WO2013137175A1 - Composition polymérisable, article moulé en résine, et article moulé en résine composite - Google Patents

Composition polymérisable, article moulé en résine, et article moulé en résine composite Download PDF

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WO2013137175A1
WO2013137175A1 PCT/JP2013/056597 JP2013056597W WO2013137175A1 WO 2013137175 A1 WO2013137175 A1 WO 2013137175A1 JP 2013056597 W JP2013056597 W JP 2013056597W WO 2013137175 A1 WO2013137175 A1 WO 2013137175A1
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chain transfer
transfer agent
group
polymerizable composition
carbon
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PCT/JP2013/056597
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Japanese (ja)
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明彦 吉原
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日本ゼオン株式会社
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Publication of WO2013137175A1 publication Critical patent/WO2013137175A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/144—Side-chains containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/16—End groups
    • C08G2261/164—End groups comprising organic end groups
    • C08G2261/1644—End groups comprising organic end groups comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • 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

Definitions

  • the present invention relates to a polymerizable composition, a resin molded body, and a resin composite molded body. More specifically, the present invention relates to a polymerizable composition that gives a resin composite molded article having excellent adhesion to different materials, a resin molded article obtained using this polymerizable composition, and a resin composite molded article.
  • a cycloolefin polymer obtained by polymerizing a polymerizable monomer containing a cycloolefin monomer such as a norbornene-based monomer in the presence of a metathesis polymerization catalyst has a low water absorption, electrical characteristics, mechanical characteristics, impact resistance characteristics, Since it is excellent in heat resistance, weather resistance, etc., it has been put to practical use for molded articles in a wide range of fields.
  • Such a cycloolefin polymer is suitably used as an electrical insulating material such as a printed wiring board or a terminal electrode of an electronic component because of its excellent electrical characteristics and heat resistance.
  • an electrical insulating material that insulates the wiring layer or a terminal electrode of an electronic component mounted on such a printed wiring board is sealed. Since the electrical insulating material used for stopping requires solder heat resistance in addition to electrical characteristics, a cycloolefin polymer is suitably used as such an electrical insulating material.
  • Patent Document 1 the surface of a metal material to be bonded to a cycloolefin polymer is treated with a predetermined coupling agent in advance, thereby improving the adhesion between the cycloolefin polymer and the metal material.
  • a predetermined coupling agent in advance
  • Patent Document 1 the technique described in Patent Document 1 has a problem in that the surface of the metal material needs to be previously treated with a predetermined coupling agent, and the manufacturing process becomes complicated.
  • An object of the present invention is to provide a polymerizable composition that gives a resin composite molded article having excellent adhesion to different materials, a resin molded article obtained by using this polymerizable composition, and a resin composite molded article. It is in.
  • the present inventors have found that a polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, and a chain transfer agent having an organic acid group has an adhesive property to different materials.
  • the present inventors have found that an excellent resin composite molded body can be provided, and have completed the present invention based on this finding.
  • a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, and a chain transfer agent having an organic acid group [2] The polymerizable composition according to the above [1], wherein the chain transfer agent having an organic acid group is a chain transfer agent having an acid anhydride group, [3] The polymerizable composition according to [2], wherein the chain transfer agent having an acid anhydride group is a compound represented by the following general formula (1): (In the above general formula (1), R 1 is an optionally substituted hydrocarbon group having 3 to 30 carbon atoms, and R 2 is a hydrogen atom or an optionally substituted carbon.
  • a polymerizable composition that provides a resin composite molded article having excellent adhesion to different materials.
  • a resin molded body and a resin composite molded body obtained using such a polymerizable composition and having excellent adhesion to different materials are provided.
  • the (crosslinkable) resin molded body and the (crosslinked) resin composite molded body may be collectively referred to as a resin composite molded body.
  • the polymerizable composition of the present invention comprises a cycloolefin monomer, a metathesis polymerization catalyst, and a chain transfer agent having an organic acid group.
  • the cycloolefin monomer used in the present invention is a compound having an alicyclic structure formed of carbon atoms and having a polymerizable carbon-carbon double bond in the alicyclic structure.
  • polymerizable carbon-carbon double bond refers to a carbon-carbon double bond involved in chain polymerization (metathesis ring-opening polymerization).
  • Examples of the alicyclic structure of the cycloolefin monomer include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a combination polycyclic ring.
  • the cycloolefin monomer used in the present invention is preferably a polycyclic cycloolefin monomer from the viewpoint of improving the mechanical strength of the resulting resin composite molded article.
  • the number of carbon atoms constituting each ring structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.
  • the cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. Good.
  • the cycloolefin monomer those having at least one crosslinkable carbon-carbon unsaturated bond are preferably used from the viewpoint of improving the mechanical strength of the obtained resin composite molded article.
  • the “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in metathesis ring-opening polymerization but participates in a crosslinking reaction.
  • the “crosslinking reaction” refers to a reaction that forms a bridge structure, and usually refers to a radical crosslinking reaction or a metathesis crosslinking reaction, particularly a radical crosslinking reaction.
  • crosslinkable carbon-carbon unsaturated bond examples include carbon-carbon unsaturated bonds excluding aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond.
  • the position of the unsaturated bond is not particularly limited, and any position other than the alicyclic structure other than the alicyclic structure formed by carbon atoms. For example, at the end or inside of the side chain.
  • the aliphatic carbon-carbon double bond includes those existing as a vinyl group (CH 2 ⁇ CH—), a vinylidene group (CH 2 ⁇ C ⁇ ), or a vinylene group (—CH ⁇ CH—),
  • a vinyl group and / or vinylidene group preferably exists as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.
  • a norbornene monomer having at least one crosslinkable carbon-carbon unsaturated bond is particularly preferable.
  • the “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. Examples include norbornenes, dicyclopentadiene, and tetracyclododecene.
  • cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond examples include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene -2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylnorbornene, 5-allylnorbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, 2-ethylidene-1, 4,5,8-dimethano-1,
  • any one of a plurality of carbon-carbon unsaturated bonds is involved in metathesis ring-opening polymerization, and thus polymerizable. It acts as a carbon-carbon double bond, and as a result of the metathesis ring-opening polymerization, the remaining carbon-carbon unsaturated bond that did not participate in the metathesis ring-opening polymerization acts as a crosslinkable carbon-carbon unsaturated bond.
  • Any of a plurality of carbon-carbon unsaturated bonds may act as a polymerizable carbon-carbon double bond, and any of them may be a crosslinkable carbon- It may act as a carbon unsaturated bond.
  • cycloolefin monomer in addition to a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond, a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is used.
  • cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond examples include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, tetracyclododecene, 1 4,5,8-dimethano
  • cycloolefin monomers can be used alone or in combination of two or more.
  • a mixture of a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is used.
  • the blending ratio of the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is What is necessary is just to select suitably as desired. These blending ratios are preferable because the heat resistance and mechanical strength are improved in a balanced manner in the resulting resin composite molded article.
  • the polymerizable composition of the present invention may contain any monomer copolymerizable with the above-described cycloolefin monomer as long as the expression of the effect of the present invention is not inhibited.
  • the cycloolefin monomer can be subjected to metathesis ring-opening polymerization, and usually a plurality of ions, atoms, polyatomic ions, compounds and the like are bonded with a transition metal atom as a central atom.
  • the complex which consists of is mentioned.
  • transition metal atoms atoms of Group 5, Group 6 and Group 8 (according to the long-period periodic table; the same shall apply hereinafter) are used.
  • the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum.
  • Examples of the Group 6 atom include molybdenum and tungsten.
  • the Group 8 atom examples include examples thereof include ruthenium and osmium. Of these transition metal atoms, Group 8 ruthenium and osmium are preferred. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable.
  • the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex has excellent catalytic activity during bulk polymerization, when the molded composition is obtained by subjecting the polymerizable composition of the present invention to bulk polymerization, the resulting molded body has less odor derived from unreacted monomers. A high-quality molded product with good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.
  • Examples of the ruthenium carbene complex include those represented by the following general formula (2) or general formula (3).
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom.
  • X 1 and X 2 each independently represents an arbitrary anionic ligand.
  • An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.
  • L 1 and L 2 each independently represent a heteroatom-containing carbene compound or a neutral electron donating compound other than the compound.
  • a hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.
  • heteroatom-containing carbene compound examples include compounds represented by the following general formula (4) or general formula (5).
  • R 5 to R 8 are each independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R 5 to R 8 may be bonded together in any combination to form a ring.
  • the neutral electron-donating compound may be any ligand as long as it has a neutral charge when separated from the central metal.
  • Specific examples thereof include phosphines, ethers and pyridines, and trialkylphosphine is more preferable.
  • R 3 and R 4 may be bonded to each other to form a ring, and R 3 , R 4 , X 1 , X 2 , L 1 and L 2 May be bonded together in any combination to form a multidentate chelating ligand.
  • a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a metathesis polymerization catalyst from the viewpoint of increasing the production efficiency of the molded product.
  • the hetero atom constituting the heterocyclic structure include an O atom and an N atom, and an N atom is preferable.
  • an imidazoline structure and an imidazolidine structure are preferable.
  • the ruthenium catalyst having a compound having such a heterocyclic structure as a ligand is represented by the above general formula (2) or (3), and a ligand comprising a heteroatom-containing carbene compound as L 1 or L 2
  • a ruthenium catalyst having the following can be preferably used.
  • heteroatom-containing carbene compound examples include, for example, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1 , 3-Di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1 , 3-Dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-
  • the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound include benzylidene (1,3-dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitymy
  • the use amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5, in a molar ratio of (metal atom in catalyst: cycloolefin monomer).
  • the range is from 000 to 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000. If the amount of the metathesis polymerization catalyst used is too small, the polymerization activity is too low and the reaction takes time, resulting in poor production efficiency. If the amount used is too large, the reaction is too intense, so that the catalyst is cured in an insufficiently molded state, or the catalyst Tends to precipitate, and tends to be difficult to store uniformly.
  • the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent, if necessary.
  • solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbon
  • the chain transfer agent having an organic acid group used in the present invention may be a compound having an organic acid in the molecule and acting as a chain transfer agent.
  • the organic acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, and a thiol group.
  • those having a carboxylic acid group are preferable, and in particular, carbon-carbon unsaturated.
  • a carboxylic acid having a bond is more preferable.
  • the number of organic acid groups in the chain transfer agent may be one or plural, and when it has a plurality of organic acid groups, an anhydride group structure may be formed.
  • the polymerizable composition of the present invention and the resin composite molded body obtained using the same are excellent in adhesiveness to different materials. It becomes possible.
  • a chain transfer agent having an organic acid group it is possible to provide sufficient adhesion to different materials even when the different materials are not subjected to surface treatment in advance.
  • chain transfer agent having an organic acid group examples include 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11 -Aliphatic carboxylic acids having a carbon-carbon unsaturated bond at the terminal, such as dodecenoic acid, p-vinylbenzoic acid, p-allylbenzoic acid, 3-vinylphenylacetic acid, 4-vinylphenylacetic acid, 4-allylphenylacetic acid Acid; isocyanuric acids such as 1,3-diallylmonocarboxyl isocyanuric acid, 1,3-carboxylmonoallyl isocyanuric acid; and the like. These can be used alone or in combination of two or more. Among these, an aliphatic carboxylic acid having a carbon-carbon unsaturated bond at the terminal is preferable.
  • an acid anhydride group as an organic acid group that is, a chain transfer agent having an acid anhydride group may be used.
  • a chain transfer agent having a group the polymerizable composition of the present invention and the resin composite molded body obtained using the same are excellent in heat resistance while being excellent in adhesion to different materials. can do.
  • a chain transfer agent having an acid anhydride group as the chain transfer agent having an organic acid group, the effect of improving the adhesion to different materials can be further enhanced.
  • any compound having an acid anhydride group in the molecule and acting as a chain transfer agent may be used.
  • examples include those having an anhydride group of an organic acid such as an anhydride group, and those having an anhydride group of an inorganic acid such as a phosphoric anhydride group.
  • a chain transfer agent which has an acid anhydride group what has a carboxylic acid anhydride group is preferable, and the compound represented by following formula (1) is more preferable.
  • R 1 is an optionally substituted hydrocarbon group having 3 to 30 carbon atoms
  • R 2 is a hydrogen atom or an optionally substituted carbon number. 1 to 30 hydrocarbon groups, and at least one of R 1 and R 2 has a structure having an unsaturated bond at the terminal. That is, when R 2 is a hydrogen atom or a hydrocarbon group having 1 carbon atom, R 1 is a hydrocarbon group having an unsaturated bond at the terminal, and R 2 is a hydrocarbon group having 2 to 30 carbon atoms. When it is a hydrogen group, one or both of R 1 and R 2 become a hydrocarbon group having an unsaturated bond at the terminal.
  • the chain transfer agent having an acid anhydride group is used as the chain transfer agent having an organic acid group, so that the crosslinking reaction can be sufficiently performed without adding a crosslinking agent to the polymerizable composition.
  • a crosslinking agent need not necessarily be contained.
  • R 1 is an optionally substituted hydrocarbon group having 3 to 30 carbon atoms, and the hydrocarbon group constituting R 1 has 3 to 25 carbon atoms. And those of 4 to 20 are more preferred.
  • the substituent is not particularly limited. For example, a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, —C (C ⁇ O) — OR 9 group; and the like.
  • R 9 is an alkyl group having 1 to 6 carbon atoms.
  • R 2 is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and when R 2 is a hydrocarbon group, The hydrocarbon group constituting R 2 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of the substituent include the same as those for R 1 described above. A hydrogen atom is preferable.
  • R 1 may have a substituent having 3 to 3 carbon atoms from the viewpoint that the effects of the present invention become more remarkable.
  • 30 hydrocarbon groups having a terminal unsaturated bond and R 2 being a hydrogen atom are preferred.
  • R 1 is more preferably a linear hydrocarbon group having an unsaturated bond at the terminal, and, apart from the terminal unsaturated bond, one or more unsaturated bonds in the carbon chain.
  • those having one unsaturated bond in the carbon chain are even more preferable, and a group represented by the following general formula (6) is particularly preferable.
  • R 10 is an alkylene group having 1 to 10 carbon atoms.
  • the amount of the chain transfer agent having an organic acid group is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 0 to 100 parts by weight of the cycloolefin monomer. 1 to 3 parts by weight. If the amount of the chain transfer agent having an organic acid group is too small, the effect of adding a chain transfer agent having an organic acid group, that is, the effect of improving the adhesion to different materials such as metal materials may not be obtained. On the other hand, when there are too many compounding quantities of the chain transfer agent which has an organic acid group, there exists a possibility that the heat resistance fall and water absorption of a resin molding or a resin composite molded object may deteriorate.
  • the chain transfer agent having an organic acid group is preferably 0.01 to 2 parts by weight, more preferably 0. .05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight. Even in this case, if the amount of the chain transfer agent having an organic acid group is too small, the effect of adding the chain transfer agent having an organic acid group, that is, the effect of improving the adhesion to different materials may not be obtained. On the other hand, if the amount of the chain transfer agent having an organic acid group is too large, heat resistance and water absorption may be deteriorated.
  • Chain transfer agent having an epoxy group, chain transfer agent having a (meth) acryloyl group when a chain transfer agent other than the chain transfer agent having an acid anhydride group is used as the chain transfer agent having an organic acid group, the chain transfer agent having an epoxy group and a (meth) acryloyl group are included. It is preferable to further use at least one of the chain transfer agents. In the present invention, when a chain transfer agent other than the chain transfer agent having an acid anhydride group is used as the chain transfer agent having an organic acid group, the chain transfer agent having an epoxy group and the chain having a (meth) acryloyl group are used.
  • the polymerizable composition of the present invention and the resin composite molded body obtained using the same are excellent in heat resistance while being excellent in adhesiveness to different materials.
  • the transfer agents By using at least one of the transfer agents in combination, the polymerizable composition of the present invention and the resin composite molded body obtained using the same are excellent in heat resistance while being excellent in adhesiveness to different materials. Can be. Further, by using at least one of a chain transfer agent having an epoxy group and a chain transfer agent having a (meth) acryloyl group in combination, the effect of improving the adhesion to different materials can be further enhanced.
  • any compound having an epoxy group and acting as a chain transfer agent may be used, but those having a carbon-carbon unsaturated bond in the molecule are preferred, and a carbon-carbon unsaturated group is present at the terminal. Those having a saturated bond are more preferred.
  • chain transfer agent having an epoxy group examples include alkenyl glycidyl ethers such as allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether; butadiene monoepoxide, 4,5-epoxy-2-pentene, 1 1,2-epoxy-5,9-cyclododecadiene and other diene or polyene monoepoxides; 1,2-epoxy-3-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene Alkenyl epoxides such as 1,2-epoxy-9-decene; Epoxides having a cyclic structure such as 1,2-epoxy-4-vinylcyclohexane; 1,3-diallylmonoglycidyl isocyanuric acid, 1,3-glycidyl Isocyanuric acids such as monoallyl iso
  • alkenyl glycidyl ethers are preferred.
  • the amount of the chain transfer agent having an epoxy group is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, still more preferably 100 parts by weight of the cycloolefin monomer. 0.1 to 1 part by weight.
  • the chain transfer agent having a (meth) acryloyl group may be any compound having a (meth) acryloyl group and acting as a chain transfer agent, but carbon-carbon unsaturation other than the (meth) acryloyl group in the molecule. Those having a bond are preferable, and those having a carbon-carbon unsaturated bond other than the (meth) acryloyl group at the terminal are more preferable.
  • chain transfer agent having a (meth) acryloyl group examples include carbon-carbon unsaturation such as vinyl methacrylate, hexenyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, and styryl acrylate.
  • Examples include (meth) acrylate having a bond. These can be used alone or in combination of two or more.
  • the amount of the chain transfer agent having a (meth) acryloyl group in the polymerizable composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer. 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
  • the total amount of the chain transfer agent having an organic acid group, the chain transfer agent having an epoxy group, and the chain transfer agent having a (meth) acryloyl group is within the above range.
  • the chain transfer agent having an organic acid group, the chain transfer agent having an epoxy group, and (meth) from the viewpoint that the effect of improving the adhesion to different materials and the effect of improving the heat resistance become more remarkable.
  • the total amount of the chain transfer agent having an acryloyl group is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 100 parts by weight of the cycloolefin monomer. Is 0.5 to 4 parts by weight.
  • the compounding quantity of the chain transfer agent which has an organic acid group, the chain which has an epoxy group is “the amount of the chain transfer agent having an organic acid group”: “the chain transfer agent having an epoxy group and the (meth) acryloyl group” Is preferably in the range of 1: 1 to 1:30, more preferably in the range of 1: 2 to 1:20.
  • a chain transfer agent having an epoxy group and a chain transfer agent having a (meth) acryloyl group as the chain transfer agent, a chain transfer agent having an organic acid group, What is necessary is just to use in combination with at least one of the chain transfer agent which has an epoxy group, and the chain transfer agent which has a (meth) acryloyl group, but the improvement effect of the adhesiveness with respect to a dissimilar material, and the improvement effect of heat resistance are more remarkable.
  • the agent is used in combination with a chain transfer agent having an organic acid group and a chain transfer agent having a (meth) acryloyl group, or a chain transfer agent having an organic acid group and a chain transfer having an epoxy group. More preferably, the agent is used in combination with a chain transfer agent having a (meth) acryloyl group.
  • the polymerizable composition of the present invention may contain a crosslinking agent in addition to the components described above.
  • a crosslinking agent By containing a crosslinking agent, the polymerizable composition of the present invention (in particular, polymerization using a chain transfer agent other than a chain transfer agent having an acid anhydride group having a crosslinking action as a chain transfer agent having an organic acid group).
  • the polymer obtained by bulk polymerization of the conductive composition can be made into a thermoplastic resin that can be efficiently post-crosslinked.
  • “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin.
  • a radical generator is usually preferably used.
  • the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators.
  • organic peroxide examples include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy)
  • diazo compound examples include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis.
  • Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1, 1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2- Triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.
  • the 1-minute half-life temperature of the radical generator is not particularly limited, but is usually in the range of 150 to 300 ° C, preferably 180 to 250 ° C.
  • the 1-minute half-life temperature is a temperature at which half of the radical generator decomposes in 1 minute.
  • the 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, NOF Corporation).
  • the blending amount of the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of the crosslinking agent is within such a range, the resulting crosslinked resin composite molded article has a sufficient crosslinking density, which is preferable.
  • the crosslinking reaction can be carried out without blending a crosslinking agent in the polymerizable composition. It is not necessary to contain a cross-linking agent because it can sufficiently proceed, but even when using a chain transfer agent having an acid anhydride group, a cross-linking agent is added from the viewpoint of further improving heat resistance. Also good.
  • the polymerizable composition of the present invention may contain other fillers, polymerization regulators, polymerization reaction retarders, flame retardants, antioxidants, crosslinking aids, and other colorants as desired.
  • a compounding agent can be added.
  • the filler is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used, but inorganic fillers are preferred.
  • the inorganic filler examples include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc.
  • metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten
  • carbon particles such as carbon black, graphite, activated carbon, and carbon balloon
  • silica, silica balloon, alumina Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite
  • inorganic carbonate particles such as calcium carbonate, magnesium carbonate,
  • Inorganic sulfate particles inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate; Aluminum nitride, silicon carbide grains And whiskers, and the like.
  • organic filler include compound particles such as wood powder, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more.
  • the inorganic filler when using an inorganic filler, from the viewpoint of increasing the affinity with a polymer obtained by polymerizing a cycloolefin monomer (cycloolefin polymer), the inorganic filler includes known fatty acids, fats and oils, surfactants, Surface treatment may be performed with molecules, titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like.
  • a silane coupling agent is preferably used because of excellent compatibility with the cycloolefin polymer.
  • silane coupling agent examples include allyltrimethoxysilane, 3-butenyltrimethoxysilane, p-styryltrimethoxysilane, N- ⁇ - (N- (vinylbenzyl) aminoethyl) - ⁇ -aminopropyltri Methoxysilane and its salts, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, ⁇ -methacrylic Roxyethyltrimethoxysilane, ⁇ -methacryloxyethyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxybutyltrimethoxysilane,
  • the blending amount of the filler is usually 1 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight, more preferably 500 to 800 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.
  • the polymerization regulator is blended for the purpose of controlling the polymerization activity and improving the polymerization reaction rate.
  • Specific examples thereof include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium. These polymerization regulators may be used alone or in combination of two or more.
  • the polymerization regulator is used in a molar ratio of (metal atom in the metathesis polymerization catalyst: polymerization regulator), usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20. More preferably, it is in the range of 1: 0.5 to 1:10.
  • the polymerization reaction retarder functions to suppress the viscosity increase of the polymerizable composition.
  • Polymerization retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used.
  • the amount of the polymerization reaction retarder used is usually 1: 0.01 to 1: 100, preferably 1: 0.1 to 1:10, in a molar ratio of (metal atom in catalyst: polymerization reaction retarder). More preferably, it is in the range of 1: 0.2 to 1: 5.
  • the flame retardant is not particularly limited, and is a known flame retardant, for example, halogen flame retardant, phosphorus-nitrogen flame retardant, phosphate ester flame retardant, nitrogen flame retardant, antimony flame retardant, and inorganic flame retardant. It can be appropriately selected from the group consisting of flame retardants. What is necessary is just to adjust the compounding quantity suitably so that a desired effect may be acquired.
  • the heat resistance of the obtained resin composite molded article can be improved to a high degree without inhibiting the crosslinking reaction, which is preferable.
  • a phenolic antioxidant and an amine antioxidant are preferable, and a phenolic antioxidant is particularly preferable.
  • These antioxidants may be used alone or in combination of two or more.
  • the blending amount of the antioxidant is appropriately selected according to the purpose of use, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the cycloolefin monomer. The range is preferably 0.01 to 1 part by weight.
  • a crosslinking aid may be blended in addition to the crosslinking agent.
  • a crosslinking aid a compound having two or more crosslinkable carbon-carbon unsaturated bonds that are not involved in ring-opening polymerization and can participate in a crosslinking reaction induced by a radical generator is preferable.
  • Such a crosslinkable carbon-carbon unsaturated bond is preferably present, for example, as a terminal vinylidene group, particularly as an isopropenyl group or a methacryl group, more preferably as a methacryl group, in the compound constituting the crosslinking aid. preferable.
  • crosslinking aid examples include polyfunctional compounds having two or more isopropenyl groups such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1, 3 -Butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2 '-Bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc.
  • polyfunctional compounds having two or more isopropenyl groups such as p-diisopropenylbenzene, m
  • polyfunctional compounds having two or more methacryl groups polyfunctional compounds having three methacryl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferable.
  • Crosslinking aids can be used alone or in combination of two or more.
  • the amount of the crosslinking aid added to the polymerizable composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, particularly 100 parts by weight of the cycloolefin monomer.
  • the amount is preferably 1 to 30 parts by weight.
  • the polymerizable composition of the present invention can be obtained by mixing the above components.
  • a mixing method a conventional method may be followed.
  • a liquid (catalyst solution) in which a ruthenium carbene complex as a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent, a cycloolefin monomer, and, if desired, other blends It can be prepared by adding to a liquid (monomer liquid) containing the agent and stirring.
  • chain transfer agents other than the chain transfer agent having an organic acid group, the chain transfer agent having an epoxy group, and the chain transfer agent having a (meth) acryloyl group described above. You may use it in combination.
  • chain transfer agents include divinylbenzene, allyltrimethoxysilane, and allyl isocyanate.
  • the blending amount is usually 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.
  • the resin composite molded article of the present invention can be obtained by bringing the above-described polymerizable composition of the present invention into contact with a different material and bulk polymerizing the cycloolefin monomer.
  • Examples of a method for obtaining a resin composite molded body by bulk polymerization of the polymerizable composition include, for example, (a) a method in which a polymerizable composition is applied on a support made of a different material, and then bulk polymerization, and (b) polymerization.
  • (c) impregnating the polymerizable composition into a fibrous reinforcement and then contacting the dissimilar material examples include a bulk polymerization method.
  • the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be carried out smoothly, and in the injection in the method (b), even if it is a space portion having a complicated shape, the foam bite is rapidly formed.
  • the polymerizable composition can be spread without causing it, and in the method (c), the fibrous reinforcing material can be impregnated with the polymerizable composition quickly and uniformly.
  • a resin composite molded body such as a film or plate can be obtained.
  • the thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less.
  • the polymerizable composition coated on the support is optionally dried and then bulk polymerized. Bulk polymerization is performed by heating the polymerizable composition at a predetermined temperature.
  • the method for heating the polymerizable composition is not particularly limited, and the polymerizable composition applied to the support is heated on a heating plate, and heated (hot press) while being pressed using a press. Examples thereof include a method, a method of pressing with a heated roller, and a method of heating in a heating furnace.
  • a resin composite molded body having an arbitrary shape can be obtained.
  • the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape.
  • a conventionally known mold for example, a split mold structure, that is, a mold having a core mold and a cavity mold, can be used, and a polymerizable composition is formed in these voids (cavities). Is injected to cause bulk polymerization.
  • the core mold and the cavity mold are produced so as to form a gap that matches the shape of the target molded product.
  • the shape, material, size, etc. of the mold are not particularly limited.
  • the position and shape of the dissimilar material in the mold may be determined by a known method with reference to insert molding or transfer molding.
  • the molding die may have a plurality of portions having different temperatures in order to improve the finish of the surface of the molded product, and may be provided with a demolding mechanism such as a pin so that the obtained molded product can be easily demolded.
  • a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds.
  • a sheet-like or film-like resin composite molded body can also be obtained by bulk polymerization.
  • the filling pressure (injection pressure) when filling the polymerizable composition into the mold cavity is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer surface formed on the inner peripheral surface of the cavity tends not to be transferred well. If the filling pressure is too high, the mold must be rigid and economical. is not.
  • the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
  • Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in the mold, and a method for heating the mold in an electric furnace.
  • a known method and apparatus such as a transfer mold molding machine, a potting apparatus, and a RIM (reaction injection molding machine) can be used.
  • the method (c) is preferably used for obtaining a sheet-shaped or film-shaped resin composite molded body.
  • the impregnation of the polymerizable composition into the fibrous reinforcing material is performed by using a predetermined amount of the polymerizable composition such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, and a slit coating method. It can apply by apply
  • the polymerizable composition After impregnating the polymerizable composition into the fibrous reinforcing material, the polymerizable composition is bulk polymerized by heating to a predetermined temperature in a state where the impregnated material is in contact with a different material, and a desired resin composite Get.
  • an impregnated material obtained by impregnating a polymerizable composition into a fibrous reinforcing material in a state where it is in contact with a different material for example, the impregnated material is placed on a support made of a different material.
  • the method of heating like the method of b) is mentioned.
  • the thickness of the resin composite molded body obtained by the method (c) is not particularly limited, but is usually 1 ⁇ m to 10 mm.
  • the content of the fibrous reinforcing material in the molded body may be appropriately selected according to the purpose of use, but is usually in the range of 5 to 50% by volume, preferably 15 to 40% by volume. If the content of the fibrous reinforcing material is within this range, the resulting laminate has good mechanical strength.
  • the body is obtained.
  • the pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.
  • the hot pressing may be performed in a vacuum or a reduced pressure atmosphere.
  • the hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).
  • SMC sheet mold compound
  • BMC bulk mold compound
  • Resin such as polyethylene terephthalate, a polypropylene, polyethylene, a polycarbonate, a polyethylene naphthalate, a polyarylate, nylon; Iron, stainless steel, copper, aluminum, nickel, 42 alloy, chromium, A metal material such as gold or silver can be used, but it is preferable to use a metal material as a different material from the viewpoint that the effects of the present invention become more remarkable.
  • the shape of the different material is not particularly limited, but a metal foil or a metal frame is preferable.
  • a resin-coated copper foil Resin Coated Copper (RCC)
  • the thickness of the metal foil as the different material is usually 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 3 to 75 ⁇ m from the viewpoint of workability and the like. Also, when a metal frame is used for a different material, copper subjected to nickel-palladium-gold plating (copper plated in the order of nickel, palladium, gold from the outermost layer) is preferable because of excellent heat resistance and corrosion resistance. What is necessary is just to select the thickness of a metal frame timely as needed.
  • the heating temperature for polymerizing the polymerizable composition is usually more than 50 ° C., preferably more than 50 ° C. and not more than 250 ° C., more preferably 70 to 200 ° C., further preferably 80 to 150 ° C. .
  • the crosslinking agent has a half-life temperature of 1 minute or less, preferably a 1-minute half-life temperature of 10 ° C. or less, more preferably 1
  • the minute half-life temperature is 20 ° C. or less.
  • the polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes.
  • the polymerization conversion rate is preferably 90% or more, more preferably 95% or more, and further preferably 99% or more. Heating the polymerizable composition under such conditions is preferable because a resin composite molded body with less unreacted monomer can be obtained. If the polymerization temperature is too low, the mechanical strength of the resulting resin composite molded article may be lowered. Similarly, when the polymerization conversion rate is too low, the mechanical strength of the resulting resin composite molded body may be lowered.
  • the polymerization conversion rate can be quantified using, for example, gas chromatography. Moreover, you may make heat processing into a resin molding after superposition
  • the heating temperature of the heat treatment is usually in the range of 100 to 300 ° C., more preferably 120 to 250 ° C., and further preferably 140 to 200 ° C.
  • the heating time may be appropriately selected, but is usually in the range of 0.1 to 240 minutes, preferably 1 to 180 minutes, more preferably 10 to 120 minutes.
  • the molecular weight of the polymer (cycloolefin polymer) constituting the resin composite molded body obtained as described above is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: toluene). Usually, it is in the range of 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 100,000.
  • the resin composite molded body of the present invention may be a resin in which a part of the constituent resin is cross-linked depending on the shape thereof.
  • the temperature may be too high.
  • a crosslinking reaction may occur in the high temperature portion, and crosslinking may occur.
  • the surface portion that easily dissipates heat is not substantially crosslinked, it can be post-crosslinked, so that it can exhibit a desired effect as a post-crosslinked molded article.
  • the bulk polymerization may be performed without using a different material and in contact with the different material (for example, in the method (b), the different material is not placed in the mold).
  • the polymerizable composition may be injected into the mold to cause bulk polymerization).
  • a resin molded body that is not in contact with a different material can also be obtained.
  • the crosslinked resin composite molded body of the present invention is obtained by crosslinking the above-described resin molded body.
  • Crosslinking of the resin molded body can be performed by maintaining the molded body at a temperature higher than the temperature at which the crosslinking reaction occurs.
  • the heating temperature is usually in the range of 100 to 300 ° C, preferably 150 to 250 ° C.
  • the heating time is in the range of 0.1 to 240 minutes, preferably 1 to 180 minutes, more preferably 10 to 120 minutes.
  • the heating temperature may be higher than the temperature at which the crosslinking agent reacts.
  • the radical generator is used as the crosslinking agent.
  • the temperature is higher than the temperature at which a crosslinking reaction is induced by the decomposition of.
  • the temperature is one minute half-life temperature of the radical generator or more, preferably 5 ° C. or more higher than the one-minute half-life temperature, more preferably 10 ° C. or more higher than the one-minute half-life temperature.
  • it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C.
  • the heating time is in the range of 0.1 to 240 minutes, preferably 1 to 180 minutes, more preferably 10 to 120 minutes.
  • the atmosphere at the time of heating is not particularly limited, and may be selected as appropriate in a vacuum, in the air, or in an inert gas such as argon or nitrogen.
  • the apparatus used at this time is not specifically limited, For example, what is necessary is just to use oven, a hot press, a hotplate, etc. suitably according to the shape of a desired crosslinked-resin composite molded object.
  • the resin composite molded body and the cross-linked resin composite molded body of the present invention thus obtained are obtained using the above-described polymerizable composition of the present invention, and the polymerizable composition of the present invention is a cycloolefin. It contains a monomer, a metathesis polymerization catalyst, and a chain transfer agent having an organic acid group.
  • the resin composite molded body and the cross-linked resin composite molded body obtained by the action of the chain transfer agent having an organic acid group are converted into different materials. It can be made to have excellent adhesiveness to.
  • the resin composite molded body and the cross-linked resin composite molded body of the present invention have characteristics inherent to cycloolefin resins such as low linear expansion coefficient, high mechanical strength, and low dielectric loss tangent. It can be suitably used for material applications, in particular, sealing materials such as coils, capacitors, and semiconductors, and multilayer circuit board applications.
  • Tg measurement A test piece (size: width 5 mm ⁇ length 45 mm ⁇ thickness 1 mm) collected from the resin molded body was subjected to measurement with a dynamic viscoelasticity tester (manufactured by Seiko Instruments Inc., model number: EXSTAR DMS6100), and the test piece was measured from room temperature to 300 Tg was determined from the peak value of tan ⁇ with a frequency of 1 Hz.
  • Example 1 In a glass flask, 51 parts by weight of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts by weight of triphenylphosphine are dissolved in 952 parts by weight of toluene. As a result, a catalyst solution was prepared.
  • silica MCF-200C, manufactured by Tatsumori Co., Ltd., center particle size 11.3 ⁇ m
  • 2- (2 -Norbornyl) Ethyltrimethoxysilane 10 parts was sprayed and then stirred at 120 ° C. for 15 minutes to obtain silica surface-treated with a silane coupling agent (surface-treated silica).
  • SAYTEX8010 halogen flame retardant
  • PATOX-M antimony flame retardant
  • 2,7-octadiene 2,7-octadiene as a chain transfer agent
  • (2,7-octadien-1-yl) succinic anhydride is a group represented by the general formula (1) in which R 2 is a hydrogen atom and R 1 is a group represented by the general formula (6).
  • R 10 in the general formula (6) corresponds to a C 3 alkylene group.
  • the polymerizable composition thus obtained was molded into a flat plate mold having a thickness of 1 mm, a length of 100 mm, and a width of 100 mm (a mold formed by sandwiching a U-shaped spacer between a pair of chrome-plated iron plates with a heater).
  • the resin molding was obtained by heating for 30 seconds under the conditions of a product surface temperature of 95 ° C. and a back surface temperature of 95 ° C. as mold temperatures.
  • the obtained resin molded body was cut into a predetermined size (width 5 mm ⁇ length 45 mm ⁇ thickness 1 mm), and placed in an oven at 200 ° C. for 1 hour for heat treatment (crosslinking).
  • the obtained polymerizable composition was applied to one surface of a nickel plate (a nickel-plated copper plate) to form a polymerizable composition layer on the surface of the nickel plate.
  • a laminated structure having a three-layer structure of nickel plate / polymerizable composition layer / nickel plate was obtained by superimposing a nickel plate different from the above on the surface of the formed polymerizable composition layer.
  • the laminated structure is configured such that the area where the nickel plate and the polymerizable composition layer overlap is 12.5 mm ⁇ 25.0 mm, and the pair of nickel plates is in the length direction.
  • the thickness of the polymerizable composition layer was adjusted to 1 mm as the thickness after the bulk ring-opening polymerization.
  • the obtained laminated structure is put in a mold having a predetermined temperature, heated at 95 ° C. for 30 seconds, and bulk polymerized to obtain a resin having a three-layer structure of nickel plate / resin layer / nickel plate
  • a composite molded body was obtained.
  • die was counted, and the adhesiveness between a nickel plate and a resin molded object was determined.
  • the results are shown in Table 1.
  • the obtained resin composite molded body was placed in an oven at 200 ° C. for 1 hour and heat-treated (crosslinked) to obtain a resin composite molded body having a three-layer structure of nickel plate / resin layer / nickel plate.
  • Example 2 Example 1 except that the amount of (2,7-octadien-1-yl) succinic anhydride as a chain transfer agent was changed from 1.5 parts to 0.3 parts when preparing the monomer liquid.
  • a polymerizable composition was prepared, each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. The results are shown in Table 1.
  • a polymerizable composition was prepared in the same manner as in Example 1 except that 1 part and 20 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a crosslinking assistant were further added. And each molded object was manufactured using the obtained polymeric composition, and each evaluation was performed. The results are shown in Table 1.
  • Example 4 When preparing the monomer liquid, the blending amount of undecenyl methacrylate as the chain transfer agent was changed from 2.85 parts to 2.7 parts, and the blending amount of 10-undecenoic acid as the chain transfer agent was changed to 0.8.
  • a polymerizable composition was prepared in the same manner as in Example 3 except that the amount was changed from 15 parts to 0.3 part, and each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. It was. The results are shown in Table 1.
  • Example 5 When preparing the monomer liquid, the amount of undecenyl methacrylate as the chain transfer agent was changed from 2.85 parts to 2.4 parts, and the amount of 10-undecenoic acid as the chain transfer agent was changed to 0.2.
  • a polymerizable composition was prepared in the same manner as in Example 3 except that the amount was changed from 15 parts to 0.6 part, and each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. It was. The results are shown in Table 1.
  • Example 6 When preparing the monomer liquid, the amount of undecenyl methacrylate as the chain transfer agent was changed from 2.85 parts to 1.43 parts, and allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) as the chain transfer agent. A polymerizable composition was prepared in the same manner as in Example 3 except that 0.71 part was further added, and each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. The results are shown in Table 1.
  • Example 7 When preparing the monomer liquid, the amount of 10-undecenoic acid as the chain transfer agent was changed from 0.15 parts to 3 parts, and undecenyl methacrylate was not blended as the chain transfer agent. In the same manner as in Example 3, a polymerizable composition was prepared, each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. The results are shown in Table 1.
  • Example 1 except that 3 parts of undecenyl methacrylate was used in place of 1.5 parts of (2,7-octadien-1-yl) succinic anhydride as a chain transfer agent when preparing the monomer liquid.
  • a polymerizable composition was prepared, each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. The results are shown in Table 1.
  • Example 4 When preparing the monomer liquid, it was the same as Example 3 except that 3 parts of allyl glycidyl ether as a chain transfer agent was blended instead of blending undecenyl methacrylate and 10-undecenoic acid as chain transfer agents. Then, a polymerizable composition was prepared, each molded body was produced using the obtained polymerizable composition, and each evaluation was performed. The results are shown in Table 1.
  • Examples 3 to 6 in which at least one of a chain transfer agent having a chain and a chain transfer agent having a (meth) acryloyl group is further used in combination the resulting resin molded product does not swell after heating at 200 ° C. Furthermore, the glass transition temperature was sufficiently high, and therefore the heat resistance was extremely excellent.
  • Comparative Examples 1 to 5 using only a chain transfer agent having an epoxy group and a chain transfer agent having a (meth) acryloyl group without using a chain transfer agent having an organic acid group as a chain transfer agent, In the case of a composite molded body with a nickel plate, peeling between the nickel plate and the resin layer occurred remarkably, resulting in a very small number of good molded products at the time of demolding. From this result, it can be determined that the composite molded bodies obtained in Comparative Examples 1 to 5 have poor adhesion to different materials (nickel plates).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne une composition polymérisable comprenant un monomère de cyclooléfine, un catalyseur de polymérisation par métathèse et un agent de transfert de chaîne ayant un groupe acide organique. De préférence, l'agent de transfert de chaîne est un agent de transfert de chaîne ayant un groupe anhydride d'acide. En variante, l'agent de transfert de chaîne comprend en outre, de préférence, en plus d'un agent de transfert de chaîne ayant un groupe acide organique, un agent de transfert de chaîne ayant un groupe époxy et/ou un agent de transfert de chaîne ayant un groupe (méth)acryloyle. Selon la présente invention, une composition polymérisable peut être produite, qui permet la production d'un article moulé en résine composite ayant une excellente adhérence à différents matériaux.
PCT/JP2013/056597 2012-03-15 2013-03-11 Composition polymérisable, article moulé en résine, et article moulé en résine composite WO2013137175A1 (fr)

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JPWO2016152362A1 (ja) * 2015-03-26 2017-11-09 京セラ株式会社 誘電体フィルム、およびこれを用いたフィルムコンデンサ、連結型コンデンサ、ならびにインバータ、電動車輌
EP3284766A1 (fr) * 2016-08-16 2018-02-21 Bostik Sa Nouveaux polymères hydrocarbonés à groupements terminaux dithiocyclocarbonate
JP2018512075A (ja) * 2015-03-17 2018-05-10 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ フレキシブル導電振動膜、フレキシブル振動センサ及びその製造方法と応用
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JP2018512075A (ja) * 2015-03-17 2018-05-10 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ フレキシブル導電振動膜、フレキシブル振動センサ及びその製造方法と応用
JPWO2016152362A1 (ja) * 2015-03-26 2017-11-09 京セラ株式会社 誘電体フィルム、およびこれを用いたフィルムコンデンサ、連結型コンデンサ、ならびにインバータ、電動車輌
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FR3055134A1 (fr) * 2016-08-16 2018-02-23 Bostik Sa Nouveaux polymeres hydrocarbones a groupements terminaux dithiocyclocarbonate
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JP2021070742A (ja) * 2019-10-30 2021-05-06 アキレス株式会社 難燃性シクロオレフィン系樹脂成形体
JP7477957B2 (ja) 2019-10-30 2024-05-02 アキレス株式会社 難燃性シクロオレフィン系樹脂成形体製造方法

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