WO2016103778A1 - Composition polymère et corps moulé - Google Patents

Composition polymère et corps moulé Download PDF

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Publication number
WO2016103778A1
WO2016103778A1 PCT/JP2015/071657 JP2015071657W WO2016103778A1 WO 2016103778 A1 WO2016103778 A1 WO 2016103778A1 JP 2015071657 W JP2015071657 W JP 2015071657W WO 2016103778 A1 WO2016103778 A1 WO 2016103778A1
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group
ring
cyclic olefin
parts
polymer
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PCT/JP2015/071657
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Japanese (ja)
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昌嗣 加藤
慎介 宮澤
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日本ゼオン株式会社
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Priority to US15/535,208 priority Critical patent/US10233301B2/en
Publication of WO2016103778A1 publication Critical patent/WO2016103778A1/fr

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    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08K3/40—Glass
    • 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 provides a substrate that is suitable for plating formation by a three-dimensional circuit forming technique (LDS) method, has excellent electrical insulation characteristics, high strength, and excellent plating adhesion even in a high-temperature and high-humidity environment.
  • LDS three-dimensional circuit forming technique
  • the present invention relates to a polymer composition and a molded article comprising an alicyclic structure-containing polymer.
  • the alicyclic structure-containing polymer is suitably used as an electrically insulating material because of its low dielectric loss tangent.
  • metal oxides that can form simple metal nuclei by electromagnetic radiation are used for plating formation by a three-dimensional circuit formation technology (LDS) method, which can easily form finer circuits, which are being put into practical use in recent years.
  • a substrate material made of a synthetic resin such as polybutylene terephthalate is preferably used (Patent Document 1). Further, when polycarbonate is used as a synthetic resin for the substrate material used in the LDS method, the polycarbonate is decomposed by the metal compound, the melt stability is lowered, and the problem that processing becomes difficult is solved.
  • Patent Document 2 It has been proposed to blend a rubbery polymer such as ABS (Patent Document 2).
  • Patent Document 3 proposes a resin molding material excellent in both impact resistance and electrical characteristics by blending a styrene-ethylene-propylene-styrene block copolymer rubber with a norbornene resin. .
  • the inventors of the present invention applied a polymer composition of a norbornene-based resin described in Patent Document 3 to a styrene-ethylene-propylene-styrene block copolymer rubber by simple irradiation by magnetic beam irradiation described in Patent Documents 1 and 2.
  • a metal oxide capable of forming a metal nucleus was blended and plating was formed by the LDS method, it was confirmed that sufficient plating adhesion could not be obtained. Therefore, when titanium dioxide proposed as a particularly preferable inorganic filler in Patent Document 2 was blended, although the plating adhesion was slightly improved, it was insufficient.
  • the present invention has been made in view of the above-described prior art, and has crystallinity having a repeating unit derived from a polycyclic norbornene monomer having three or more rings as a substrate material for plating formation by the LDS method.
  • An object is to achieve good electrical characteristics (low dielectric loss tangent), plating adhesion, and reflow heat resistance by using a cyclic olefin ring-opening polymer hydrogenated product.
  • the inventors of the present invention have good electrical characteristics (low dielectric loss tangent) when a glass filler and a specific metal oxide are used as an inorganic filler in a polymer composition.
  • the inventors have found that the strength can be maintained even when exposed to high temperature and high humidity conditions, and the present invention has been completed.
  • a polymer composition containing 5 to 100 parts by weight of glass filler and (C) 5 to 20 parts of metal oxide is provided.
  • the metal oxide is preferably CuCr 2 O 4 having a spinel structure.
  • (D) 1 to 20 parts of talc is preferably contained.
  • the molded object which uses the polymer composition of the said this invention, and the molded object which has a function of the dielectric antenna for high frequencies are provided.
  • the polymer composition of the present invention comprises (A) a crystalline cyclic olefin ring-opened polymer hydrogenated product (hereinafter referred to as a cyclic cyclic olefin ring-opened polymer hydrogenated product having repeating units derived from a polycyclic norbornene-based monomer having three or more rings. May be simply referred to as “crystalline cyclic olefin ring-opened polymer hydrogenated product.”) 100 parts by weight of (B) 5 to 100 parts by weight of glass filler and (C) 5 to 20 parts of metal oxide To do.
  • A a crystalline cyclic olefin ring-opened polymer hydrogenated product
  • B 5 to 100 parts by weight of glass filler
  • C 5 to 20 parts of metal oxide To do.
  • Crystalline cyclic olefin ring-opened polymer hydrogenated product used in the present invention is a polycyclic norbornene monomer having three or more rings ( Hereinafter, the monomer containing at least a “polycyclic norbornene-based monomer” is subjected to ring-opening polymerization, and the main chain carbon-carbon double bond of the obtained ring-opening polymer is hydrogenated. It is obtained by doing and has crystallinity.
  • the method of obtaining the (A) crystalline cyclic olefin ring-opening polymer hydrogenated product is not particularly limited, and examples thereof include a method described in JP-A-2006-52333. That is, this method is a syndiotactic process in which a ring-opening polymer is obtained by solution polymerization of a norbornene monomer having three or more rings using a Group 6 transition metal compound of the periodic table as a polymerization catalyst. A cyclic olefin ring-opening polymer having stereoregularity is obtained, and the main (A) crystalline cyclic olefin ring-opening polymer is obtained by hydrogenating the main chain carbon-carbon double bond of the ring-opening polymer. The hydrogenated product can be obtained efficiently.
  • the crystalline cyclic olefin ring-opening polymer used in the present invention can be obtained by using a polycyclic norbornene-based monomer having three or more rings as at least a part of the monomer.
  • the polycyclic norbornene monomer having three or more rings may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule. That is, the polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed to the norbornene ring in the molecule. . From the viewpoint of particularly improving the heat resistance of the molded article made of the polymer composition, a compound represented by the following formula (1) or (2) is particularly preferable as the polycyclic norbornene-based monomer.
  • R 1 , R 2 , R 4 to R 7 are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Or a substituent containing a silicon atom, an oxygen atom or a nitrogen atom. R 1 and R 2 , R 4 and R 6 may be bonded to each other to form a ring.
  • Examples of the halogen atom for R 1 , R 2 , R 4 to R 7 include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert- Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group; Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, penten
  • substituents include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group;
  • R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • the divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent for R 3 include an alkylene group such as a methylene group and an ethylene group; a vinylene group and the like.
  • substituent include those exemplified as the substituents for the hydrocarbon groups of R 1 , R 2 and R 4 to R 7 .
  • m is 1 or 2.
  • polycyclic norbornene monomer represented by the formula (1) examples include dicyclopentadiene, methyldicyclopentadiene, tricyclo [5.2.1.0 2,6 ] dec-8-ene, tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 2 , 11 . 0 4,9] pentadeca -4,6,8,13- tetraene (1,4-methano -1,4,4a, 9, 9a, also referred to as 10-hexa hydro anthracene) can be mentioned.
  • tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene.
  • Tetracyclododecenes having a substituted or alkyl group 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl-8 Methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclod
  • Tetracyclododecenes having substituents containing oxygen atoms Tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide
  • Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene
  • tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; Can be mentioned.
  • hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene and the like.
  • Hexacycloheptadecenes having a substituted or alkyl group 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene and 12-cyclopentenylhexacycloheptadecene; having aromatic rings such as 12-phenylhexacycloheptadecene Oxacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhex
  • polycyclic norbornene monomers can be used singly or in combination of two or more.
  • the cyclic olefin ring-opening polymer hydrogenated product is 50% by weight based on the entire polycyclic norbornene-based monomer. It is preferable to use those containing at least% of dicyclopentadiene, and it is particularly preferable to use dicyclopentadiene alone.
  • polycyclic norbornene monomers include endo isomers and exo isomers, both of which can be used as monomers, and one isomer can be used alone.
  • an isomer mixture in which endo and exo isomers are present in an arbitrary ratio can be used.
  • the ratio of one stereoisomer is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic
  • a monomer other than the polycyclic norbornene monomer is copolymerized with the polycyclic norbornene monomer within a range that gives a polymer having crystallinity. Also good.
  • Monomers that can be copolymerized with polycyclic norbornene monomers include bicyclic norbornene compounds, monocyclic olefins, cyclic dienes, and derivatives thereof that do not have a ring structure condensed to a norbornene skeleton. .
  • bicyclic norbornene compound having no ring structure condensed to the norbornene skeleton include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5 -Norbornenes having an unsubstituted or alkyl group such as cyclohexyl norbornene and 5-cyclopentyl norbornene; Alkenyl groups such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene Norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5- Toxicarbonylnorbornene, 5-methyl
  • the monocyclic olefin examples include cyclohexene, cycloheptene, and cyclooctene.
  • Specific examples of the cyclic diene include cyclohexadiene and cycloheptadiene.
  • the monomer it is preferable that 80% by weight or more of the polycyclic norbornene monomer is included with respect to the whole monomer used, and the monomer used is substantially only the polycyclic norbornene monomer. It is particularly preferred that
  • a ring-opening polymerization catalyst capable of giving syndiotactic stereoregularity to the cyclic olefin ring-opening polymer.
  • a ring-opening polymerization catalyst is not particularly limited as long as it can give syndiotactic stereoregularity to the cyclic olefin ring-opening polymer, but a metal compound represented by the following formula (3) , which may be referred to as “metal compound (3)”).
  • M is a metal atom selected from Group 6 transition metal atoms in the periodic table
  • R 8 is a phenyl group optionally having a substituent at at least one of the 3, 4, and 5 positions.
  • R 9 is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group
  • X is A group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group
  • L is an electron-donating neutral ligand
  • a is 0 or 1
  • b is an integer of 0-2 is there.
  • R 10 is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.
  • the metal atom (M) constituting the metal compound (3) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.
  • the metal compound (3) comprises a metal imide bond.
  • R 8 is a substituent on the nitrogen atom constituting the metal imide bond.
  • Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions may include an alkyl group such as a methyl group or an ethyl group; a fluorine atom, a chlorine atom, or a bromine atom A halogen atom such as methoxy group, ethoxy group, isopropoxy group or the like; and further, substituents present in at least two positions of 3,4,5 are bonded to each other. Also good.
  • phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include a phenyl group; a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl group, 4 -Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; two groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group; Substituted phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group, 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2- And 2-naphthyl group which may have a substituent such as naphthyl group.
  • Metal compound (3) substituents on the nitrogen atom may be used as (R 8 in the formula (3)), the R 10 in the group represented by -CH 2 R 10, optionally substituted
  • the number of carbon atoms of the alkyl group that may be used is not particularly limited, but is usually 1 to 20, preferably 1 to 10.
  • the alkyl group may be linear or branched.
  • the substituent that this alkyl group may have is not particularly limited, and examples thereof include a phenyl group that may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; Is mentioned.
  • Examples of the aryl group of R 10 which may have a substituent include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the substituent of the aryl group is not particularly limited, and examples thereof include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; Can be mentioned.
  • R 10 is an alkyl group having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, etc. Is preferred.
  • the metal compound (3) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (3), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In addition, when there are two or more groups represented by X in the metal compound (3), these groups may be bonded to each other.
  • Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group.
  • Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
  • the metal compound (3) may have one metal alkoxide bond or one metal aryloxide bond.
  • the substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R 9 in formula (3)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups.
  • the alkyl group which may have a substituent and the aryl group which may have a substituent which can be the group represented by R 9 are the same as those in the group represented by R 10 described above. Can be used.
  • the metal compound (3) may have one or two electron-donating neutral ligands.
  • this electron-donating neutral ligand (L in Formula (3)) for example, an electron-donating compound containing an atom of Group 14 or Group 15 of the Periodic Table can be mentioned.
  • Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine.
  • ethers are particularly preferably used.
  • the metal compound (3) particularly preferably used as a ring-opening polymerization catalyst for obtaining a cyclic olefin ring-opening polymer having syndiotactic stereoregularity is a tungsten compound having a phenylimide group (in the formula (3)) , M is a tungsten atom, and R 8 is a phenyl group), among which tetrachlorotungstenphenylimide (tetrahydrofuran) is particularly preferable.
  • the metal compound (3) is an oxyhalide of a Group 6 transition metal and phenyl isocyanates which may have a substituent at at least one of the 3, 4, and 5 positions, or a monosubstituted methyl isocyanate And an electron-donating neutral ligand (L) and, if necessary, an alcohol, a metal alkoxide, a metal aryloxide, etc. (for example, a method described in JP-A-5-345817) ) Can be synthesized.
  • the synthesized metal compound (3) may be purified and isolated by crystallization or the like, or the catalyst synthesis solution can be used as it is as a ring-opening polymerization catalyst without purification.
  • the amount of the metal compound (3) used as the ring-opening polymerization catalyst is usually 1: 100 to 1: 2,000,000, preferably 1 in terms of a molar ratio of (metal compound (3): whole monomer used). : 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.
  • the metal compound (3) can be used alone, but an organic metal reducing agent is used in combination with the metal compound (3) from the viewpoint of increasing the polymerization activity. It is preferable to do.
  • organometallic reducing agents used include Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms.
  • organolithium, organomagnesium, organozinc, organoaluminum, or organotin are preferably used, and organoaluminum or organotin are particularly preferably used.
  • Organic lithium includes n-butyllithium, methyllithium, phenyllithium and the like.
  • the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide and the like.
  • the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc.
  • organic aluminum examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Is mentioned.
  • organic tin examples include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
  • the amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and particularly preferably 0.5 to 20 moles, relative to the metal compound (3). If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.
  • the polymerization reaction for obtaining a crystalline cyclic olefin ring-opened polymer is usually carried out in an organic solvent.
  • the organic solvent to be used is not particularly limited as long as the target ring-opening polymer or a hydrogenated product thereof can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction.
  • organic solvent examples include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane.
  • aliphatic hydrocarbons such as pentane, hexane, and heptane
  • cyclopentane cyclohexane
  • methylcyclohexane dimethylcyclohexane
  • trimethylcyclohexane ethylcyclohexane
  • diethylcyclohexane diethylcyclohexane
  • decahydronaphthalene bicycloheptane
  • tricyclodecane examples include ali
  • Alicyclic hydrocarbons such as hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; If solvents.
  • aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.
  • the ring-opening polymerization reaction can be initiated by mixing the monomer, the metal compound (3), and, if necessary, an organometallic reducing agent.
  • the order in which these components are added is not particularly limited.
  • a mixture of the metal compound (3) and the organometallic reducing agent may be added to the monomer and mixed, or a mixture of the monomer and the metal compound (3) may be added to the organometallic reducing agent.
  • the metal compound (3) may be added to and mixed with the mixture of the monomer and the organometallic reducing agent.
  • the total amount of each component may be added at once, or may be added in multiple portions, and added continuously over a relatively long time (for example, 1 minute or more).
  • a relatively long time for example, 1 minute or more.
  • the concentration of the monomer during the polymerization reaction in the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, particularly 3 to 40% by weight. preferable. If the monomer concentration is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.
  • An activity regulator may be added to the polymerization reaction system.
  • the activity adjusting agent can be used for the purpose of stabilizing the ring-opening polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer.
  • the activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound.
  • ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine; Amines such as triisopropylamine, quinuclidine, N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine, etc.
  • Phosphines of the above phosphates such as trimethyl phosphate and triphenyl phosphate; phosphine oxides such as triphenyl phosphine oxide; and the like.
  • These activity regulators can be used singly or in combination of two or more.
  • the amount of the activity regulator to be added is not particularly limited, but it is usually selected from 0.01 to 100 mol% with respect to the metal compound used as the ring-opening polymerization catalyst.
  • a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer.
  • molecular weight regulators include ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, and the like
  • the amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer used.
  • the polymerization temperature is not particularly limited, but is usually in the range of ⁇ 78 ° C. to + 200 ° C., and preferably in the range of ⁇ 30 ° C. to + 180 ° C.
  • the polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.
  • the ring-opening polymerization reaction of the monomer containing the polycyclic norbornene-based monomer under the conditions as described above is performed.
  • a cyclic olefin ring-opening polymer having tic stereoregularity can be obtained.
  • the ratio of racemo dyad in the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is usually 60% or more, preferably 65% or more, more preferably 70 to 99%.
  • the ratio of racemo dyad (degree of syndiotactic stereoregularity) in the crystalline cyclic olefin ring-opening polymer can be adjusted by selecting the kind of the ring-opening polymerization catalyst.
  • the weight average molecular weight (Mw) measured by gel permeation chromatography of the crystalline cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is 10,000 to 100,000 in terms of polystyrene. It is preferably 15,000 to 80,000.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the hydrogenated product of the crystalline cyclic olefin ring-opening polymer (A) obtained from the crystalline cyclic olefin ring-opening polymer having such a weight average molecular weight is used, the moldability is excellent and the resulting molded body has heat resistance. It is preferable at the point which is excellent in.
  • the weight average molecular weight of the crystalline cyclic olefin ring-opening polymer can be adjusted by adjusting the addition amount of the molecular weight modifier used during the polymerization.
  • the molecular weight distribution of the crystalline cyclic olefin ring-opened polymer subjected to the hydrogenation reaction is particularly limited. Although not, it is usually 1.5 to 4.0, preferably 1.6 to 3.5.
  • Use of the hydrogenated product of the crystalline cyclic olefin ring-opening polymer (A) obtained from the crystalline cyclic olefin ring-opening polymer having such a molecular weight distribution is preferable in terms of excellent moldability.
  • the molecular weight distribution of the crystalline cyclic olefin ring-opening polymer hydrogenated product can be adjusted by the monomer addition method and the monomer concentration during the ring-opening polymerization reaction.
  • the hydrogenation reaction of the crystalline cyclic olefin ring-opened polymer (hydrogenation of the main chain carbon-carbon double bond) is performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst.
  • a hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.
  • the homogeneous catalyst includes a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Combinations of butyl lithium, tetrabutoxy titanate / dimethyl magnesium and the like can be mentioned.
  • a transition metal compound such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Combinations of butyl lithium, tetrabutoxy titanate / dimethyl magnesium and the like can be mentioned.
  • noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium and the like.
  • the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.
  • the hydrogenation reaction is usually performed in an inert organic solvent.
  • inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
  • the inert organic solvent is usually the same as the solvent used in the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.
  • the suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst system used, but the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur.
  • the hydrogen pressure is usually from 0.01 to 20 MPa, preferably from 0.05 to 15 MPa, more preferably from 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required.
  • the reaction time is not particularly limited as long as the desired hydrogenation rate can be obtained, but is usually 0.1 to 10 hours.
  • the hydrogenation rate (ratio of hydrogenated main chain carbon-carbon double bond) in the hydrogenation reaction of the crystalline cyclic olefin ring-opening polymer is not particularly limited, but is preferably 70% or more, more preferably 80%. Above, particularly preferably 90% or more, most preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the (A) crystalline cyclic olefin ring-opening polymer hydrogenated product.
  • the (A) crystalline cyclic olefin ring-opening polymer hydrogenated product obtained as described above is a polycyclic ring having three or more rings as represented by the following formula (4) or formula (5). It has a repeating unit derived from the formula norbornene monomer.
  • R 1 and R 2 each independently include a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, an oxygen atom or a nitrogen atom
  • R 1 and R 2 may be bonded to form a ring
  • R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • the ratio of racemo dyad in the crystalline cyclic olefin ring-opening polymer hydrogenated product is not particularly limited as long as the hydrogenated product has crystallinity, but is usually 60% or more, preferably 65% or more, more Preferably it is 70 to 99%.
  • the tacticity of the polymer does not change in the hydrogenation reaction, it is based on having syndiotactic stereoregularity by subjecting the cyclic olefin ring-opening polymer having syndiotactic stereoregularity to the hydrogenation reaction.
  • (A) a crystalline cyclic olefin ring-opening polymer hydrogenated product having crystallinity can be obtained.
  • the resulting polymer composition is a molded body that is not easily deformed by the influence of heat. It will be something that can be given.
  • the ratio of the racemo dyad in the (A) crystalline cyclic olefin ring-opening polymer water additive depends on the ratio of the racemo dyad in the crystalline cyclic olefin ring-opening polymer subjected to the hydrogenation reaction.
  • the ratio of racemo dyad in the crystalline cyclic olefin ring-opened polymer hydrogenated product can be quantified based on the spectrum data obtained by measuring a 13 C-NMR spectrum.
  • the quantification method varies depending on the polymer.
  • a mixed solvent of 1,3,5-trichlorobenzene-d3 / orthodichlorobenzene-d4 (volume ratio: 2/1) was used as a solvent, and a 13 C-NMR measurement was performed at 200 ° C., and the ratio of the racemo dyad from the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad Can be determined.
  • the (A) crystalline cyclic olefin ring-opening polymer hydrogenated product used in the present invention has crystallinity
  • its melting point is not particularly limited, but preferably has a melting point of 200 ° C. or higher, More preferably, it has a melting point of 230 to 290 ° C.
  • a crystalline cyclic olefin ring-opening polymer hydrogenated product having such a melting point it is possible to obtain a polymer composition particularly excellent in the balance between moldability and heat resistance.
  • the melting point of the crystalline cyclic olefin ring-opening polymer hydrogenated product adjusts the degree of syndiotactic stereoregularity (racemo dyad ratio) or selects the type of monomer used. Can be adjusted.
  • (B) Glass filler A well-known thing can be used as (B) glass filler used in this invention, and it is not limited in the shape.
  • glass fiber, glass bead, glass powder, glass flake, glass balloon, etc. are mentioned. Among these, it is preferable to use glass fiber because of the high mechanical strength of the molded product.
  • the shape and form of the glass fiber used in the present invention are not particularly limited. Specific examples include milled fiber, cut fiber, chopped strand, roving and the like, and chopped strand is particularly preferred from the viewpoint of high mechanical strength of the molded product and ease of handling.
  • the length of the glass fiber used in the present invention is preferably 3 mm to 40 mm, more preferably 5 to 30 mm.
  • the cross-sectional shape of the glass fiber used in the present invention is arbitrary, such as a circle, an ellipse, a flat shape, and a rectangle, and these glass fibers can be used in any ratio.
  • the glass filler used in the present invention may be surface-treated with a silane compound, an epoxy compound, a urethane compound, or the like.
  • the blending amount of the (B) glass filler is 5 to 100 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the (A) hydrogenated crystalline cyclic olefin ring-opening polymer. . If the blending amount of the glass filler is too small, the heat resistance during reflow and the strength of the molded product are inferior, and if the blending amount of the glass filler is too large, the dielectric loss tangent is increased and the moldability is poor.
  • the (C) metal oxide is a metal oxide capable of forming a single metal nucleus by irradiation with electromagnetic radiation, and as a result of absorbing electromagnetic radiation, the metal in a single form in a chemical reaction.
  • a metal-containing (inorganic or organic) compound to be liberated instead of directly absorbing the electromagnetic radiation into the metal-containing compound, it is possible to absorb the absorbed energy in another substance that liberates the single metal by subsequently transmitting the absorbed energy to the metal-containing compound.
  • the electromagnetic radiation is preferably laser radiation for emitting heavy metal nuclei, and the wavelength can be selected from various wavelengths as described in paragraph 0017 of JP-T-2004-534408.
  • the metal oxide is preferably insoluble and stable in an aqueous acidic or alkaline metallization bath, more preferably one that absorbs most of the light having the wavelength of incident light, and the transition metal oxide is Particularly preferred.
  • JP 2010-536947 A which contains at least two different cations and is represented by the chemical formula AB 2 O 4 or B (AB) O 4 having a spinel structure or a spinel-like structure, Those detailed in the publication paragraph 0019 are preferred.
  • the A component of the formula is a divalent metal cation, from the group consisting of cadmium, zinc, copper, cobalt, magnesium, tin, titanium, iron, aluminum, nickel, manganese, chromium, and combinations of two or more thereof. Selected.
  • the B component of the formula is a trivalent metal cation, from the group consisting of cadmium, manganese, nickel, zinc, copper, cobalt, magnesium, tin, titanium, iron, aluminum, chromium, and combinations of two or more thereof. Selected.
  • a spinel-type copper-containing metal oxide such as CuCr 2 O 4 is most preferable. Spinel-type copper-containing metal oxides are commercially available.
  • Another preferred spinel oxide is a spinel-type manganese-containing metal oxide.
  • the metal oxide having a spinel structure can be used alone or in combination of two or more.
  • the transition metal oxide represented by the chemical formula AB 2 O 4 or B (AB) O 4 having a spinel structure or a spinel-like structure may contain other metals in a range of 5% by weight or less. .
  • the (C) metal oxide is 5 to 20 parts by weight, preferably 6 to 10 parts by weight per 100 parts by weight of the hydrogenated product of the (A) crystalline cyclic olefin ring-opening polymer. Parts by weight. If it is this range, it is suitable for obtaining a plating layer with high plating formability and sufficient thickness.
  • the polymer composition of the present invention includes (D) talc in addition to (A) crystalline cyclic olefin ring-opening polymer hydrogenated product, (B) glass filter, and (C) metal oxide. May be added.
  • Talc can be selected from talc used in general resin blending, and preferably has a small particle size. The amount of talc added is usually 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the hydrogenated crystalline cyclic olefin ring-opening polymer (A). Within this range, the plating adhesion and strength are highly balanced and suitable.
  • the polymer composition of the present invention may further contain other compounding agents.
  • Other compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials.
  • thermoplastic elastomers, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, Examples include release agents, colorants such as dyes and pigments, plasticizers, antistatic agents, fluorescent whitening agents, glass fillers, and inorganic fillers other than talc.
  • the strength is improved by blending a thermoplastic elastomer.
  • the mixing method of (A) crystalline cyclic olefin ring-opening polymer hydrogenated product and (B) glass filler, (C) metal oxide, and other compounding agents used as needed is a compounding agent in the polymer. If it is a method of fully disperse
  • Examples of the compounding method include a method of kneading a resin in a molten state with a mixer, a single-screw kneader, a twin-screw kneader, a roll, a Brabender, an extruder, etc., a solidifying method by dissolving and dispersing in an appropriate solvent, and a casting method. Or a method of removing the solvent by a direct drying method.
  • a biaxial kneader is used, after kneading, it is usually extruded in a rod shape in a molten state, cut into an appropriate length with a strand cutter, and pelletized in many cases.
  • the molded body of the present invention is obtained by using the polymer composition of the present invention.
  • the molded body of the present invention preferably has a function of a high frequency dielectric antenna.
  • the molded article of the present invention is obtained by forming the polymer composition of the present invention into a known thermoplastic resin molding method, for example, an injection molding method, an extrusion molding method, a cast molding method, an inflation molding method, a blow molding method, or a vacuum molding method. It can be manufactured by being molded by a press molding method, a compression molding method, a rotational molding method, a calendar molding method, a rolling molding method, a cutting molding method, or the like.
  • an injection molding method or a press molding method that is excellent in dimensional accuracy and can be molded into an aspherical shape is preferable, and an injection molding method is particularly preferable.
  • the hydrogenation rate of the cyclic olefin ring-opening polymer hydrogenated product A was 99% or more, the ratio of racemo dyad was 85%, and the melting point was 265 ° C.
  • the number average molecular weight (Mn) of the obtained ring-opening polymer was 14,200, the weight average molecular weight (Mw) was 27,000, and the molecular weight distribution (Mw / Mn) was 1.90.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and then 0.1 part of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added. Then, using a thin film evaporator (product name “Film Truder”, manufactured by Buss), the volatile matter was removed under the conditions of a temperature of 260 ° C. (533 ° K), a pressure of 1 kPa or less, and a residence time of 1.2 hours. Evaporation gave hydrogenated product B of a ring-opening copolymer of tetracyclododecene-dicyclopentadiene.
  • the glass transition temperature of the ring-opening copolymer hydrogenated product B was 142 ° C.
  • the ring-opening copolymer hydrogenated B of tetracyclododecene-dicyclopentadiene has a number average molecular weight (Mn) of 18300, a weight average molecular weight (Mw) of 42000, and a molecular weight distribution (Mw / Mn) of 2.3.
  • the hydrogenation rate of the obtained ring-opening polymer hydrogenated product was 99% or more.
  • Cyclic olefin ring-opening polymer hydrogenated product A 100 parts, glass fiber (product name “CSG 3PA-830”, manufactured by Nittobo), product name “Irganox (registered trademark) 1010”, manufactured by BASF Japan) 0 8 parts, 6 parts of metal oxide (product name “Black 3702”, manufactured by Asahi Sangyo) and 10 parts of filler (product name “SG-95”, manufactured by Nippon Talc) were mixed in a blender. Next, the mixture was kneaded for 2 minutes at 290 ° C. and 100 rpm with a twin-screw kneader (TEM-35B manufactured by Toshiba Machine Co., Ltd.) to form a pellet.
  • TEM-35B twin-screw kneader
  • the molding temperature is 290 ° C
  • the injection pressure is 0.7MPa
  • the mold temperature is 150 ° C
  • the holding time in the mold is 80mm.
  • a test piece 1 having a thickness of 10 mm, a thickness of 4 mm, a test piece 2 having a length of 100 mm, a width of 1 mm, and a thickness of 1 mm, and a test piece 3 having a length of 60 mm, a width of 60 mm, and a thickness of 2 mm were formed.
  • the composition of each composition and the evaluation results are shown in Table 1.
  • the polymer compositions of the present invention had good electrical characteristics, plating properties and reflow resistance, and had little change in strength due to moisture absorption.
  • the amount of glass filler is small, deformation is observed during the reflow test (Comparative Example 1), and when the amount of glass filler is large, the electrical characteristics deteriorate (Comparative Example 2).
  • an electrical property will deteriorate, and when there are few, a plating characteristic will deteriorate (Comparative Examples 3 and 4).

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

Abstract

La présente invention concerne une composition polymère qui contient 5 à 100 parties en poids de (B) une charge à base de verre et 5 à 20 parties en poids de (C) un oxyde métallique pour 100 parties en poids de (A) un produit hydrogéné d'un polymère cristallin oléfinique cyclique à ouverture de cycle, qui comporte un motif répété dérivé d'un monomère de norbornène polycyclique comportant un noyau tricyclique ou un noyau cyclique de rang supérieur. La présente invention concerne une composition polymère qui est appropriée à la formation d'un placage par un procédé de structuration directe par laser, et qui est capable de fournir un substrat qui présente d'excellentes caractéristiques en matière d'isolation électrique et une grande résistance, de même qu'une remarquable adhérence à un placage même dans un environnement caractérisé par une température et une humidité élevées.
PCT/JP2015/071657 2014-01-30 2015-07-30 Composition polymère et corps moulé WO2016103778A1 (fr)

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WO2012033076A1 (fr) * 2010-09-07 2012-03-15 日本ゼオン株式会社 Composition de résine et objet moulé à partir de cette dernière
JP2013256596A (ja) * 2012-06-13 2013-12-26 Nippon Zeon Co Ltd 樹脂組成物及びその成形品
JP2014065756A (ja) * 2012-09-24 2014-04-17 Nippon Zeon Co Ltd 樹脂組成物及びその成形体

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WO2012033076A1 (fr) * 2010-09-07 2012-03-15 日本ゼオン株式会社 Composition de résine et objet moulé à partir de cette dernière
JP2013256596A (ja) * 2012-06-13 2013-12-26 Nippon Zeon Co Ltd 樹脂組成物及びその成形品
JP2014065756A (ja) * 2012-09-24 2014-04-17 Nippon Zeon Co Ltd 樹脂組成物及びその成形体

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