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WO2012033076A1 - Composition de résine et objet moulé à partir de cette dernière - Google Patents

Composition de résine et objet moulé à partir de cette dernière Download PDF

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Publication number
WO2012033076A1
WO2012033076A1 PCT/JP2011/070221 JP2011070221W WO2012033076A1 WO 2012033076 A1 WO2012033076 A1 WO 2012033076A1 JP 2011070221 W JP2011070221 W JP 2011070221W WO 2012033076 A1 WO2012033076 A1 WO 2012033076A1
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WIPO (PCT)
Prior art keywords
group
resin composition
cyclic olefin
ring
opening polymer
Prior art date
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Ceased
Application number
PCT/JP2011/070221
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English (en)
Japanese (ja)
Inventor
角替　靖男
郁 三井
昭弘 高山
進太郎 池田
純正 田形
慎介 宮澤
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Zeon Corp
Original Assignee
Zeon Corp
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Filing date
Publication date
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Priority to JP2011554311A priority Critical patent/JP4973815B2/ja
Priority to KR1020137005760A priority patent/KR20130101008A/ko
Priority to CN201180053111.3A priority patent/CN103237843B/zh
Publication of WO2012033076A1 publication Critical patent/WO2012033076A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • 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
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/724—Hydrogenation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/8506—Containers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/855—Optical field-shaping means, e.g. lenses
    • H10H20/856—Reflecting means

Definitions

  • the present invention relates to a resin composition capable of giving a molded body that is sufficiently crystallized and hardly deforms due to the influence of heat even when injection molding is performed at a relatively low mold temperature, and the molded body. .
  • Patent Document 1 A film obtained from a composition in which a nucleating agent is blended with a crystalline cyclic olefin polymer hydride obtained by ring-opening polymerization of a monomer having 2-norbornene as a main component and hydrogenation is more It is known to realize low water vapor permeability (Patent Document 2).
  • the aliphatic polyester resin is a crystalline resin
  • the crystallization speed is very slow, there is a problem that it takes a high temperature and a long time to obtain a molded body by injection molding using a mold.
  • LED Light Emitting Diode
  • LED Light Emitting Diode
  • LED emits light by directly converting electrical energy into light, so it has good energy efficiency, and has a long life and small size and light weight compared to incandescent bulbs and fluorescent lamps.
  • It is a light source having a feature that it can be made into a light source. Therefore, in recent years, it has been used as a general lighting fixture in place of an electronic device such as a mobile phone, a light source of a backlight of a large-sized liquid crystal display device, a light source of a road traffic display board, an incandescent bulb and a fluorescent lamp.
  • the LED is generally composed of a semiconductor chip that is a light-emitting element, a sealing material that protects the semiconductor chip, and a light reflector for adjusting the direction of light.
  • the light reflector is used for the purpose of reflecting the light emitted from the semiconductor chip and collecting the light in a necessary direction, and is an important member for improving the brightness of the LED.
  • High light reflectance is required for the light reflector (LED light reflector) constituting the LED.
  • the LED light reflector is further heated during molding (heating for melt molding), manufacturing (heating and soldering for sealing material curing), and during use (heat dissipation of the semiconductor chip). Affected by. Therefore, as a material for the LED light reflector, a composition obtained by blending a white pigment such as titanium oxide with a polyamide resin excellent in heat resistance is widely used (Patent Documents 4, 5, etc.).
  • LED light reflectors composed of the compositions described in Patent Documents 4 and 5 cannot be said to have sufficient heat resistance, and the light reflectivity may decrease due to heat received during molding or the like.
  • a composition obtained by blending a white pigment such as titanium oxide with a polyamide resin requires a high temperature for molding, and since the viscosity at the time of melting is high, it is suitable for molding into a light reflector. There was also a problem with difficulty. For this reason, there is a strong demand for the development of a molding material for an LED light reflector that can provide a light reflector with good moldability and that is less likely to cause a decrease in light reflectance due to the influence of heat.
  • the present invention has been made in view of the above-described prior art, and a molded body in which crystallization sufficiently proceeds and deformation due to the influence of heat hardly occurs even when injection molding is performed at a relatively low mold temperature. It is an object to provide a resin composition that can be provided, and a molded body thereof. Furthermore, an object of the present invention is to provide an LED light reflector that can be imparted with good moldability by the resin composition and is less likely to cause a decrease in light reflectance due to the influence of heat.
  • the following resin compositions (1) to (5) and molded articles (6) and (7) are provided.
  • a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer, 1 to 4 parts by weight of wax, and a nucleus with respect to 100 parts by weight of the hydrogenated product A resin composition comprising an agent.
  • the molded product according to (6) which is an LED light reflector.
  • the resin composition of the present invention it is possible to obtain a molded body in which crystallization sufficiently proceeds and deformation due to the influence of heat hardly occurs even when injection molding is performed at a relatively low mold temperature.
  • an LED light reflector that has excellent light reflectivity and that maintains the excellent light reflectivity for a long period of time without decreasing even under high temperature conditions, has good moldability. Can be obtained at The molded body of the present invention is hardly deformed by the influence of heat.
  • the resin composition of the present invention has a crystalline cyclic olefin ring-opening polymer hydrogenated product (hereinafter simply referred to as “crystalline cyclic olefin ring-opening”) having a repeating unit derived from a polycyclic norbornene monomer.
  • Polymeric hydrogenated product ") 1 to 4 parts by weight of wax and nucleating agent with respect to 100 parts by weight of the hydrogenated product.
  • the crystalline cyclic olefin ring-opening polymer hydrogenated product used in the present invention is obtained by ring-opening polymerization of a monomer containing at least a polycyclic norbornene monomer, and the main chain double chain of the obtained ring-opening polymer. It is obtained by hydrogenating the bond and has crystallinity.
  • the method for obtaining the crystalline cyclic olefin ring-opened polymer hydrogenated product is not particularly limited, and examples thereof include a method described in JP-A-2006-52333. According to this method, a cyclic olefin ring-opening polymer having syndiotactic stereoregularity is obtained, and hydrogenation thereof can be used to efficiently obtain the target cyclic olefin ring-opening polymer hydrogenated product. it can.
  • the 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 may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule.
  • 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.
  • R 3 is an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms.
  • m is 1 or 2.
  • 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;
  • the divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent of R 3 includes an alkylene group such as a methylene group or an ethylene group; an alkenylene such as a vinylene group; Groups; alkynylene groups such as ethynylene groups; arylene groups such as phenylene groups; combinations thereof; and the like.
  • Examples of the substituent include those exemplified as the substituents for the hydrocarbon groups of R 1 , R 2 and R 4 to R 7 .
  • 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.
  • it 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 For example, the ratio of endo-form or exo-form 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- Toxylcarbonylnorbornene, 5-
  • 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
  • Such 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.
  • 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 that may have a substituent of R 10 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.
  • 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; or a mixture thereof 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).
  • the monomer or metal compound (3) is divided into a plurality of times. It is preferable to add them continuously or continuously, and it is particularly preferable to add the monomers in a plurality of times or continuously.
  • 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 Phosphines 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
  • 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 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 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 cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is preferably 10,000 to 100,000 in terms of polyisoprene, More preferably, it is 15,000 to 80,000.
  • Use of a cyclic olefin ring-opened polymer hydrogenated product obtained from a cyclic olefin ring-opened polymer having such a weight average molecular weight is preferable in terms of excellent moldability and excellent heat resistance of the obtained molded body.
  • the weight average molecular weight of the cyclic olefin ring-opening polymer can be adjusted by adjusting the addition amount of the molecular weight modifier used at the time of polymerization.
  • the molecular weight distribution of the cyclic olefin ring-opened polymer to be subjected to the hydrogenation reaction is not particularly limited, Usually, it is 1.5 to 4.0, preferably 1.6 to 3.5.
  • Use of a cyclic olefin ring-opened polymer hydrogenated product obtained from a cyclic olefin ring-opened polymer having such a molecular weight distribution is preferred in terms of excellent moldability.
  • the molecular weight distribution of the 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 cyclic olefin ring-opening polymer can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst.
  • Any 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.
  • Homogeneous catalysts include catalyst systems composed of combinations of transition metal compounds and alkali metal compounds, 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.
  • transition metal compounds and alkali metal compounds 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. .
  • 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 double bonds) in the hydrogenation reaction of the cyclic olefin ring-opening polymer is not particularly limited, but is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more, most preferably 99% or more.
  • the hydrogenated crystalline cyclic olefin ring-opened polymer obtained as described above is a repeating unit derived from a polycyclic norbornene-based monomer represented by the following formula (4) or formula (5): It is what has.
  • 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 used in the present invention is not particularly limited as long as the hydrogenated product has crystallinity, but usually 55% or more, preferably 60% or more, More preferably, it is 65 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 crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer having crystallinity can be obtained.
  • the resulting resin composition can give a molded product that is hardly deformed by the influence of heat.
  • the ratio of the racemo dyad of the crystalline cyclic olefin ring-opening polymer hydrogenated product depends on the ratio of the racemo dyad of the 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 spectral data obtained by measuring a 13 C-NMR spectrum.
  • the quantification method varies depending on the polymer. For example, in the case of a hydrogenated ring-opened polymer of dicyclopentadiene, 13 C-NMR measurement is performed at 150 ° C. using orthodichlorobenzene-d4 as a solvent, and meso-dyad.
  • the ratio of racemo dyad can be determined from the intensity ratio of the 43.35 ppm signal from the origin and the 43.43 ppm signal from the racemo dyad.
  • the crystalline cyclic olefin ring-opening polymer hydrogenated product used for constituting the resin composition of the present invention is not particularly limited as long as it has crystallinity, but has a melting point of 200 ° C. or higher. It is preferable to have a melting point of 230 to 290 ° C. By using a crystalline cyclic olefin ring-opening polymer hydrogenated product having such a melting point, it is possible to obtain a resin composition particularly excellent in balance between moldability and heat resistance.
  • the melting point of the crystalline cyclic olefin ring-opening polymer hydrogenated product can be adjusted by adjusting the degree of syndiotactic stereoregularity (racemo dyad ratio), selecting the type of monomer used, etc. Can be adjusted.
  • the wax blended in the resin composition of the present invention may be a natural wax or a synthetic wax.
  • oily substances having a high melting point such as esters of higher fatty acids and monohydric or dihydric higher alcohols, neutral fats, higher fatty acids, hydrocarbons and the like exhibiting properties similar to these.
  • Wax is usually a soft and smooth solid at room temperature, its melting point is usually 25 to 120 ° C., and gas burns well.
  • waxes obtained from animals, plants, and minerals waxes obtained from animals, plants, and minerals, petroleum waxes (paraffin wax, microcrystalline wax, solid hydrocarbons at room temperature, mainly composed of hydrocarbons extracted during the distillation of crude oil) Or petrolatum), hydrocarbon wax synthesized by Fischer-Tropsch method (Fischer-Tropsch wax), and polyalkylene wax.
  • hydrocarbon waxes represented by C n H 2n + 2 such as petroleum wax, Fischer-Tropsch wax and polyalkylene wax, are preferable because of the high transparency of the obtained molded product, and Fischer-Tropsch wax is preferred. More preferred.
  • the hydrocarbon wax contains 95% by weight or more of a linear or branched saturated hydrocarbon.
  • the blending amount of the wax is selected in the range of 1 to 4 parts by weight, preferably 1 to 3 parts by weight with respect to 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product.
  • the amount is too small, crystallization at a low mold temperature does not proceed sufficiently, and when the amount is too large, the heat resistance is low, which is not preferable.
  • nucleating agent mix blended with the resin composition of this invention.
  • examples thereof include sorbitol compounds, metal salts of organic phosphoric acid, metal salts of organic carboxylic acids, hindered amine compounds, hindered phenol compounds, kaolin and talc.
  • sorbitol-based compound examples include dibenzylidene sorbitol, diparamethyldibenzylidene sorbitol, and the like.
  • metal salts of organic phosphoric acid include sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy) -12H-dibenzo [d, g] [1,2,3] dioxaphosphocin-6-oxide) aluminum hydroxide salt and the like.
  • metal salts of organic carboxylic acids examples include sodium benzoate, calcium oxalate, magnesium stearate, potassium benzoate and the like.
  • hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate. Etc.
  • hindered phenol compound examples include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl- 3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-trimethyl-2,4,6- And tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl) benzene.
  • a metal salt of organic phosphoric acid and talc are preferable.
  • the metal salt of organic phosphoric acid sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate is particularly preferable.
  • talc examples include a powder obtained by pulverizing a mineral generally called talc.
  • the talc which is a raw material, contains hydrous magnesium silicate (3MgO ⁇ 4SiO 2 ⁇ H 2 O) as a main component and contains Al 2 O 3 , Fe 2 O 3 , CaO, K 2 O, Na 2 O and the like as subcomponents. Is a natural mineral.
  • the whiteness of talc used in the present invention is usually 90% or more, preferably 90 to 97%, more preferably 93 to 97%.
  • talc is available from Nippon Talc and Hayashi Kasei.
  • the whiteness is influenced by the composition of talc, and when it is in the above range, a molded article having excellent heat resistance can be obtained without being colored even by melt molding.
  • the whiteness is measured according to JIS P 8123.
  • the average particle diameter (D50) of talc is not particularly limited as long as it is commercially available, but is preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the average particle diameter (D50) is measured by a laser diffraction method.
  • the amount of the nucleating agent is not particularly limited, but is usually in the range of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product. Selected.
  • talc may be blended when hydrogenating a cyclic olefin ring-opening polymer with a homogeneous catalyst. it can.
  • the resin composition of the present invention may be composed of only a crystalline cyclic olefin ring-opening polymer hydrogenated product, a wax and a nucleating agent, or may be composed of other components.
  • Other components include white pigments, glass fibers, antioxidants, fillers, colorants, flame retardants, flame retardant aids, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, near infrared absorbers, Examples include a lubricant and a polymer material other than the crystalline cyclic olefin ring-opening polymer hydrogenated product.
  • the white pigment is not particularly limited, but for example, silica, alumina, titanium oxide, magnesium oxide, magnesium carbonate, basic magnesium carbonate, calcium oxide, calcium carbonate, calcium sulfate, precipitated calcium carbonate, calcium sulfite, potassium titanate Lead titanate, barium sulfate, barium carbonate, barium sulfate, white lead, zinc white, basic lead sulfate, lithopone, zinc sulfide, zirconium oxide, barite, chalk, clay, talc powder, diatomaceous earth, etc. . These may be used alone or in combination of two or more.
  • the shape of the white pigment may be any shape such as plate, granule, sphere, fiber, or indefinite shape. Among these, it is preferable to use titanium oxide as a white pigment.
  • the kind of titanium oxide is not particularly limited, and any of rutile type titanium oxide and anatase type titanium oxide can be used. However, it is particularly preferable to use rutile type titanium oxide from the viewpoint of thermal stability.
  • the shape of the titanium oxide is not particularly limited, and may be any of a spherical shape, a scale shape, an amorphous shape, and the like.
  • the average particle diameter of titanium oxide is usually 0.05 to 5 ⁇ m, preferably 0.05 to 1 ⁇ m, and more preferably 0.1 to 1 ⁇ m. By using titanium oxide having such an average particle size, it is possible to obtain a composition capable of molding an LED light reflector that is particularly excellent in the reflectance of visible light.
  • the particle diameter of titanium oxide indicates the diameter in the case of a spherical shape, and the longest distance between both ends in other cases. Moreover, an average particle diameter is the value which measured several single particle diameters with the electron microscope (Transmission type (TEM) or scanning type (SEM)), and averaged.
  • TEM Transmission type
  • SEM scanning type
  • the amount of the white pigment may be determined in consideration of the balance between the light reflectance of the resulting composition, heat resistance, and moldability, and is not particularly limited. Is usually selected in the range of 20 to 200 parts by weight, preferably 25 to 100 parts by weight, per 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product.
  • glass fibers include glass fibers, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and the like. These may be used alone or in combination of two or more.
  • the LED light reflector When the LED light reflector is molded, it is preferable to use glass fiber and / or titanium oxide, and it is particularly preferable to use glass fiber and titanium oxide from the viewpoint of heat resistance.
  • the total amount of both is usually selected in the range of 21 to 200 parts by weight, preferably 45 to 190 parts by weight, more preferably 50 to 180 parts by weight.
  • antioxidant when the LED light reflector is molded, it is also preferable to add an antioxidant. It does not specifically limit as antioxidant, For example, a phenolic antioxidant, phosphorus antioxidant, and sulfur type antioxidant can be used. Among these, it is preferable to use a phenolic antioxidant.
  • phenolic antioxidant conventionally known ones can be used, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2 , 4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like, and JP-A 63-179953 and JP-A 1-168643.
  • Alkyl-substituted phenol compounds 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1,3 5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine Triazine group-containing phenol compound of;., Etc.
  • alkyl-substituted phenolic antioxidants are particularly preferably used.
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-diphenyl).
  • -T-butylphenyl) phosphite 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Phosphite compounds; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4′isopropylidene-bis (phenyl-di-alkyl phosphite) Examples thereof include diphosphite compounds such as (the alkyl moiety having 12 to 15 carbon atoms).
  • sulfur-based antioxidant examples include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipro Pionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, etc. Can be mentioned.
  • the amount of the antioxidant is not particularly limited, but is usually 0.001 to 5 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product. It is selected in the range of 3 parts by weight.
  • the resin composition of the present invention can be prepared by blending a crystalline cyclic olefin ring-opened polymer hydrogenated product with a wax, a nucleating agent, and other components as required, and mixing them according to a conventional method.
  • the mixing method is not particularly limited.
  • the mixing may be performed by melt kneading using a single-screw kneader, a twin-screw kneader, or the like, or dry blending using a mixer or the like.
  • LED light reflector molding in addition to the crystalline cyclic olefin ring-opening polymer hydrogenated product, wax, and nucleating agent, white pigment and glass fiber, and other components (for example, oxidation) It is preferable to prepare the resin composition by blending and mixing an inhibitor). By using such a resin composition, an LED light reflector that is more excellent in light reflectivity and that maintains its excellent light reflectivity for a long period of time without deterioration even under high temperature conditions can be obtained. It can be obtained by moldability.
  • the light reflectance of the LED light reflector molding resin composition (spectral reflectance at a wavelength of 450 nm, before deterioration) is not particularly limited, but is preferably 80% or more, more preferably 85 to 95%. .
  • the light reflectance of the LED light reflector molding resin composition can be adjusted by the type and blending amount of the white pigment.
  • the melt flow rate (280 ° C., 2.16 kgf) of the LED light reflector molding resin composition is not particularly limited, but is preferably 5 to 150 g / 10 minutes, and preferably 10 to 100 g / 10 minutes. More preferred.
  • the melt flow rate of the LED light reflector molding resin composition can be adjusted by the molecular weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product used and the type and blending amount of the white pigment.
  • the resin composition of the present invention even when injection molding is performed at a relatively low mold temperature, crystallization can proceed sufficiently, and a molded body that hardly undergoes deformation due to the influence of heat can be provided.
  • the molded article of the present invention is obtained by melt-molding the resin composition of the present invention.
  • the melt molding method include injection molding, extrusion molding, press molding, blow molding, and calendar molding.
  • the melt molding method may be selected according to the target shape and the like, but since the resin composition of the present invention has excellent moldability (melt moldability), an injection molding method with excellent mass productivity should be applied. Is preferred.
  • the shape of the molded body is not particularly limited.
  • Examples of the molded body include electronic components such as connectors, relays, capacitors, sensors, antennas, IC trays, chassis, coil seals, motor cases, power supply boxes, etc .; LED light reflectors; reflectors for vehicle lamps; Automotive parts such as cases, sensor cases, module parts cases; optical lens barrels; flexible printed circuit boards; release films for laminated printed wiring boards; solar cell boards; microwave ovens, rice cookers, electric jar pots, drying washing machines, Home appliance parts such as dishwashers and air conditioners; packaging and packaging films; food sheets and trays; LED mold materials; pump casings, impellers, pipe joints, bathroom panels and other residential parts.
  • the molded article of the present invention is preferably an LED light reflector.
  • an LED light reflector for example, a light source of a backlight of a large liquid crystal display device, a light source of a backlight of a liquid crystal display of a small electronic device such as a luminaire, a mobile phone, or a light source of an electric display panel such as a road traffic display board Examples thereof include a light reflector of the LED used.
  • the shape of the LED light reflector may be determined as appropriate according to the application and the like, and the LED light reflector may be configured in combination with other materials as necessary. According to a conventional method, an LED can be configured by combining a semiconductor chip or a sealing material with the obtained LED light reflector.
  • the solidified polymer was recovered by filtration.
  • the obtained ring-opening polymer was dried at 40 ° C. under reduced pressure for 20 hours.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of this polymer are 10,100 and 17,200, respectively, and the molecular weight distribution (Mw / Mn) obtained therefrom is 1.70. It was.
  • the hydrogenation rate of the crystalline cyclic olefin ring-opening polymer hydrogenated product A was 99% or more, the ratio of racemo dyad was 79%, and the melting point was 260 ° C.
  • the amount of 1-hexene used in the polymerization reaction, the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the obtained ring-opening polymer, and the resulting ring-opening polymer hydrogen The hydrogenation rate and melting point of the additive are summarized in Table 1 below.
  • Example 1 Crystalline cyclic olefin ring-opening polymer hydrogenated product A 100 parts, wax (melting point 69 ° C., trade name “LUVAX 1266”, manufactured by Nippon Seiki Co., Ltd.), antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, trade name “Irganox (registered trademark) 1010” (manufactured by BASF Japan) 0.8 part, and nucleating agent (phosphoric acid 2,2 After mixing 0.8 parts of '-methylenebis (4,6-di-tert-butylphenyl) sodium, trade name “ADEKA STAB (registered trademark) NA-11” (manufactured by ADEKA), a small kneader (Micro15 Compounder, DSM Xplore) And kneaded for 2 minutes under the conditions of 290 ° C.
  • wax melting point
  • Examples 2 to 5 and Comparative Examples 1 to 5 Except having changed the compounding quantity (weight part) of the composition as shown in following Table 2 in Example 1, it obtained the molded object similarly to Example 1, and evaluated it. The evaluation results are shown in Table 2.
  • talc used as a nucleating agent is a trade name “MS” (whiteness 93%, average particle diameter (D50) 14 ⁇ m, manufactured by Nippon Talc Co., Ltd.), and glass fiber of inorganic filler is a product.
  • CSG 3PA-830 manufactured by Nittobo Co., Ltd.
  • the titanium oxide are trade names “FTR-700” (rutile titanium oxide having an average particle size of 0.2 ⁇ m, manufactured by Sakai Chemical Industry Co., Ltd.).
  • Adipic acid ester used as the plasticizer was di-2-ethylhexyl adipate (DOA), and phthalic acid ester was di-2-ethylhexyl phthalate (DOP).
  • DOA di-2-ethylhexyl adipate
  • DOP di-2-ethylhexyl phthalate
  • the resin compositions of the present invention have a good moldability, and progress in crystallization even at a low mold temperature, so that a molded product having excellent heat resistance can be obtained. It was. On the other hand, when the amount of wax is small, the progress of crystallization hardly occurs, and the obtained molded article has insufficient long-term heat resistance (Comparative Examples 1 and 2). On the other hand, when the amount of wax is large, crystallization proceeds, but the long-term heat resistance of the molded product is inferior due to the low heat resistance of the wax (Comparative Example 3). In addition, when a plasticizer was used instead of wax, crystallization at low temperature was insufficient, and the resulting molded article was largely deformed after a heat-resistant long-term stability test and had insufficient heat resistance. (Comparative Examples 4 and 5).

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Abstract

Cette invention concerne une composition de résine et un objet obtenu par moulage de cette dernière. Ladite composition de résine comprend ; un polymère à noyau ouvert d'oléfine cyclique, hydrogéné cristallin ayant une unité récurrente dérivée d'un monomère de norbornène polycyclique ; 1 à 4 parties de cire pour 100 parties dudit polymère hydrogéné, en poids ; et un agent de nucléation. Avec cette invention, il est possible d'obtenir une composition de résine permettant de produire un objet moulé qui résiste aux déformations dues aux effets de la chaleur et qui se cristallise suffisamment même avec un moulage par injection à une température de moulage relativement basse ; et de fabriquer ledit objet moulé facilement, en particulier un réflecteur de lumière émise par des diodes qui conserve intacte une capacité de réflexion excellente, même sous une température élevée.
PCT/JP2011/070221 2010-09-07 2011-09-06 Composition de résine et objet moulé à partir de cette dernière Ceased WO2012033076A1 (fr)

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JP2013235872A (ja) * 2012-05-02 2013-11-21 Dainippon Printing Co Ltd 樹脂付リードフレーム、多面付ｌｅｄパッケージ、樹脂付リードフレームの製造方法およびｌｅｄパッケージの製造方法
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
JP2015054885A (ja) * 2013-09-11 2015-03-23 日本ゼオン株式会社 結晶性樹脂組成物
JP2015163682A (ja) * 2014-01-30 2015-09-10 日本ゼオン株式会社 重合体組成物及び成形体
JP2015178580A (ja) * 2014-03-20 2015-10-08 日本ゼオン株式会社 樹脂組成物及びその利用
KR20150117265A (ko) * 2013-02-12 2015-10-19 니폰 제온 가부시키가이샤 수지 조성물 및 그의 성형체
JP2016105518A (ja) * 2016-03-03 2016-06-09 大日本印刷株式会社 樹脂付リードフレーム、多面付ｌｅｄパッケージ、樹脂付リードフレームの製造方法およびｌｅｄパッケージの製造方法
WO2018030105A1 (fr) * 2016-08-08 2018-02-15 日本ゼオン株式会社 Composition de résine, et corps moulé de résine
WO2018174029A1 (fr) 2017-03-21 2018-09-27 日本ゼオン株式会社 Matière de moulage, article moulé en résine, récipient pour produit cosmétique, récipient à semi-conducteur et procédé de production pour récipient à semi-conducteur
US10233301B2 (en) 2014-01-30 2019-03-19 Zeon Corporation Polymer composition and molded body
WO2019167683A1 (fr) 2018-02-28 2019-09-06 日本ゼオン株式会社 Tissu non-tissé, et filtre
WO2020017219A1 (fr) 2018-07-19 2020-01-23 日本ゼオン株式会社 Matériau de moulage et corps moulé
US10767019B2 (en) 2015-09-28 2020-09-08 Zeon Corporation Resin composition, microporous membrane, separator and secondary battery
US10896827B2 (en) 2016-06-28 2021-01-19 Zeon Corporation Support for manufacturing semiconductor packages, use of support for manufacturing semiconductor packages, and method for manufacturing semiconductor packages
US11046046B2 (en) 2015-09-28 2021-06-29 Zeon Corporation Laminate, method for producing same, and flexible printed circuit board
WO2021172192A1 (fr) 2020-02-27 2021-09-02 Ｍｃｐｐイノベーション合同会社 Feuille de résine et matériau de carte de circuit imprimé l'utilisant
WO2023008524A1 (fr) 2021-07-28 2023-02-02 三菱ケミカル株式会社 Composition de résine, feuille de résine, stratifié, objet durci en feuille, et matériau de carte de circuit imprimé
WO2023053927A1 (fr) 2021-09-30 2023-04-06 日本ゼオン株式会社 Composition de résine thermoplastique retardateur de flamme, corps moulé et film étiré

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JP2013235872A (ja) * 2012-05-02 2013-11-21 Dainippon Printing Co Ltd 樹脂付リードフレーム、多面付ｌｅｄパッケージ、樹脂付リードフレームの製造方法およびｌｅｄパッケージの製造方法
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
KR102110151B1 (ko) * 2013-02-12 2020-05-13 니폰 제온 가부시키가이샤 수지 조성물 및 그의 성형체
KR20150117265A (ko) * 2013-02-12 2015-10-19 니폰 제온 가부시키가이샤 수지 조성물 및 그의 성형체
EP2957596A4 (fr) * 2013-02-12 2016-08-31 Zeon Corp Composition de résine et produit moulé de celle-ci
US9631083B2 (en) 2013-02-12 2017-04-25 Zeon Corporation Resin composition and molded product thereof
JP2015054885A (ja) * 2013-09-11 2015-03-23 日本ゼオン株式会社 結晶性樹脂組成物
US10233301B2 (en) 2014-01-30 2019-03-19 Zeon Corporation Polymer composition and molded body
JP2015163682A (ja) * 2014-01-30 2015-09-10 日本ゼオン株式会社 重合体組成物及び成形体
WO2016103778A1 (fr) * 2014-01-30 2016-06-30 日本ゼオン株式会社 Composition polymère et corps moulé
JP2015178580A (ja) * 2014-03-20 2015-10-08 日本ゼオン株式会社 樹脂組成物及びその利用
US10767019B2 (en) 2015-09-28 2020-09-08 Zeon Corporation Resin composition, microporous membrane, separator and secondary battery
US11046046B2 (en) 2015-09-28 2021-06-29 Zeon Corporation Laminate, method for producing same, and flexible printed circuit board
JP2016105518A (ja) * 2016-03-03 2016-06-09 大日本印刷株式会社 樹脂付リードフレーム、多面付ｌｅｄパッケージ、樹脂付リードフレームの製造方法およびｌｅｄパッケージの製造方法
US10896827B2 (en) 2016-06-28 2021-01-19 Zeon Corporation Support for manufacturing semiconductor packages, use of support for manufacturing semiconductor packages, and method for manufacturing semiconductor packages
EP3498775A4 (fr) * 2016-08-08 2020-03-18 Zeon Corporation Composition de résine, et corps moulé de résine
WO2018030105A1 (fr) * 2016-08-08 2018-02-15 日本ゼオン株式会社 Composition de résine, et corps moulé de résine
US10844162B2 (en) 2016-08-08 2020-11-24 Zeon Corporation Resin composition and molded resin object
JPWO2018030105A1 (ja) * 2016-08-08 2019-06-06 日本ゼオン株式会社 樹脂組成物及び樹脂成形体
WO2018174029A1 (fr) 2017-03-21 2018-09-27 日本ゼオン株式会社 Matière de moulage, article moulé en résine, récipient pour produit cosmétique, récipient à semi-conducteur et procédé de production pour récipient à semi-conducteur
US11325287B2 (en) 2017-03-21 2022-05-10 Zeon Corporation Shaping material, resin shaped product, cosmetic container, semiconductor container, and method of producing semiconductor container
WO2019167683A1 (fr) 2018-02-28 2019-09-06 日本ゼオン株式会社 Tissu non-tissé, et filtre
WO2020017219A1 (fr) 2018-07-19 2020-01-23 日本ゼオン株式会社 Matériau de moulage et corps moulé
WO2021172192A1 (fr) 2020-02-27 2021-09-02 Ｍｃｐｐイノベーション合同会社 Feuille de résine et matériau de carte de circuit imprimé l'utilisant
WO2023008524A1 (fr) 2021-07-28 2023-02-02 三菱ケミカル株式会社 Composition de résine, feuille de résine, stratifié, objet durci en feuille, et matériau de carte de circuit imprimé
WO2023053927A1 (fr) 2021-09-30 2023-04-06 日本ゼオン株式会社 Composition de résine thermoplastique retardateur de flamme, corps moulé et film étiré

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CN103237843B (zh) 2015-08-05

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