JP2013056991A - Resin composition, and molded product made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for LED light reflectors, which is molded into a light reflector with good moldability, and gives a light reflector in which deterioration in light reflectivity due to the influence of heat scarcely occurs.SOLUTION: The resin composition contains: 100 pts.wt of a hydrogenated crystalline cyclic olefin ring-opening polymer, which is obtained by hydrogenating a cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer by using a homogeneous ruthenium catalyst, in the presence of an inorganic oxide containing, as a main component, silicon oxide and/or magnesium oxide, and containing aluminum oxide in a content ratio of 5 wt.% or less; and 0.5-8 pts.wt of the inorganic oxide.

Description

  LED (Light Emitting Diode) 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 the feature of being possible. Therefore, it is widely used as a backlight for electronic devices such as mobile phones and a light source for road traffic display boards. Further, with the development of blue LEDs and white LEDs in recent years, they are also used as light sources for backlights of general lighting fixtures and large liquid crystal display devices that replace incandescent bulbs and fluorescent lamps.

  An 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 luminance of the LED.

  The light reflector (LED light reflector) used for constituting the LED is required to have a high light reflectance, and further, during the molding of the light reflector (such as heating for melt molding), the manufacture of the LED It is required that the light reflectivity is not easily lowered even under the influence of heat (such as heating or soldering for curing the sealing material) and when using the LED (heat dissipation of the semiconductor chip). Therefore, as a material of the LED light reflector, for example, a composition formed by blending a white pigment such as titanium oxide with a polyamide resin having excellent heat resistance as described in Patent Document 1 and Patent Document 2 is widely used. It is used.

  However, even a light reflector made of a composition using a polyamide resin still has insufficient heat resistance, and heat is generated by heat generated during the formation of the light reflector, during the manufacture of the LED, and during the use of the LED. In some cases, the reflectivity was lowered. In addition, a composition in which a white pigment such as titanium oxide is blended 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. Therefore, there is a strong demand for a material that can provide a light reflector with good moldability and that provides a light reflector that is less likely to cause a decrease in light reflectance due to the influence of heat.

JP-A-2-288274 JP 2006-257314 A

  The present invention is a material for an LED light reflector that can be formed into a light reflector with good moldability and that can provide a light reflector that is less likely to cause a decrease in light reflectance due to the influence of heat. The purpose is to provide.

  Under such conventional technology, the present inventors provide a crystalline cyclic olefin ring-opening polymer hydrogenated product that gives a light reflector having high heat resistance (Japanese Patent Application No. 2010-200353), and further contains a nucleating agent. Thus, it has been found that crystallization is promoted and higher heat resistance is realized (Japanese Patent Application No. 2010-275702).

  As a result of further diligent investigations by the present inventors, when a certain inorganic oxide is selected as the nucleating agent, the cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene monomer is used. When hydrogenation using a ruthenium catalyst is carried out in the presence of a nucleating agent, the amount of the nucleating agent is greater than the addition of the nucleating agent to the hydrogenated cyclic olefin ring-opening polymer after hydrogenation in the absence of the nucleating agent. However, when they are compared in the same amount, the inventors have found that a material that is less likely to be deformed can be obtained while suppressing an excellent decrease in light reflectance even under high temperature conditions, and the present invention has been completed.

Thus, according to the present invention,
Presence of an inorganic oxide containing a cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer, containing silicon oxide and / or magnesium oxide as a main component and having an aluminum oxide content of 5% by weight or less A resin composition containing 100 parts by weight of a crystalline cyclic olefin ring-opening polymer hydrogenated product obtained by hydrogenation using a homogeneous ruthenium catalyst, and 0.5 to 8 parts by weight of the inorganic oxide. Provided.
The content ratio of the total amount of silicon oxide and magnesium oxide in the inorganic oxide is preferably 50% by weight or more, and more preferably 90% by weight or more.
The inorganic oxide is preferably talc or magnesium oxide.
Moreover, according to this invention, the optical molded object which consists of a resin composition mentioned above is provided.

The crystalline cyclic olefin ring-opening polymer hydrogenated product used in the present invention (hereinafter sometimes simply referred to as “cyclic olefin ring-opened polymer hydrogenated product”) is a repeating unit derived from a polycyclic norbornene monomer. A cyclic olefin ring-opening polymer having a hydrogen content using a homogeneous ruthenium catalyst in the presence of an inorganic oxide inorganic substance containing silicon oxide and / or magnesium oxide as a main component and having an aluminum oxide content of 5% by weight or less. It has become.
A method for obtaining a crystalline cyclic olefin ring-opened polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer is not particularly limited, but is described in, for example, JP-A-2006-52333. By such a method, ring-opening polymerization is performed using a polycyclic norbornene-based monomer as at least a part of the monomer to obtain a cyclic olefin ring-opening polymer having syndiotactic stereoregularity, A method of hydrogenating it is preferred. Hereinafter, the crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having crystallinity based on having syndiotactic stereoregularity will be described.

  The cyclic olefin ring-opening polymer used for obtaining a hydrogenated product of a crystalline cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer contains at least a polycyclic norbornene-based monomer. It can be used as 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. From the viewpoint of particularly improving the heat resistance of the molded product obtained from the resin composition, a compound represented by the following formula (1) or formula (2) is used as the polycyclic norbornene monomer. It is particularly preferred.

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Specific examples of the polycyclic norbornene monomer represented by the formula (1) 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 a 10-hexahydro-anthracene) can be mentioned.

  Moreover, as a polycyclic norbornene-type monomer represented by Formula (2), the tetracyclododecene when m of Formula (2) is 1, and m of Formula (2) are 2. The hexacycloheptadecenes in the case can be mentioned. Specific examples of 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-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride Tetracyclododecenes having substituents containing oxygen atoms such as tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imides Decenes; 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.

  Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. 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 an aromatic ring such as 12-phenylhexacycloheptadecene Hexacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene Hexacycloheptadecenes having a substituent containing an oxygen atom such as 12,13-dicarboxylic acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13 -Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene compound having a substituent containing a silicon atom such as trimethoxysilyl hexamethylene cycloheptanone decene and the like.

  In obtaining a cyclic olefin ring-opening polymer using a polycyclic norbornene-based monomer, one type of polycyclic norbornene-based monomer may be used alone, or two or more types of polycyclic norbornene-based monomers may be used. A combination of monomers can also be used.

  From the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the molded product obtained from the resin composition, a cyclic olefin ring-opening polymer used for the hydrogenation reaction is obtained. As the polycyclic norbornene-based monomer, a monomer containing dicyclopentadiene is preferably used, and a monomer containing 50% by weight or more of dicyclopentadiene is used with respect to the whole polycyclic norbornene-based monomer used. It is more preferable to use dicyclopentadiene alone.

  In addition, polycyclic norbornene monomers include endo isomers and exo isomers, both of which can be used as monomers, and one isomer can be used alone. Alternatively, an isomer mixture in which endo and exo isomers are present in an arbitrary ratio can be used. However, from the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the molded product obtained from the resin composition, the proportion of one stereoisomer should be increased. 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. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

  In obtaining the cyclic olefin ring-opened polymer, a monomer other than the polycyclic norbornene monomer may be copolymerized with the polycyclic norbornene monomer within the scope of the present invention. Examples of 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 fused to a norbornene skeleton. Can do.

  Specific examples of a bicyclic norbornene compound having no ring structure condensed to a 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- -Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5 , 5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene and the like norbornenes having a polar group containing an oxygen atom; And norbornenes having a polar group containing a nitrogen atom such as 5-cyanonorbornene.

  Specific examples of the monocyclic olefin include cyclohexene, cycloheptene, and cyclooctene. Specific examples of the cyclic diene include cyclohexadiene and cycloheptadiene.

  From the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the molded product obtained from the resin composition, a cyclic olefin ring-opening polymer used for the hydrogenation reaction is obtained. It is preferable that 80% by weight or more of a polycyclic norbornene-based monomer is included as a monomer for the purpose, and the monomer used is substantially a polycyclic norbornene-based monomer. It is particularly preferable that it is composed of only.

  In order to obtain a cyclic olefin ring-opening polymer hydrogenated product having syndiotactic stereoregularity, it is necessary to subject the cycloolefin ring-opening polymer having syndiotactic stereoregularity to a hydrogenation reaction. Therefore, in ring-opening polymerization of a polycyclic norbornene-based monomer, it is necessary to use a ring-opening polymerization catalyst capable of giving syndiotactic stereoregularity to the cyclic olefin ring-opening polymer. The ring-opening polymerization catalyst to be used is not particularly limited as long as it can give syndiotactic stereoregularity to the cyclic olefin ring-opening polymer, but comprises a metal compound represented by the following formula (3). A ring-opening polymerization catalyst is preferred.

(In the formula, M is a metal atom selected from group 6 transition metal atoms in the periodic table, N is a nitrogen atom, O is an oxygen atom, and R ⁸ is at least in the 3, 4, and 5 positions. A phenyl group which may have a substituent at one position, or a group represented by —CH ₂ R ¹⁰ , wherein R ⁹ has an alkyl group which may have a substituent and a substituent; X may be a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L may be an electron-donating neutral ligand, a is 0 or 1, b is an integer of 0 to 2. R ¹⁰ is selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Group.)

  The metal atom (M in formula (3)) constituting the metal compound represented by formula (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 represented by the formula (3) includes a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R ⁸ in the formula (3)) is a phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions, or — A group represented by CH ₂ R ¹⁰ (wherein 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); It is. Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, and a bromine atom A halogen atom such as; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. Also good. Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, and 3-methoxyphenyl. Groups, monosubstituted phenyl groups such as 4-cyclohexylphenyl group, 4-methoxyphenyl group; 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, 3,5-dimethoxyphenyl group Disubstituted phenyl groups such as 3,4,5-trimethylphenyl groups, 3,4,5-trichlorophenyl groups and the like; 2-naphthyl groups, 3-methyl-2-naphthyl groups, 4-methyl 2-naphthyl group which may have a substituent such as a 2-naphthyl group;

In the metal compound represented by the formula (3), in the group represented by —CH ₂ R ¹⁰ that can be used as a substituent on the nitrogen atom (R ⁸ in the formula (3)), R ¹⁰ is a hydrogen atom. Represents a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms of the alkyl group which may be a substituent and can be a group represented by R ¹⁰ is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Can be mentioned.

In the metal compound represented by the formula (3), an aryl group which may be used as a substituent on the nitrogen atom (R ⁸ in the formula (3)) and may have a substituent includes a phenyl group, Examples thereof include a 1-naphthyl group, a 2-naphthyl group, and an aryl group in which a hydrogen atom of these groups is replaced with another substituent. Further, the substituent of this aryl group is not particularly limited, but for example, a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group; an alkoxyl group such as a methoxy group or an ethoxy group; Can be mentioned.

The group represented by R ¹⁰ has 1 carbon number such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group. ˜20 alkyl groups are particularly preferably used.

  The metal compound represented by Formula (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 represented by the formula (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, and a t-butyldimethylsilyl group.

The metal compound represented by the formula (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 represented by the formula (3) may have one or two electron-donating neutral ligands. As 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; Among these, ethers are particularly preferably used.

As a ring-opening polymerization catalyst for obtaining a cyclic olefin ring-opening polymer having syndiotactic stereoregularity, the metal compound represented by the formula (3) particularly preferably used is a tungsten compound having a phenylimide group ( A compound in which M in the formula (3) is a tungsten atom and R ⁸ is a phenyl group), among which tetrachlorotungstenphenylimide (tetrahydrofuran) is particularly preferable.

  The metal compound represented by the formula (3) includes an oxyhalide of a Group 6 transition metal and phenyl isocyanates optionally having a substituent at at least one of the 3, 4, and 5 positions, or Mixing mono-substituted methyl isocyanates with an electron-donating neutral ligand (L) and, if necessary, alcohols, metal alkoxides, metal aryloxides (for example, JP-A-5-345817) Can be synthesized by the method described in 1). The synthesized metal compound represented by the formula (3) may be purified and isolated by crystallization, or the catalyst synthesis solution may be used as it is as a ring-opening polymerization catalyst without purification. You can also.

  The amount of the metal compound represented by the formula (3) used as the ring-opening polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually 1: 100 to 1: 2,000,000, preferably Is used in an amount of 1: 500 to 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.

  In using the metal compound represented by the formula (3) as a ring-opening polymerization catalyst, the metal compound represented by the formula (3) can be used alone, but from the viewpoint of increasing the polymerization activity, the formula (3 It is preferable to use a metal compound represented by 3) in combination with an organometallic reducing agent. Examples of the organometallic reducing agent that can be used include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, or organic tin is preferably used, and organic aluminum or organic tin is particularly preferably used. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin 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 0.5 to 20 moles relative to the metal compound represented by the formula (3). Double is particularly preferred. 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 the cyclic olefin ring-opening 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. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Can mixtures of these solvents. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.

  The ring-opening polymerization reaction can be started by mixing the monomer, the metal compound represented by the formula (3), and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a mixture of a metal compound represented by the formula (3) and the organometallic reducing agent may be added to the monomer and mixed, or the monomer and the organometallic reducing agent may be represented by the formula (3). A mixture with a metal compound to be added may be added and mixed, or a metal compound represented by formula (3) may be added to and mixed with a mixture of a monomer and an organometallic reducing agent. . Moreover, when mixing each component, the whole quantity of each component may be added at once, may be added in multiple times, and it is continuous over a comparatively long time (for example, 1 minute or more). It can also be added. Among them, from the viewpoint of controlling the polymerization temperature and the molecular weight of the resulting ring-opening polymer to obtain a resin composition particularly excellent in moldability, a plurality of monomers or metal compounds represented by formula (3) are used. It is preferable to add in portions or continuously, and it is particularly preferable to add the monomer in portions 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, and 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. Specifically, 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 , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; but like, but not limited to. 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 may be usually selected between 0.01 and 100 mol% with respect to the metal compound used as the ring-opening polymerization catalyst.

  Further, a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight modifiers include α-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, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1, - pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. 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.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. 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.

  Using the ring-opening polymerization catalyst containing the metal compound represented by the formula (3) as described above, the ring-opening polymerization reaction of the monomer containing the polycyclic norbornene monomer is performed under the conditions as described above. Thus, a cyclic olefin ring-opening polymer having syndiotactic stereoregularity can be obtained. Since the tacticity of the polymer does not change during the hydrogenation reaction, the cyclic olefin ring-opening polymer having this syndiotactic stereoregularity is subjected to a hydrogenation reaction, thereby having syndiotactic stereoregularity. Based on this, a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having crystallinity 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 to be subjected to the hydrogenation reaction is not particularly limited, but is preferably 10,000 to 100,000 in terms of polystyrene. More preferably, it is 8,000-80,000. By using a crystalline cyclic olefin ring-opening polymer hydrogenated product obtained from a cyclic olefin ring-opening polymer having such a weight average molecular weight, a resin composition particularly excellent in balance between moldability and heat resistance is obtained. Can be obtained. 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 during the polymerization.

  The molecular weight distribution of the cyclic olefin ring-opening polymer to be subjected to the hydrogenation reaction [ratio of number average molecular weight and weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (Mw / Mn)] is not particularly limited, but usually It is 1.5 to 4.0, preferably 1.6 to 3.5. By using a cyclic olefin ring-opened polymer hydrogenated product obtained from a cyclic olefin ring-opened polymer having such a molecular weight distribution, a resin composition particularly excellent in moldability can be obtained. 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-opened polymer (hydrogenation of the main chain double bond) can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. The hydrogenation catalyst is generally used as a homogeneous catalyst in the hydrogenation of an olefin compound, and is not particularly limited as long as it is a ruthenium compound, and examples thereof include the following.
For example, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, dichlorotris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonyltris (Tricyclohexylphosphine) ruthenium, RuH (OCOPh) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-CH ₃ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-C ₂ H ₅ ) (CO) (PPh) _{3) 2, RuH (OCOPh-} C 5 H 11) (CO) (PPh 3) 2, RuH (OCOPh-C 8 H 17) (CO) (PPh 3) 2, RuH (OCOPh-OCH 3) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-OC ₂ H ₅ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh) (CO) (P (c-C ₆ H ₁₁ ) ₃ ) ₂ , RuH (OCOPh-NH ₂ ) (CO) (PPh ₃ ) ₂ Can do.

The hydrogenation reaction is carried out in the presence of an inorganic oxide containing silicon oxide and / or magnesium oxide as a main component and having an aluminum oxide content of 5% by weight or less (hereinafter sometimes referred to as “specific inorganic oxide”). “Containing silicon oxide and / or magnesium oxide as a main component” means that the total amount of silicon oxide and magnesium oxide in this inorganic oxide is 50% by weight or more, preferably 90% by weight or more. Say. The content of aluminum oxide in the inorganic oxide is 5% by weight or less, preferably 1% by weight or less.
Examples of such specific inorganic oxides include talc, silicon oxide, and magnesium oxide.
In the production method of the present invention, with respect to 100 parts by weight of the cyclic olefin ring-opening polymer to be hydrogenated, in the presence of such a specific inorganic oxide, preferably 0.05 to 8 parts by weight, more preferably 0.00. The hydrogenation reaction proceeds in the presence of 1 to 8 parts by weight. When the amount of the specific inorganic oxide used in the hydrogenation reaction is less than 0.5 parts by weight, the specific inorganic oxide is added to the obtained cyclic olefin ring-opening polymer hydrogenated product. .

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such 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.

  Although the suitable range of conditions varies depending on the hydrogenation catalyst system used, 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 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 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. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 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 higher the hydrogenation rate, the better the heat resistance of the cyclic olefin ring-opening polymer hydrogenated product.

  The cyclic olefin ring-opening polymer hydrogenated product obtained as described above has a repeating unit derived from a polycyclic norbornene-based monomer as represented by the following formula (4) or formula (5). Is.

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

  Moreover, in the cyclic olefin ring-opened polymer hydrogenated product obtained as described above, the syndiotactic stereoregularity of the ring-opened polymer subjected to the hydrogenation reaction is maintained. Therefore, the cyclic olefin ring-opening polymer hydrogenated product obtained as described above has syndiotactic stereoregularity. The ratio of racemo dyad in the cyclic olefin ring-opening polymer hydrogenated product according to 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 Is 65-99%. By using the hydrogenated cyclic olefin ring-opening polymer having such syndiotactic stereoregularity, the LED light reflector obtained from the resin composition containing the hydrogenated product has a light reflectivity due to the influence of heat. It is possible to provide a light reflector that is particularly unlikely to deteriorate. The ratio of the racemo dyad of the 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 the racemo dyad of the cyclic olefin ring-opening polymer hydrogenated product can be measured and quantified by ¹³ C-NMR spectrum analysis. The method of quantification 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.

  As long as the cyclic olefin ring-opening polymer hydrogenated product according to the present invention has crystallinity, its melting point is not particularly limited, but preferably has a melting point of 200 ° C. or higher, and is 230 to 290. More preferably, it has a melting point of ° C. By using a cyclic olefin ring-opening polymer hydrogenated product having such a melting point, it is possible to obtain a resin composition that gives a molded product particularly excellent in balance between moldability and heat resistance. The melting point of the cyclic olefin ring-opening polymer hydrogenated product can be adjusted by adjusting the degree of syndiotactic stereoregularity (racemo dyad ratio) and the type of monomer used. can do.

The resin composition of the present invention is a cyclic olefin ring-opened polymer hydrogenated product containing the specific inorganic oxide described above, and is usually provided in a pelletized state. Other compounding agents may be mixed in the resin composition as necessary. The mixing method is not particularly limited as long as the compounding agent is sufficiently dispersed in the polymer. For example, 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, or the like, a method of dissolving and dispersing in an appropriate solvent, a coagulation method, a casting method, or a direct drying method There is a method of removing the solvent by a method.
When 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.
Further, the specific inorganic oxide also functions as a nucleating agent that promotes the crystallization of the cyclic olefin ring-opening polymer hydrogenated product, so that the amount of the crystalline cyclic olefin ring-opened polymer hydrogenated product is 100 parts by weight. It can be added in a range where the total amount of the specific inorganic compound (the sum of the amount used during the hydrogenation reaction and the amount added later as the nucleating agent) is 0.5 to 8 parts by weight. If the amount of the specific inorganic oxide is too small, the function as a nucleating agent is not sufficiently exhibited, so that the heat resistance cannot be improved. On the other hand, if the amount is too large, the heat resistance stability of the reflectance decreases.

  When using a resin composition for manufacture of LED light reflector, a white pigment can be mix | blended. Examples of white pigments include titanium oxide, white lead, zinc white, barium sulfate, calcium sulfate, basic lead sulfate, lithopone, zinc sulfide, lead titanate, zirconium oxide, barite, barium carbonate, chalk, precipitated calcium carbonate. , Limestone, magnesium carbonate, alumina, clay, talc powder, diatomaceous earth. A white pigment may be used individually by 1 type, and can also be used in combination of 2 or more type. Among these white pigments, titanium oxide is preferably used.

  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. Further, 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 μm, preferably 0.05 to 1 μm, and more preferably 0.1 to 1 μm. By using titanium oxide having such an average particle diameter, an LED light reflector having particularly excellent visible light reflectance can be obtained. 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.

  The blending amount of the white pigment in the resin composition used for manufacturing the LED light reflector may be determined in consideration of the balance between the light reflectance and the moldability of the resulting composition, but is not particularly limited. The amount is usually selected in the range of 20 to 100 parts by weight, preferably 25 to 90 parts by weight, more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product.

  The resin composition used for the production of the LED light reflector may be composed of only the crystalline cyclic olefin ring-opening polymer hydrogenated product and the white pigment, or may be composed of other materials. . Other materials that can be incorporated into the resin composition used in the manufacture of the LED light reflector include antioxidants, nucleating agents (excluding the specific inorganic oxides described above), fillers such as glass fibers, flame retardants, and flame retardants. Auxiliaries, colorants other than white pigments, antistatic agents, plasticizers, UV absorbers, light stabilizers, near infrared absorbers, lubricants (waxes), and repeating units derived from polycyclic norbornene monomers Examples include polymer materials other than the crystalline cyclic olefin ring-opening polymer hydrogenated product. Among these, it is preferable to add an antioxidant from the viewpoint that the resin composition used for the production of the LED light reflector is less likely to cause a decrease in light reflectance due to the influence of heat.

The antioxidant is not particularly limited, and for example, a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant can be used. Among these, it is preferable to use a phenolic antioxidant.
Although the compounding quantity of antioxidant is not specifically limited, 0.001-5 weight part normally with respect to 100 weight part of crystalline cyclic olefin ring-opening polymer hydrogenated products, Preferably it is 0.1-3 weight part The range is selected.

  In preparing the resin composition used for the production of the LED light reflector, a white pigment or the like may be blended and mixed with the crystalline cyclic olefin ring-opening polymer hydrogenated product according to a conventional method. The mixing method is not particularly limited. For example, 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.

  The light reflectance (spectral reflectance at a wavelength of 450 nm, before deterioration) of the LED light reflector is not particularly limited, but is preferably 80% or more, and more preferably 85 to 95%. The light reflectance of the LED light reflector can be adjusted by the type and amount of the white pigment.

  Although the melt flow rate (280 degreeC, 2.16kgf) of the resin composition used for manufacture of LED light reflector is not specifically limited, It is preferable that it is 5-150 g / 10min, and is 10-100 g / 10min. It is more preferable. The melt flow rate of the resin composition can be adjusted by the molecular weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product used, the type and blending amount of the white pigment.

  The resin composition used for manufacturing the LED light reflector reflects light emitted from the semiconductor chip of the LED by applying a melt molding method such as injection molding, extrusion molding, press molding, blow molding, or calendar molding. Can be formed into a reflector (reflector). The molding method may be determined according to the shape of the target LED light reflector, etc., but since the resin composition of the present invention has excellent moldability (melt moldability), the injection molding method is excellent in mass productivity. Is preferably applied to the LED light reflector.

  The LED light reflector obtained by using the resin composition of the present invention includes, for example, a light source for a backlight of a large liquid crystal display device, a light source for a backlight of a liquid crystal display of a small electronic device such as a lighting device or a mobile phone, and road traffic. It can be used as a reflector of an LED used as a light source for an electric display panel such as a display panel. Moreover, what is necessary is just to determine the shape of an LED light reflector suitably according to the use etc., and it can also comprise an LED light reflector in combination with another material as needed. There is no restriction | limiting in the method of comprising LED using a LED light reflector, What is necessary is just to combine a semiconductor chip and a sealing material with a LED light reflector according to a conventional method.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the part and% in each example are a basis of weight unless there is particular notice.

Moreover, the measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight of cyclic olefin ring-opening polymer (weight average molecular weight and number average molecular weight) Gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), H type column (manufactured by Tosoh Corporation) Using tetrahydrofuran as a solvent, it was measured at 40 ° C. and determined as a polystyrene equivalent value.
(2) Hydrogenation rate in cyclic olefin ring-opened polymer hydrogenated product It was determined by ¹ H-NMR measurement at 145 ° C. as an orthodichlorobenzene-d ₄ solvent.
(3) Melting | fusing point of cyclic olefin ring-opening polymer hydrogenated substance It heated up at 10 degree-C / min and measured using the differential scanning calorimeter.
(4) (ΔHm−ΔHc) / ΔHm
Using a differential scanning calorimeter, 10 mg of the molded product was heated according to JIS K 7122 at a heating rate of 10 ° C./min. (J / g) was obtained and calculated. The maximum value of the numerical value is 1.0, which means that the larger the numerical value is, the more the crystallization is progressing. It is not preferable because stability is lowered and solder heat resistance is insufficient. Here, the numerical values of 0.9 or more were rated as ◯, 0.6 or more and less than 0.9 as Δ, and those smaller than 0.6 as x.
(5) Initial reflectance For flat plates molded for evaluation of injection moldability, a spectral color difference meter (trade name “SE-2000”) manufactured by Nippon Denshoku Industries Co., Ltd. is used and a standard white plate as a standard sample is 450 nm. The spectral reflectance of wavelength light was measured. In addition, in the evaluation of injection moldability, when only a flat plate not suitable for the measurement of the initial reflectance was obtained, the flat plate was produced by changing the molding conditions, and the measurement was performed by selecting a portion having no defect. .
(6) Reflectance after heat-resistant long-term stability test The flat plate whose initial reflectivity was measured was subjected to heat treatment at 180 ° C. for 6 hours using an oven, and then subjected to a 450 nm wavelength by the same method as the initial reflectivity measurement method. The spectral reflectance of light was measured.
(7) Deformation after heat-resistant long-term stability test The flat plate whose initial reflectivity was measured was subjected to heat treatment at 180 ° C. for 6 hours using an oven, and then the dimensional deformation of the molded body was confirmed. The case where there was no deformation was rated as ◯, and the case where warpage of 0.2 mm or more was observed was rated as x.

[Synthesis Example 1]
After fully drying, 857.2 parts of a 70% cyclohexane solution of dicyclopentadiene (endo content rate of 99% or more) (600 parts as the amount of dicyclopentadiene) was charged into a SUS pressure-resistant reaction vessel purged with nitrogen, Furthermore, 3,076 parts of cyclohexane and 23.2 parts of 1-hexene were added, and subsequently, 2 parts of a 19% n-hexane solution of diethylaluminum ethoxide was added and heated to 40 ° C. while stirring. Subsequently, a solution obtained by dissolving 0.88 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 11 parts of toluene was added to initiate a ring-opening polymerization reaction. After 4 hours, 0.4 part of isopropanol was added to stop the polymerization reaction. The number average molecular weight (Mn) and the polymerization average molecular weight (Mw) of the obtained ring-opening polymer are 21,900 and 67,400, respectively, and the molecular weight distribution (Mw / Mn) obtained therefrom is 3.08. there were.

[Synthesis Example 2]
After sufficiently drying, 200 parts of a cyclohexane solution of the ring-opening polymer obtained in Synthesis Example 1 (30 parts as the amount of the ring-opening polymer) was added to a nitrogen-substituted SUS pressure-resistant reaction vessel and stirred. Add a suspension solution of 0.022 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium and 0.3 part of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) to 100 parts of cyclohexane. The hydrogenation reaction was performed at a hydrogen pressure of 4.4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction solution is poured into a large amount of isopropyl alcohol to completely precipitate the polymer, separated by filtration and collected, and then dried under vacuum at 80 ° C. for 20 hours to obtain a crystalline cyclic olefin ring-opening weight. Combined hydrogenated product A, 28 parts (yield 93%) was obtained. The hydrogenation rate of the cyclic olefin ring-opening polymer hydrogenated product A was 99% or more, and the melting point was 262 ° C.

[Example 1]
10 parts hydrogenated cyclic olefin ring-opened polymer obtained in Synthesis Example 2, titanium oxide (rutile titanium oxide having an average particle size of 0.2 μm, trade name “FTR-700”, manufactured by Sakai Chemical Industry Co., Ltd .; aluminum oxide 5 parts of an amount of 10 ppm or less), 2 parts of glass fiber (trade name “CSG 3PA-830”, manufactured by Nittobo Co., Ltd.), wax (melting point 69 ° C., trade name “LUVAX (registered trademark) 1266”, manufactured by Nippon Seiki Co., Ltd.) 0.2 parts, antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, trade name “Irganox (registered trademark) 1010”, after mixing BASF Japan Ltd.) 0.1 parts of a small kneading machine (DSM Xplore Ltd., 290 ° C. using Micro15Compounder), 2 minutes at 1.67 s ^-1, the condition Kneaded to and pelletized. Then, with a small injection molding machine (Micro Injection Molding Machine 10cc, manufactured by DSM Xplore), the molding temperature was 290 ° C, the injection pressure was 0.7 MPa, the holding time in the mold was 10 seconds, the mold temperature was 100 ° C, and the length was 70 mm. A flat plate having a width of 30 mm and a thickness of 3 mm was formed. The obtained flat plate had an initial reflectance of 91%. Using a differential scanning calorimeter, ΔHm−ΔHc) / ΔHm was determined for the fragments of the molded plate, a heat-resistant long-term stability test was performed, and it was confirmed that there was no deformation. The reflectance after the heat-resistant long-term stability test was 89%. Moreover, the composition of each composition and the respective evaluation results are summarized in Table 1.

[Example 2]
The amount of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd .; amount of aluminum oxide 0.7%) added during the hydrogenation reaction in Synthesis Example 2 was 0.15 part. In the pelletizing step, a molded body was obtained and evaluated in the same manner as in Example 1 except that 0.15 part of talc was added in the same manner as titanium oxide and wax. Each evaluation result is shown in Table 1.

[Examples 3 and 4]
In the same manner as in Synthesis Example 2 except that the amount of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) added during the hydrogenation reaction was changed as shown in Table 1, a crystalline cyclic olefin was opened. A ring polymer hydrogenated product was obtained and evaluated. Moreover, from the obtained ring-opened polymer hydride, a molded product was obtained in the same manner as in Example 1 and evaluated. The results are summarized in Table 1.
Example 5
The amount of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd .; amount of aluminum oxide 0.7%) added during the hydrogenation reaction is 0.06 part, and the amount of talc added during pelletization A molded body was obtained and evaluated in the same manner as in Example 2 except that 0.03 part was obtained. Each evaluation result is shown in Table 1.

Example 6
In the same manner as in Synthesis Example 2, except that the talc added during the hydrogenation reaction was changed to 0.3 parts of magnesium oxide (trade name “Pyroxuma (registered trademark) 5Q”, manufactured by Kyowa Chemical Industry Co., Ltd.) A ring polymer hydrogenated product was obtained and evaluated. Moreover, the molded object was obtained similarly to Example 1 and the evaluation was performed. The results are summarized in Table 1.

[Comparative Example 1]
A crystalline cyclic olefin ring-opened polymer hydride was obtained in the same manner as in Synthesis Example 2 except that talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) was not added during the hydrogenation reaction. And evaluated it. Other than using this ring-opening polymer hydride and adding 0.1 part of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) in the step of pelletizing the ring-opening polymer hydride Were obtained in the same manner as in Example 2 and evaluated. Each evaluation result is summarized in Table 1.

[Comparative Example 2]
A molded body was obtained in the same manner as in Comparative Example 1 except that the amount of talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) added in the pelletizing step was changed to 0.8 parts. The evaluation was performed. The molded body after the heat-resistant long-term stability test had a warp of 0.3 mm. The results are summarized in Table 1.

[Comparative Example 3]
Crystalline cyclic olefin ring-opening polymer in the same manner as in Synthesis Example 2 except that talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) was changed to 0.06 parts during the hydrogenation reaction. A hydrogenated product was obtained and evaluated. Moreover, from the obtained ring-opened polymer hydride, a molded product was obtained in the same manner as in Example 1 and evaluated. The molded body after the heat-resistant long-term stability test had a warp of 0.3 mm. The results are summarized in Table 1.

[Comparative Example 4]
Hydrogenation of a crystalline cyclic olefin ring-opening polymer in the same manner as in Synthesis Example 2, except that talc (hydrous magnesium silicate, trade name “Talc MS”, manufactured by Nippon Talc Co., Ltd.) was changed to 3 parts during the hydrogenation reaction. Things were obtained and evaluated. Moreover, from the obtained ring-opened polymer hydride, a molded product was obtained in the same manner as in Example 1 and evaluated. The reflectivity after the heat test decreased by 11% to 72%, and excessive addition of talc significantly reduced the reflectivity.

[Comparative Example 5]
Synthetic Example 2 except that synthetic hydrotalcite (trade name “KYOWARD (registered trademark) 700” manufactured by Kyowa Chemical Industry Co., Ltd .; aluminum oxide amount 10.5%) was added instead of talc during the hydrogenation reaction. In the same manner, a crystalline cyclic olefin ring-opening polymer hydride was obtained. However, the hydrogenation rate was 96%, resulting in poor hydrogenation. From the obtained ring-opened polymer hydride, a molded product was obtained in the same manner as in Example 1 and evaluated. The molded body after the heat-resistant long-term stability test had a warp of 0.8 mm. The results are summarized in Table 1.

[Comparative Example 6]
Crystalline cyclic olefin ring-opening polymer hydrogen in the same manner as in Synthesis Example 2 except that activated alumina (trade name “NHKD-24HD”, manufactured by Sumitomo Chemical Co., Ltd.) was added instead of talc during the hydrogenation reaction. The compound was obtained. However, the hydrogenation rate was 95%, resulting in poor hydrogenation. From the obtained ring-opened polymer hydride, a molded product was obtained in the same manner as in Example 1 and evaluated. The molded body after the heat-resistant long-term stability test had a warp of 0.9 mm. The results are summarized in Table 1.

From this result, the following can be understood.
When hydrogenating a cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer, when talc is present (Examples 1 and 2), and cyclic olefin ring-opening polymer hydrogenation Comparing with the case where talc is added to the product (Comparative Example 1), it can be seen that even if the amount of talc is the same, there is a difference in the heat-resistant long-term stability.
When the amount of talc is large, it can be seen that when talc is added to the cyclic olefin ring-opening polymer hydrogenated product, the reflectance after the heat resistance test is greatly reduced (Example 3 and Comparative Example 2).
Even if the amount of talc added during the hydrogenation reaction is 0.2 parts, the amount of talc added during the hydrogenation reaction is 0.5 parts by adding talc to 0.5 parts during pelletization. It can be seen that the same effects as those obtained in Examples 4 and 5 and Comparative Example 3 can be obtained.
Moreover, when there is too much addition amount of talc, it turns out that the fall of the reflectance in a heat-resistant long-term stability test becomes large (comparative example 4).
Furthermore, it can be seen that the same effect as that of talc can be obtained even if the inorganic oxide is changed to magnesium oxide instead of talc (Example 6). On the other hand, hydrotalcite or activated alumina containing a large amount of aluminum oxide is used instead of talc. It can be seen that the decrease in reflectivity in the heat-resistant long-term stability test becomes large and deformation after the heat-resistant test is confirmed (Comparative Examples 5 and 6).

Claims (5)

Presence of an inorganic oxide containing a cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer, containing silicon oxide and / or magnesium oxide as a main component and having an aluminum oxide content of 5% by weight or less A resin composition comprising 100 parts by weight of a crystalline cyclic olefin ring-opening polymer hydrogenated product obtained by hydrogenation using a homogeneous ruthenium catalyst and 0.5 to 8 parts by weight of the inorganic oxide. The resin composition according to claim 1, wherein a content ratio of the total amount of silicon oxide and magnesium oxide of the inorganic oxide is 50% by weight or more. The resin composition according to claim 1, wherein a content ratio of the total amount of silicon oxide and magnesium oxide in the inorganic oxide is 90% by weight or more. The resin composition according to claim 1, wherein the inorganic oxide is talc or magnesium oxide. The LED light reflector formed by melt-molding the resin composition in any one of Claims 1-6.