WO2002098974A1 - Composition de resine, preimpregne, et produit en couches - Google Patents

Composition de resine, preimpregne, et produit en couches Download PDF

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Publication number
WO2002098974A1
WO2002098974A1 PCT/JP2002/005352 JP0205352W WO02098974A1 WO 2002098974 A1 WO2002098974 A1 WO 2002098974A1 JP 0205352 W JP0205352 W JP 0205352W WO 02098974 A1 WO02098974 A1 WO 02098974A1
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WIPO (PCT)
Prior art keywords
component
resin composition
weight
curable resin
alicyclic olefin
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PCT/JP2002/005352
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English (en)
Japanese (ja)
Inventor
Hitomi Takeuchi
Hitoshi Shimizu
Fumio Takano
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Zeon Corporation
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Publication of WO2002098974A1 publication Critical patent/WO2002098974A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • the present invention relates to a curable resin composition, a prepreg impregnated with the composition, and a laminate using the same.
  • a fiber base material such as a glass fiber nonwoven fabric or an aromatic polyamide fiber (aramid fiber) nonwoven fabric is impregnated with a resin.
  • Pre-preda has been proposed.
  • a resin composition varnish
  • a prepreg with a low solid content concentration.
  • air bubbles remain in the pre-predator, and furthermore, the air bubbles cannot be extruded due to poor fluidity during molding, and air bubbles remain in the laminated body.
  • the plating liquid may penetrate into the bubbles, causing insulation failure and reducing the electrical reliability in some cases.
  • epoxy resin is used to impregnate the fiber base
  • a xy resin is generally used.
  • Epoxy resins are characterized by low viscosity even at high solids concentrations and high fluidity even during semi-curing. By using this epoxy resin, it is possible to extrude the air bubbles remaining in the pre-predder at the time of pressure molding, and it is possible to obtain a laminate having few residual air bubbles.
  • the laminates are required to have improved electrical properties such as dielectric constant.
  • a curable resin composition comprising an alicyclic olefin polymer and a thermosetting component (International Publication WO98 / 15595).
  • alicyclic olefin polymer a polymer having no polar group having a relatively low weight average molecular weight Mw, or a polymer having a weight average molecular weight of
  • an object of the present invention is to provide a curable resin composition comprising an alicyclic olefin polymer and a thermosetting component and having good impregnation and fluidity, a prepreg impregnated with the same and a prepreg manufactured using the prepreg.
  • An object of the present invention is to provide a laminate having few bubbles. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the use of an alicyclic olefin polymer having a polar group having a relatively low weight-average molecular weight Mw can improve impregnation and fluidity.
  • a curable resin composition containing 100 parts by weight of an alicyclic olefin polymer component and 10 to 90 parts by weight of a thermosetting component is provided.
  • at least one of the component polymers constituting the alicyclic olefin polymer component has a polar group; and (2) the component polymer constituting the alicyclic olefin polymer component.
  • At least one of the curable resin compositions is characterized in that the weight average molecular weight Mw is at least 50,000 and less than 50,000, and as a second invention, a fiber base material is provided. A prepreg impregnated with the curable resin composition is provided. As a third invention, a laminate having a layer obtained by curing the prepreg is provided. BEST MODE FOR CARRYING OUT THE INVENTION
  • the curable resin composition of the present invention contains an alicyclic olefin polymer component and a thermosetting component.
  • the alicyclic olefin polymer component is composed of one or more alicyclic olefin polymers (component polymers).
  • the alicyclic olefin polymer according to the present invention comprises a polymer containing a repeating unit derived from an olefin having an alicyclic structure (hereinafter, also referred to as an alicyclic olefin).
  • alicyclic structures examples include a cycloalkane structure and a cycloalkene structure. From the viewpoints of mechanical strength, heat resistance, and the like, a cycloalkyne structure is preferable.
  • alicyclic structures can be monocyclic or polycyclic (condensed polycyclic, bridged, , Etc.). Although there is no particular limitation on the number of carbon atoms constituting the alicyclic structure, when the number is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15, Various properties such as strength, heat resistance and moldability are highly balanced and suitable.
  • the proportion of the repeating unit derived from the olefin having such alicyclic structure in the alicyclic olefin polymer is appropriately selected according to the purpose of use, but is usually 30 to 100% by weight, preferably 50 to 100% by weight. It is 100% by weight, more preferably 70 to 100% by weight. If the proportion of the repeating unit derived from an alicyclic olefin is too small, heat resistance, dielectric properties, and low water absorption are unfavorably poor.
  • one of the component polymers constituting the alicyclic olefin polymer component is an alicyclic olefin polymer having a polar group.
  • Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Carboxyl groups or carboxylic anhydride groups are preferred. These polar groups can be used alone or in combination of two or more. The content of the polar group in the alicyclic olefin polymer component is appropriately selected depending on the purpose of use, but it is usually determined with respect to all the repeating units of all the component polymers constituting the alicyclic olefin polymer component.
  • Cycloaliphatic olefin polymers are usually polymerized by addition or ring-opening polymerization of alicyclic olefins and, if necessary, hydrogenation of unsaturated bonds, or addition polymerization of aromatic olefins. Then, it is obtained by hydrogenating the aromatic ring portion of the polymer.
  • the alicyclic olefin polymer having a polar group includes, for example, 1) a polar group-containing compound by introducing a compound having a polar group into the alicyclic olefin polymer through a modification reaction.
  • a polar group-containing compound by introducing a compound having a polar group into the alicyclic olefin polymer through a modification reaction.
  • Examples of the alicyclic olefin used to obtain the alicyclic olefin polymer include bicyclo [2.2.1] hepta-12-ene (common name norbornane), 5-methyl-bicyclo [2 2.1) Hepta-2-ene, 5,5-dimethyl-1-bicyclo [2.2.1] Hepter 2-ene, 5-ethyl-bicyclo [2.2.1] Hepta-2-ene , 5-butyl-bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.1]-hepta-2-ene, 5-hexyl-bicyclo [2 2.
  • aromatic olefin examples include styrene, ⁇ -methylstyrene, dibutylbenzene and the like.
  • the alicyclic or aromatic olefins can be used alone or in combination of two or more.
  • the method for polymerizing alicyclic olefins and aromatic olefins and the method for hydrogenation as required are not particularly limited, and can be performed according to known methods.
  • one of the component polymers constituting the alicyclic olefin polymer component has a weight average molecular weight Mw (hereinafter, may be simply referred to as Mw) of 500 to 5,000.
  • Mw weight average molecular weight
  • it is an alicyclic polymer having a molecular weight of 5,000 or more and 4,000 or less.
  • the alicyclic olefin polymer having Mw of 5,000 or more and less than 50,000, preferably 5,000 or more and 4,000 or less simultaneously has the polar group described in detail above. May be present, or an alicyclic olefin polymer different from the alicyclic olefin polymer having a polar group.
  • the weight average molecular weight is a weight average molecular weight in terms of polystyrene (or polyisoprene) measured by gel permeation chromatography (GPC) using chloroform or tetrahydrofuran as a solvent.
  • GPC gel permeation chromatography
  • porcine form is used for Mw measurement of a polymer having no polar group
  • tetrahydrofuran is used for Mw measurement of a polymer having a polar group.
  • the amount of the polymer ⁇ ⁇ whose M w is 500 or more and less than 500 It is usually at least 10% by weight, preferably 20 to 100% by weight, based on the total amount of all the component polymers constituting the olefin polymer component. / 0 , more preferably 20 to 90% by weight, the formation of bubbles can be suppressed.
  • the alicyclic olefin polymer component according to the present invention includes, in addition to the polymer having Mw in the above-described range, for example, a polymer having Mw of 500 or more and less than 900 ° An alicyclic olefin polymer having a relatively high Mw such as 2 can be used together.
  • These polymers having a relatively high Mw are used in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 90% by weight or less, based on the total amount of all the component polymers constituting the alicyclic olefin polymer component.
  • a proportion of 10 to 80% by weight the formation of bubbles is suppressed, the moldability is excellent, and the mechanical and thermal properties of the laminate are improved.
  • an alicyclic olefin polymer having an Mw of more than 900, 3 ⁇ an alicyclic olefin polymer having an Mw of less than 50,000, an alicyclic olefin polymer component Although it is possible to use as a component polymer constituting the above, from the viewpoint of securing good fluidity, the use ratio is preferably 10% by weight or less, more preferably 10% by weight or less in the alicyclic olefin polymer component. Is less than 5% by weight.
  • a molecular weight modifier such as a bullet compound or a gen compound may be added to the monomer in an amount of 0.1 to 0.1 wt.
  • a method of adding about 1 to 10 mol% can be mentioned.
  • a relatively low Mw polymer can be obtained by using a small amount of the molecular weight modifier, and a relatively low Mw polymer can be obtained by using a large amount. can get.
  • vinyl compound used as a molecular weight modifier examples include ⁇ -olefin compounds such as 1-butene, 1-pentene, 1-hexene, and 1-octene; styrene compounds such as styrene and vinylinoletoluene; ethylbutyl ether and isobutyl Ether compounds such as butyl ether and aryl glycidyl ether; aryl Halogen-containing vinyl compounds such as chloride; oxygen-containing vinyl compounds such as aryl acetate, aryl alcohol and dalicidyl methacrylate; and nitrogen-containing vinyl compounds such as acrylamide.
  • ⁇ -olefin compounds such as 1-butene, 1-pentene, 1-hexene, and 1-octene
  • styrene compounds such as styrene and vinylinoletoluene
  • ethylbutyl ether and isobutyl Ether compounds such as butyl
  • Non-conjugated diene compounds such as 1,4-pentagen, 1,5-hexadiene, 1,6-hexadiene, 2-methyl-1,4-pentadiene, 2,5-dimethinolate 1,5-hexadiene;
  • 1 Conjugated compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentagen, and 1,3-hexadiene.
  • the thermosetting component used in the present invention is composed of a compound that is cured by heating, and may contain a curing agent or a curing accelerator as needed.
  • a compound that cures by heating is a low molecular compound before heating and becomes a polymer by heating, and then cures, but it is a polymer before heating but does not cure at room temperature, but cures by heating. You may.
  • the mechanism of curing by heating is not particularly limited, and examples thereof include a mechanism by a crosslinking reaction and a condensation reaction.
  • thermosetting component examples include a thermosetting component containing a compound having two or more reactive groups in one molecule, a curing agent, and a curing accelerator.
  • Compounds having two or more reactive groups in one molecule include those having two or more epoxy groups in one molecule, those having two or more butyl groups or internal olefin groups in one molecule, Those having two or more (meth) acryloyl groups in the molecule, those having at least two or more reactive groups selected from epoxy group, butyl group, and (meth) acryloyl group in one molecule are exemplified. Of these, those having two or more epoxy groups in one molecule, or at least two or more reactive groups selected from epoxy group, butyl group, and (meth) acryloyl group in one molecule Those having a group are preferred. Furthermore, in one molecule, at least two or more selected from epoxy groups, vinyl groups, and (meth) atalyloyl groups Of those having the above reactive group, those in which at least one of the reactive groups is an epoxy group are particularly preferred.
  • Examples of the compound having two or more epoxy groups in one molecule include epoxy such as bisphenol type, novolak type, alicyclic type, heterocyclic type, condensed type, glycerin type and dicyclopentadiene type.
  • epoxy such as bisphenol type, novolak type, alicyclic type, heterocyclic type, condensed type, glycerin type and dicyclopentadiene type.
  • Compounds Specifically, a bisphenol type epoxy compound represented by the formula (E 1), a hydrogenated bisphenol type epoxy compound obtained by hydrogenating a bisphenol type epoxy compound represented by the formula (E 1), a compound represented by the formula (E 2) And the like.
  • R is a hydrocarbon group
  • n 0 or an integer of 1 or more.
  • R may be a straight chain or branched, but is preferably an isopropylidene group.
  • n is 0. Or a mixture of integers greater than or equal to 1.
  • n an integer from 0 to 5)
  • At least one of them has a reactive group.
  • the oxy group include a buridyl compound having a daricidyl group and a (meth) atalylate compound, a bur compound having a cyclohexenoxide structure, and a (meth) atalylate compound.
  • Examples thereof include 1-5-hexene, 1-aryl-1,3,5-diglycidyl isocyanurate, and 1,3-diallyl-5-glycidyl isocyanurate.
  • Polyimide can be used as a compound having two or more reactive groups in one molecule. More specifically, addition-type aromatic polyimides such as nadic acid-terminated polyimides and acetylene-terminated polyimides; polyaminobismaleimide (PI) resins, epoxy resins, acryl compounds, acryl compounds, and bur compounds on PI resins And modified bismaleimide-type polyimides such as bismaleimide 'triazine (BT) resin. These compounds having two or more reactive groups in one molecule can be used alone or in combination of two or more.
  • addition-type aromatic polyimides such as nadic acid-terminated polyimides and acetylene-terminated polyimides
  • PI polyaminobismaleimide
  • BT bismaleimide 'triazine
  • the curing agent examples include an aliphatic polyamine compound, an alicyclic polyamine compound, an aromatic polyamine compound, a bisazide compound, an acid anhydride, a dicarboxylic acid compound, a diol compound, a triol compound, a polyvalent phenol compound, a polyamide, and a diisocyanate compound. And preferably polyhydric phenol compounds and aromatic polyamine compounds, specifically, phenol novolak, tarezol novolak, diaminodiphenylmethane dicyandiamide and the like. These curing agents can be used alone or in combination of two or more. The amount of the curing agent is usually 0.01 to 20 parts by weight based on 100 parts by weight of the compound having two or more reactive groups in one molecule.
  • the curing accelerator examples include amine compounds, imidazole compounds, Known compounds such as a nitrogen-containing heterocyclic compound such as diazabicycloundecene, an organic phosphine, an organic boron complex, a quaternary ammonium compound, and a quaternary phosphonium can be used.
  • imidazole compounds are preferred because they have a high curing promoting effect, and organic phosphorus compounds and diazabicycloundecene are effective in reducing the extraction of ionic impurities.
  • imidazole-based compounds examples include 2-methylimidazole, 2-ethylimidazole, 2-ethynole 4-methinoleimidazole, bis-1-ethynole-4-methylimidazole, 1-methyl-2-ethylimidazole, 2 —Alkyl-substituted imidazole compounds such as isopyl pyrimidazole, 2,4-dimethylimidazole, and 2-heptadecylimidazole; 2-phenylimidazole, 2-phenylimidazole 4-methinoreimidazole, 1-benzyl_2-methylimidazolone, 1—Benzizole 2—Echinoleimidazonole, 1—Benzyl 2—Feninolei midazonole, Benzi midazonole, 2-Echinole-1-4-methinole 1- (2′—Cyanoethyl) imidazole, 2-Ethyru-4-methyl-1—
  • organic phosphorus compound examples include triphenylphosphine and triphenylphosphine phenol salt.
  • imidazole having a substituent having a ring structure is preferred from the viewpoint of compatibility with the alicyclic olefin polymer, and 1-benzyl-12-phenylimidazole is particularly preferred.
  • These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator can be appropriately selected according to the type of the compound having two or more reactive groups in one molecule.
  • the amount of the thermosetting component is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer component. When it is in this range, the moldability is good and the physical properties such as heat resistance are excellent, so that it is preferable.
  • thermosetting resin composition of the present invention includes a radical crosslinking agent, a flame retardant, another resin, a filler, a heat-resistant stabilizer, a weather-resistant stabilizer, a leveling agent, an antistatic agent, and a slurry.
  • Agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, emulsions, etc., and the mixing ratio is within a range that does not impair the object of the present invention. It is appropriately selected.
  • radical cross-linking agent examples include methyl ethyl ketone peroxide, cyclohexanone pentanoloxide, 1,1-bis (t-butynoleperoxy) -13,3,5-trimethylcyclohexane , 2,2-Bis (t-butylperoxy) butane, t-butylhydridoperoxide, 2,5-dimethylhexane-1,2,5-dihydrazinoleoxide, dicumylphenoloxide, 2,5-dimethinole-1,2,5 - di (t _ Buchiruperuokishi) - 3 - to relaxin, alpha, alpha-bis (t one Buchiruperuokishi _ m - isopropyl) benzene, OTA Tano I le peroxide O, dimethylsulfoxide, isobutyryl peroxide O, dimethylsulfoxide, pel O carboxymethyl dicarbonate
  • crosslinking agents can be used alone or in combination of two or more, and the amount thereof is usually 0.01 to 0.1 part by weight of the alicyclic olefin polymer component. -20 parts by weight, preferably 0.01-1 parts by weight.
  • a flame retardant generally used to make plastics flame retardant can be used, and a reactive flame retardant can also be used.
  • Concrete Phosphoric esters such as tris (tribromoneopentyl) phosphate, modifiphenyl ether, antimony trioxide, 9,10-dihydro 9-oxa 10 10-phosphaphenanthrene 1 1 0-oxide and its quinone adduct, polyphosphamide, melamine polyphosphate, tetrabromobisphenol A and the like.
  • the blending amount of the flame retardant is appropriately selected according to the purpose of use, but it is usually 0.1 to 50 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of the cyclic cyclic polymer component. 0 parts by weight is preferably employed.
  • Examples of the polymer other than the alicyclic olefin polymer component and the thermosetting component include a rubbery polymer and other resins.
  • the rubbery polymer is a polymer having a Tg of usually 30 ° C or less, and specific examples include natural rubber, polyisobutylene rubber, butyl rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile 'butadiene. Copolymer rubber, styrene. Butadiene copolymer rubber, styrene ⁇ Gen-based rubber such as isoprene copolymer rubber, styrene. Butadiene.
  • Isoprene terpolymer rubber, and hydrogenated products of these gen-based rubbers Saturated polyolefin rubbers such as ethylene propylene copolymers and other ethylene- ⁇ -olefin copolymers, propylene and other ⁇ -olefin copolymers; ethylene propylene- gen copolymers, and olefin copolymers , ⁇ -olefin 'isoprene copolymer, isobutylene'gen copolymer, iso- Polyolefin-based polymer rubber such as Tylene 'isoprene copolymer; special rubber such as urethane rubber, polyether rubber, acrylic rubber, propylene oxide rubber, ethylene acrylic rubber; styrene-butadiene-styrene block copolymer rubber Styrene-based thermoplastic elastomers such as styrene-isoprene-styrene block copolymer rubber
  • resins include, for example, polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; polyamides such as nylon 66 An ethylene-ethyl acrylate copolymer, an ethylene-butyl acetate copolymer; a polyester; a polycarbonate; an ataryl resin; and a polyimide.
  • polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene
  • polyamides such as nylon 66 An ethylene-ethyl acrylate copolymer, an ethylene-butyl acetate copolymer
  • the mixing ratio of the other polymer is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the alicyclic olefin polymer component. 0 parts by weight.
  • the filler can be blended for the purpose of improving the mechanical strength, reducing the coefficient of thermal expansion, and obtaining an arbitrary dielectric constant.
  • Well-known inorganic fillers such as O 3 -PbTio_3_MgO system can be used.
  • the shape is selected from powder, granule, needle, and fiber depending
  • the compounding amount of the filler is in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer component, and the compounding amount is determined according to the purpose. (Varnish)
  • the varnish of the present invention is obtained by dissolving the curable resin composition in a solvent.
  • This penis is suitable for impregnating the fiber base material with the curable resin composition.
  • An organic solvent is preferable as a solvent used for preparing the varnish, and in particular, by using a mixed solvent composed of a non-polar organic solvent and a polar organic solvent, excellent impregnation into a fiber substrate is achieved, and dielectric properties are improved. Low water absorption, interlayer adhesion and moldability are highly balanced.
  • the curable resin composition may not be sufficiently uniformly dispersed in the fiber base material, and may not cover the fiber interface. As a result, in particular, low water absorption and low dielectric loss tangent are inferior.
  • Non-polar organic solvents include, for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; linear aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; cyclopentane, cyclohexane and the like
  • aromatic hydrocarbons and alicyclic hydrocarbons specifically, xylene and toluene, are preferred from the viewpoint of excellent compatibility with the alicyclic olefin polymer. preferable.
  • polar organic solvents include halogenated hydrocarbons such as benzene, dichlorobenzene, and the like; ketones such as acetone, methylethylketone, methylisobutynoleketone, cyclopentanone, cyclohexanone, benzophenone, and acetophenone; Ethers such as trahydrofuran, tetrahydropyran and anisol; methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, Esters such as ethyl butyrate, butyl butyrate, amyl butyrate, ethyl lactate, dimethyl carbonate, dimethyl phthalate, methyl phthalate, and ⁇ -butyl lactone; ethylene carbonate
  • Carbonate compounds ⁇ -methylpyrrolidone, ⁇ _ethylpyrrolidone, ⁇ -phenylpyrrolidone, ⁇ -benzylpyrrolidone, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylformamide, ,, ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylylacetate
  • Amide compounds such as toamide; nitrile compounds such as acetonitrile, propionitrile, butyronitrile, benzonitrile, and forcepronitrile; Sulfoxide compounds such as dimethyl sulfoxide; and the like.
  • ketones, esters, carbonate compounds, amide compounds and the like are preferable from the viewpoint of compatibility with the alicyclic olefin polymer, and ketones are particularly preferable, and cyclopentanone and cyclohexanone such as cyclopentanone are preferable. Alkanone is particularly preferred.
  • the mixing ratio of the nonpolar solvent and the polar solvent can be appropriately selected, but is usually 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably by weight. Is in the range of 20:80 to 80:20.
  • the amount of the solvent used is usually 5 to 70% by weight, preferably 10 to 65% by weight, Preferably, the solvent is used in an amount of 20 to 60% by weight.
  • the method of dissolving the alicyclic olefin polymer component, the thermosetting component, and other components added as needed in a solvent may be in accordance with a conventional method, for example, using a stirrer and a magnetic stirrer. Stirring, high-speed homogenizer, dispurgeon, planetary stirrer, twin-screw stirrer, ball mill, three-roll method, etc. can be used.
  • the prepredder of the present invention is obtained by impregnating a fiber base material with the curable resin composition of the present invention.
  • the fibers constituting the fiber base material include polyester fibers, nylon 66 fibers, and aramide fibers (m-phenylene isophthalamide fiber, p—phenylene terephthalamide fiber, p—diphenyl ether terephthalamide fiber, and poly (ethylene terephthalamide) fiber.
  • Organic synthetic fibers such as atalylate fibers); natural fibers such as cellulose, cotton, hemp, wool, and silk; glass fibers (E glass, C glass, D glass, S glass, NE glass, H glass, etc.), asbestos, and inorganic fibers such as carbon fibers.
  • These fibers are individually formed or mixed to form a nonwoven or woven fabric.
  • preferred fibers are aramide fibers, polyester fibers and glass fibers, and particularly preferred are meta-based amide fibers, para-based amide fibers, wholly aromatic polyester fibers, E-glass fibers, and H-glass fibers.
  • Surface treatment methods include, for example, heat treatment with hot air, infrared light, near infrared light, etc .; immersion treatment with a solvent such as acid, alkali, alcohol, etc .; plasma treatment; corona treatment; ozone treatment; polyimide siloxane, aramide elastomer.
  • pre-impregnation treatment with biphenyl type epoxy resin, naphthalene type epoxy resin, coupling agent and the like can be mentioned. These surface treatments can be used alone or in combination of two or more.
  • a heat treatment or a pre-impregnation treatment with a coupling agent is effective for preventing swelling of the substrate.
  • the fiber substrate is 100-450. C, preferably in a high temperature atmosphere of 140 to 400 ° C. for heating.
  • the heating time can be appropriately selected, and is usually 5 to 120 minutes. By performing the heat treatment under reduced pressure, the heating temperature can be lowered and the heating time can be shortened.
  • Examples of the coupling agent used in the pre-impregnation treatment include epoxy silane, amino silane, acryl silane, butyl silane, ⁇ -mercaptopropyl trimethoxy silane, and the like.
  • 3-silane capping agents such as 3-mercaptopropyl trimethoxysilane, imidazole silane, triazine silane, etc .; isopropyl trisisostea porphyltitanate, isopropyl isopropyl tris i-dodecylbenzenesulfonyl titanate, isopropyl tris-n-dodecyl Benzenesulfonyl titanate, Isopropyl tris (dioctyl pyrophosphate) titanate, Tetraisopropyl monobis (dioctyl phosphate) titanate, Tetraoctyl monobis (ditridecyl phosphite) Titanate, Tetra ( 2,2-diaryloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate
  • the amount of the curable resin composition impregnated into the fiber base material is appropriately selected depending on the purpose of use, and is usually 10: by weight ratio of [curable resin composition solids]: [fiber base material].
  • the range is from 90 to 90: 10, preferably 20: 80 to 80: 20, and more preferably 30: 70 to 70: 30. When it is in this range, the moldability is good, and the dielectric properties, low water absorption and delamination strength are highly balanced, which is preferable.
  • the method for impregnating the fiber base material with the curable resin composition there is no particular limitation on the method for impregnating the fiber base material with the curable resin composition.
  • a method of removing the solvent after flowing the composition into the material, a method of spraying the composition onto a fiber base material, and then removing the solvent are exemplified.
  • the method of removing the solvent is appropriately selected according to the type of the solvent used, but the drying temperature is usually set to 50 to 200 ° C, preferably 70 to 150 ° C.
  • the curable resin composition impregnated into the fiber base material after removing the solvent is preferably in an uncured state. Thereafter, in order to cure the pre-preda, the curable resin composition is heated to a temperature at which a curing reaction occurs.
  • the thickness of the pre-preda is appropriately selected according to the purpose of use, but is usually from 10 to 100 ⁇ m, preferably from 20 to 500 ⁇ , and more preferably from 50 to 250 ⁇ m. Range. When the thickness of the pre-preda is in this range, the mechanical strength and the additivity are balanced, which is preferable.
  • the laminate of the present invention is obtained by laminating a plurality of the pre-preda of the present invention, molding under heat and pressure, curing and heat-sealing.
  • a circuit board can be obtained by laminating a conductor layer made of metal foil or the like on the prepreg of the present invention and then forming a circuit by surface etching or the like. After the circuit board is formed, the metal foil and pre-preda are stacked, heated and pressed, and the surface is etched to form a multilayer circuit board with a conductor layer not only on the outer surface of the laminate but also on the inside. Obtainable.
  • IC chips and the like can be enclosed and sealed between layers.
  • the method of laminating the conductor layer is not particularly limited.
  • a wet method such as a dry plating such as vapor deposition or sputtering, an electrolytic plating, or an electroless plating is used.
  • a method using a method such as a method.
  • the metals commonly used for conductor layers are copper, nickel, tin, silver, gold, aluminum, platinum, titanium, zinc and Chromium and the like. Of these, copper is preferred.
  • the heating temperature at the time of heating and pressurizing is in the range of 100 to 300 ° C, preferably 150 to 260 ° C. Within this range, the warpage of the laminate can be prevented, and the curing of the curable resin composition can be effectively completed.
  • the pressing force at the time of heating and pressurizing is in the range of 10 to 80 ⁇ (: ⁇ 2 , preferably 20 to 6 OK gZcm 2) , the pressure between the metal foil and the resin layer, and Adhesion can be increased, and air holes in the fiber base material can be substantially eliminated.
  • the molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • T g glass transition temperature
  • the test for delamination strength was performed according to the copper foil peel strength test of JIS C6481. More specifically, after heating and pressing the two-layer laminate, a cut of about 2 cm from the end is made between the two layers, and the cut end of one layer is cut with a jig of a peel strength tester. Grasping and pulling in the direction perpendicular to the aluminum plate surface, the peel strength was measured.
  • Solder heat resistance test was performed on 85% RH After leaving it for 4 hours, it was floated in a 260 ° C. solder bath for 20 seconds. The surface of the laminate was observed and evaluated as “A” when there was no blister and “B” when there was blister.
  • Polymer A has a weight-average molecular weight (Mw) of 61700, a molecular weight distribution (Mw / Mn) of 2.7, and a maleic acid group content of 22.3 moles 0 /.
  • Polymer B has a weight average molecular weight (Mw) of 25600, molecular weight distribution (MwZMn) of 1.8, maleic acid group content of 22.8 mol%
  • polymer C has a weight average molecular weight (Mw) of 1 0 100, molecular weight distribution (MwZMn) is 1.5, maleic acid group content is 27.7 mol. /. Met.
  • Example 1 30 parts of polymer A, 40 parts of polymer B, 30 parts of polymer C, brominated bisphenol A type epoxy resin (trade name: EP IC LON 152: manufactured by Dainippon Ink Co., Ltd.) 25 parts, hydrogenated bisphenol A type epoxy Resin (trade name: EPI CLON E XA 70 15: manufactured by Dai Nippon Ink Co., Ltd.) 15 parts and 0.1 part of 1-benzyl-2-phenylimidazole 0.1 part, xylene 163 parts and cycle pentanone 1 It was dissolved in 09 parts of a mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 34%.
  • brominated bisphenol A type epoxy resin trade name: EP IC LON 152: manufactured by Dainippon Ink Co., Ltd.
  • hydrogenated bisphenol A type epoxy Resin trade name: EPI CLON E XA 70 15: manufactured by Dai Nippon Ink Co., Ltd.
  • the viscosity of the varnish was 44 OmPa ⁇ S.
  • the aramide fiber nonwoven fabric substrate is obtained by laminating two pieces of aramide fiber nonwoven fabric.
  • One sheet of the prepredder was thermocompression-bonded with a vacuum press machine at 50 Kg / cm 2 and a temperature of 200 ° C. for 60 minutes, and the prepredder was cured to obtain a two-layer laminate.
  • Example 1 The same operation as in Example 1 was carried out except that polymer A was replaced with 30 parts and polymer C was replaced with 70 parts, without using polymer B, and xylene 144 parts and cyclopentanone 95 were used.
  • a mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 37%.
  • the varnish had a viscosity of 37 OmPa ⁇ S.
  • the varnish is dried at 80 ° C for 10 minutes and further dried at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition.
  • a two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.
  • Example 2 The same operation as in Example 1 was performed except that Polymer A and C were not used and Polymer B was used in 100 parts, and a mixed solvent of xylene 156 parts and cyclopentanone 104 parts was used. By dissolving, a varnish of a thermosetting resin composition having a solid content of 35% was obtained. The viscosity of this varnish was 43.5 mPa'S. The varnish is impregnated into the nonwoven fabric of the aramide fiber at an impregnation rate of 15 seconds, and then dried at 80 ° C for 10 minutes, and further dried at 120 ° C for 10 minutes to obtain a solidified curable resin composition.
  • a pre-preda having a content of 55% (solid content: base fiber content: 55:45 (weight ratio)) was obtained.
  • a two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.
  • Example 1 the same operation as in Example 1 was carried out except that neither Polymer A nor Polymer B was used and Polymer C was used in 100 parts, and a mixture of xylene (137 parts) and cyclopentanone (91 parts) was mixed. Dissolved in a solvent to form a thermosetting tree with a solid content of 38% A varnish of a fat composition was obtained. The viscosity of this varnish was 25 OmPa ⁇ S. After impregnating the varnish with the varnish at an impregnation speed of 5 seconds, the varnish is dried at 80 ° C for 10 minutes and further dried at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition of 57%.
  • a two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.
  • Example 1 the same operation as in Example 1 was carried out except that the polymer A was replaced with 50 parts and the polymer C was replaced with 50 parts without using the polymer B, and xylene 196 parts and cyclopentanone 13 It was dissolved in one part of the mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 30%.
  • the viscosity of this varnish was 42 OmPa ⁇ S.
  • This varnish is impregnated into the base material of the aramide fiber nonwoven at an impregnation speed of 15 seconds, and then dried at 80 ° C for 10 minutes and further at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition. 57% (solid content: base material fiber amount: 57:43 (weight ratio)) was obtained.
  • a two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.
  • the varnish obtained by dissolving the curable resin composition of the present invention in a solvent can impregnate the base material with the curable resin composition without reducing the impregnation rate even at a high solid content.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine durcissable contenant 100 parts en poids d'un ingrédient polymère oléfinique alicyclique, et 10 à 90 parts en poids d'un ingrédient thermodurcissable. La composition selon l'invention est caractérisée en ce que (1) au moins un des polymères constituant l'ingrédient polymère oléfinique alicyclique contient des groupes polaires et (2) au moins un des polymères constituant l'ingrédient polymère oléfinique alicyclique présente un poids moléculaire moyen en poids Mw de 5000 à 50000, 50000 étant exclu.
PCT/JP2002/005352 2001-06-01 2002-05-31 Composition de resine, preimpregne, et produit en couches WO2002098974A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2009038177A1 (fr) * 2007-09-19 2009-03-26 Tohoku University Composition de résine durcissable et son utilisation
WO2015093601A1 (fr) * 2013-12-20 2015-06-25 日本ゼオン株式会社 Matériau de résine et film de résine
EP2957596A4 (fr) * 2013-02-12 2016-08-31 Zeon Corp Composition de résine et produit moulé de celle-ci

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JP4872183B2 (ja) * 2004-03-19 2012-02-08 Ｊｓｒ株式会社 環状オレフィン系樹脂組成物、その成形品の処理方法、およびフィルムまたはシート
WO2008117799A1 (fr) * 2007-03-28 2008-10-02 Zeon Corporation Composite polymère de cyclo-oléfine et procédé de production de celui-ci
JP5630262B2 (ja) * 2010-12-27 2014-11-26 日本ゼオン株式会社 硬化性樹脂組成物、硬化物、積層体、多層回路基板、及び電子機器
US9453145B2 (en) * 2011-09-30 2016-09-27 Zeon Corporation Insulating adhesive film, prepreg, laminate, cured article, and composite article

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JPH0820692A (ja) * 1994-07-07 1996-01-23 Nippon Zeon Co Ltd 環状オレフィン樹脂組成物およびその架橋物
WO1998015595A1 (fr) * 1996-10-09 1998-04-16 Nippon Zeon Co., Ltd. Composition a base d'un polymere de norbornene
WO1999052980A1 (fr) * 1998-04-09 1999-10-21 Nippon Zeon Co., Ltd. Composition de resine alicyclique
JP2001098026A (ja) * 1999-09-29 2001-04-10 Nippon Zeon Co Ltd 環状オレフィン系付加重合体およびその製造方法
JP2001139777A (ja) * 1999-11-10 2001-05-22 Jsr Corp 熱硬化性樹脂組成物およびその硬化物

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JPS5388096A (en) * 1977-01-14 1978-08-03 Showa Denko Kk Adhesive resin composition having improved heat resistance
JPH05178969A (ja) * 1991-02-22 1993-07-20 Nippon Zeon Co Ltd 熱硬化性樹脂成形品

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JPH0820692A (ja) * 1994-07-07 1996-01-23 Nippon Zeon Co Ltd 環状オレフィン樹脂組成物およびその架橋物
WO1998015595A1 (fr) * 1996-10-09 1998-04-16 Nippon Zeon Co., Ltd. Composition a base d'un polymere de norbornene
WO1999052980A1 (fr) * 1998-04-09 1999-10-21 Nippon Zeon Co., Ltd. Composition de resine alicyclique
JP2001098026A (ja) * 1999-09-29 2001-04-10 Nippon Zeon Co Ltd 環状オレフィン系付加重合体およびその製造方法
JP2001139777A (ja) * 1999-11-10 2001-05-22 Jsr Corp 熱硬化性樹脂組成物およびその硬化物

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009038177A1 (fr) * 2007-09-19 2009-03-26 Tohoku University Composition de résine durcissable et son utilisation
EP2957596A4 (fr) * 2013-02-12 2016-08-31 Zeon Corp Composition de résine et produit moulé de celle-ci
US9631083B2 (en) 2013-02-12 2017-04-25 Zeon Corporation Resin composition and molded product thereof
WO2015093601A1 (fr) * 2013-12-20 2015-06-25 日本ゼオン株式会社 Matériau de résine et film de résine
JPWO2015093601A1 (ja) * 2013-12-20 2017-03-23 日本ゼオン株式会社 樹脂材料及び樹脂フィルム
US10086588B2 (en) 2013-12-20 2018-10-02 Zeon Corporation Resin material and resin film

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