition and molded articles produced by using the same
US7273915B2 (en) 2003-08-13 2007-09-25 Zeon Corporation Crosslinkable resin composition and resin formed body produced therefrom
CN100390217C (zh) * 2003-08-13 2008-05-28 日本瑞翁株式会社 聚合性组合物、以及由此得到的成型体
JP2005239975A (ja) * 2004-02-27 2005-09-08 Maruzen Petrochem Co Ltd 芳香族含有環状オレフィン共重合体の製造方法
JP4587679B2 (ja) * 2004-02-27 2010-11-24 丸善石油化学株式会社 芳香族含有環状オレフィン共重合体の製造方法
US7364672B2 (en) 2004-12-06 2008-04-29 Arlon, Inc. Low loss prepregs, compositions useful for the preparation thereof and uses therefor
WO2007026527A1 (fr) * 2005-08-30 2007-03-08 Zeon Corporation Polymère d'addition de cyclooléfines, composite et article moulé de celui-ci et matériau optique
JP2008031319A (ja) * 2006-07-28 2008-02-14 Fujifilm Corp ノルボルネン系重合体、フィルム、偏光板および液晶表示装置

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