JP6287413B2 - Resin composition and use thereof - Google Patents

Description

  The present invention relates to a resin composition comprising an alicyclic structure-containing polymer suitable for a light reflector excellent in heat resistance.

Effect of heat on resin composition containing wax and crystallization nucleating agent on hydrogenated crystalline cyclic olefin ring-opening polymer having repeating unit derived from polycyclic norbornene monomer having 3 or more rings It is known that it is suitable for an LED light reflecting plate because it is difficult to deform due to (Patent Document 1). In patent document 1, it is described that it is preferable to mix | blend glass fiber in order to subtract heat resistance.
Moreover, the resin composition which mix | blended the glass filler with the crystalline cyclic olefin ring-opening polymer hydrogenated substance which has a repeating unit derived from the polycyclic norbornene-type monomer which has a 3 or more ring is the reflow process. It is known to be suitable for a high frequency dielectric antenna because it can withstand high temperature conditions (Patent Document 2).

International Publication WO2012 / 033076 JP 2013-256596 A

The present inventor manufactured an LED light reflector using the resin composition described in Patent Document 1 in which glass fiber was blended, and was able to prevent deformation under a high temperature environment (that is, improved heat resistance). It was also confirmed that the light reflectance after the heat test was insufficient.
Therefore, as a result of diligent studies to achieve both high heat resistance and high light reflectance, the present inventor achieved this object by blending whisker having an aspect ratio within a predetermined range as an inorganic filler instead of glass fiber. As a result, the present invention has been completed.

Thus, according to the present invention, (A) (B) with respect to 100 parts by weight of a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings. There is provided a resin composition comprising 5 to 100 parts by weight of whiskers having an aspect ratio of 2 to 100 and (C) 5 to 20 parts of a white pigment.
The white pigment is preferably titanium oxide.
Moreover, according to this invention, the molded object which uses the resin composition of this invention is provided.
Among the molded products, a light reflector is particularly effective in the present invention.

<Hydrogenated crystalline cyclic olefin ring-opening polymer>
The crystalline cyclic olefin ring-opening polymer hydrogenated product used in the present invention is sometimes referred to as a polycyclic norbornene monomer having three or more rings (hereinafter simply referred to as “polycyclic norbornene monomer”). ) Is obtained by subjecting the monomer containing at least a ring-opening polymerization to hydrogenation of the main chain double bond of the obtained ring-opening polymer, and having crystallinity.

  A 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. That is, this method is a syndiotactic process in which a ring-opening polymer is obtained by solution polymerization of a norbornene monomer having three or more rings using a Group 6 transition metal compound of the periodic table as a polymerization catalyst. By obtaining a cyclic olefin ring-opening polymer having stereoregularity and hydrogenating the main chain double bond of the ring-opening polymer, the target crystalline cyclic olefin ring-opening polymer hydrogenated product can be efficiently obtained. It can be obtained.

  The crystalline cyclic olefin ring-opening polymer used in the present invention can be obtained by using a polycyclic norbornene-based monomer having three or more rings as at least a part of the monomer.

  The polycyclic norbornene monomer having three or more rings may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule. That is, the polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed to the norbornene ring in the molecule. . From the viewpoint of particularly improving the heat resistance of the molded article made of the resin composition, a compound represented by the following formula (1) or (2) is particularly preferable as the polycyclic norbornene-based monomer.

In formulas (1) and (2), R ¹ , R ² and 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 a C 1-20 divalent hydrocarbon group which may have a substituent. 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 group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, 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, pentenyl group, hexenyl group, cyclohexenyl group; ethynyl group, 1-propynyl group, 2-propynyl (propargyl) group , 3-butynyl group, pentynyl group, hexynyl group and other alkynyl groups; phenyl group, tolyl group Aralkyl groups such as benzyl groups and phenethyl groups; xylyl group, a biphenylyl group, a 1-naphthyl group, 2-naphthyl group, anthryl group, an aryl group or a phenanthryl group and the like.

  Examples of these 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 and 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 .

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 10-hexa hydro 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. And hexacycloheptadecenes in the case.

  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- Toxicarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, etc. Tetracyclododecenes having substituents containing oxygen atoms; tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide A tetracyclododecene having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; a tetracyclododecene 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, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12 , 13-dicarboxylic acid, hexacycloheptadecene 12,13-dicarboxylic anhydride, etc., hexacycloheptadecenes having a substituent containing an oxygen atom; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13- Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic acid imide; Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene compound having a substituent containing a Le hexa cycloheptanone de silicon atoms, such as Sen; and the like.

  These polycyclic norbornene monomers can be used singly or in combination of two or more.

  Among these, from the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting molded product, 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.

  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 resulting resin composition, it is preferable to increase 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. 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 a cyclic olefin ring-opening polymer, 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. .

  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-5-methyl Xoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5, Norbornenes having a polar group containing an oxygen atom, such as 5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene; 5 -Norbornenes having a polar group containing a nitrogen atom such as cyanonorbornene.

  Specific examples of the monocyclic olefin include cyclohexene, cycloheptene, and cyclooctene.

  Specific examples of the cyclic diene include cyclohexadiene and cycloheptadiene.

  Among these, from the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting molded product, in order to obtain a cyclic olefin ring-opening polymer for use in the hydrogenation reaction. As 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

  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. 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)”).

In the formula, M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ⁸ is a phenyl group optionally having a substituent at at least one of the 3, 4, and 5 positions. , Or a group represented by CH ₂ R ¹⁰ , wherein R ⁹ is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group, and 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, and b is an integer of 0-2. is there. R ¹⁰ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

The metal atom (M) constituting the metal compound (3) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.
The metal compound (3) comprises a metal imide bond. R ⁸ is a substituent on the nitrogen atom constituting the metal imide bond.

  Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions may include an alkyl group such as a methyl group or an ethyl group; a fluorine atom, a chlorine atom, or a bromine atom A halogen atom such as methoxy group, ethoxy group, isopropoxy group or the like; and further, substituents present in at least two positions of 3,4,5 are bonded to each other. Also good.

  Specific examples of the 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 A monosubstituted phenyl group such as a cyclohexylphenyl group or a 4-methoxyphenyl group; a 2-substituted group such as a 3,5-dimethylphenyl group, a 3,5-dichlorophenyl group, a 3,4-dimethylphenyl group, or a 3,5-dimethoxyphenyl group; Substituted phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group and 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2- 2-naphthyl group which may have a substituent such as a naphthyl group.

The metal compound (3) has a substituent of R ^{10 in} the group represented by —CH ₂ R ^10, which can be used as a substituent on the nitrogen atom (R ⁸ in formula (3)). The number of carbon atoms of the good alkyl group 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; Is mentioned.

Examples of the aryl group of R ¹⁰ which may have a substituent include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The substituent of the aryl group is not particularly limited, and examples thereof include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; Can be mentioned.

R ¹⁰ is an alkyl group having 1 to 20 carbon atoms such as 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 hexyl group, an octyl group, or a decyl group. 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, and a t-butyldimethylsilyl group.

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. 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.

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.

  In using the metal compound (3) as a ring-opening polymerization catalyst, 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.

  Examples of the organometallic reducing agent used include Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organolithium, organomagnesium, organozinc, organoaluminum, or organotin are preferably used, and organoaluminum or organotin are particularly preferably used.

  Examples of the organic lithium include n-butyl lithium, methyl lithium, phenyl lithium and the like. Examples of the organic magnesium include butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, allyl magnesium bromide and the like. 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. Is mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

  0.1-100 mol times is preferable with respect to a metal compound (3), as for the usage-amount of an organometallic reducing agent, 0.2-50 mol times is more preferable, and 0.5-20 mol times is especially preferable. 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.

  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. , 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. Among these 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. For example, 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.

  When mixing each component, 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). You can also Among these, from the viewpoint of controlling the polymerization temperature and the molecular weight of the resulting ring-opening polymer to obtain a resin composition having particularly excellent moldability, 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, 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 , 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 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, 2,5-dimethyl-1,5-hexadiene and other nonconjugated dienes; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1,3-penta Ene, conjugated dienes such as 1,3-hexadiene; and the like.

  The amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer used.

  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.

  By using the ring-opening polymerization catalyst containing the metal compound (3) as described above, the ring-opening polymerization reaction of the monomer containing the polycyclic norbornene-based monomer under the conditions as described above is performed. A cyclic olefin ring-opening polymer having tic stereoregularity can be obtained.

  The ratio of racemo dyad in the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is usually 60% or more, preferably 65% or more, more preferably 70 to 99%. The ratio of racemo dyad (degree of syndiotactic stereoregularity) in the crystalline cyclic olefin ring-opening polymer can be adjusted by selecting the kind of the ring-opening polymerization catalyst.

  The weight average molecular weight (Mw) measured by gel permeation chromatography of the crystalline cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is 10,000 to 100,000 in terms of polyisoprene. Preferably, it is 15,000-80,000. Using a crystalline cyclic olefin ring-opened polymer hydrogenated product obtained from a crystalline cyclic olefin ring-opened polymer having such a weight average molecular weight is excellent in moldability and excellent in heat resistance of the obtained molded body Is preferable. The weight average molecular weight of the crystalline cyclic olefin ring-opening polymer can be adjusted by adjusting the addition amount of the molecular weight modifier used during the polymerization.

  The molecular weight distribution of the crystalline cyclic olefin ring-opened polymer subjected to the hydrogenation reaction [ratio of the number average molecular weight in terms of polyisoprene and the weight average molecular weight (Mw / Mn) measured by gel permeation chromatography] is not particularly limited. However, it is 1.5-4.0 normally, Preferably it is 1.6-3.5. The use of a crystalline cyclic olefin ring-opened polymer hydrogenated product obtained from a crystalline cyclic olefin ring-opened polymer having such a molecular weight distribution is preferred in terms of excellent moldability.

  The molecular weight distribution of the crystalline cyclic olefin ring-opening polymer hydrogenated product can be adjusted by the monomer addition method and the monomer concentration during the ring-opening polymerization reaction.

  The hydrogenation reaction of the crystalline cyclic olefin ring-opened polymer (hydrogenation of the main chain double bond) 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.

  As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Combinations of butyl lithium, tetrabutoxy titanate / dimethyl magnesium and the like can be mentioned. Further examples include noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium and the like. .

  As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of 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. 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 crystalline cyclic olefin ring-opening polymer is not particularly limited, but is preferably 70% or more, more preferably 80% or more, particularly Preferably it is 90% or more, most preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the crystalline cyclic olefin ring-opening polymer hydrogenated product.

  The hydrogenated crystalline cyclic olefin ring-opened polymer obtained as described above is a polycyclic norbornene-based compound having three or more rings as represented by the following formula (4) or formula (5) It has a repeating unit derived from a monomer.

(In the formula, each of R ¹ and R ² independently contains 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, and R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. .)

(In formulas (4) and (5), R ^{1 to} R ⁷ and m represent the same meaning as described above.)
Moreover, in the crystalline cyclic olefin ring-opening polymer hydrogenated product obtained as described above, the syndiotactic stereoregularity of the ring-opening polymer subjected to the hydrogenation reaction is maintained. Therefore, the obtained crystalline cyclic olefin ring-opening polymer hydrogenated product has syndiotactic stereoregularity. 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%.

  Since 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. Thus, a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer having crystallinity can be obtained.

  By using a crystalline cyclic olefin ring-opening polymer hydrogenated product having such syndiotactic stereoregularity, the resulting resin composition can give a molded product that is hardly deformed by the influence of heat. It will be a thing. 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 crystalline cyclic olefin ring-opening polymer subjected to the hydrogenation reaction.

The ratio of the racemo dyad of the crystalline cyclic olefin ring-opening polymer hydrogenated product can be quantified based on the spectrum data obtained by measuring a ¹³ C-NMR spectrum. 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.

  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.

<Whisker>
The whisker used in the present invention is an inorganic crystal having an aspect ratio of 2 to 100, preferably 3 to 80. Specific examples of inorganic materials include metals such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon or carbides such as carbon black, graphite, activated carbon, carbon balloon, and silicon carbide; silica, silica balloon, and alumina. , Titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, beryllium oxide, barium ferrite, strontium ferrite and other metal oxides; aluminum hydroxide, magnesium hydroxide and other metal hydroxides; calcium carbonate, Metal carbonates such as magnesium carbonate and sodium bicarbonate; metal sulfates such as calcium sulfate; silicates such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; calcium titanate , Zirconate titanate Titanates such as phosphate lead; aluminum nitride, silicon nitride, nitrides such as boron nitride; and the like. Among these, white whiskers such as titanium oxide, titanate, and silicate are preferable from the viewpoint of light reflectance. These inorganic fillers can be used alone or in combination of two or more.

  The blending amount of the whisker in the present invention is 5 to 100 parts by weight of the crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings. 100 parts by weight, preferably 10 to 60 parts by weight. If the blending amount of whiskers is too small, the heat resistance during reflowing and the strength of the molded product are poor, and if the blending amount of whiskers is too large, the dielectric loss tangent is increased and the moldability is poor.

<White pigment>
In the present invention, the white pigment is used for improving the light reflectance, and is a spherical inorganic substance having an aspect ratio of substantially 1. Preferred inorganic materials are, 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, sulfuric acid Barium, barium carbonate, barium sulfate, lead white, zinc white, basic lead sulfate, lithopone, zinc sulfide, zirconium oxide, barite, chalk, stone kow, clay, talc powder, diatomaceous earth, etc., particularly titanium oxide is preferred. In the composition of the present invention, the white pigment is based on 100 parts by weight of a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings. 20 to 200 parts by weight, preferably 30 to 180 parts by weight. If it is this range, the composition excellent in the balance of light reflectance, heat resistance, and a moldability will be obtained.

<Other ingredients>
To the resin composition of the present invention, additives used for general resin compounding can be added as other compounding agents.
Other compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials. For example, thermoplastic elastomers, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, Examples include release agents, colorants such as dyes and pigments, plasticizers, antistatic agents, fluorescent brighteners, and inorganic fillers.

<Resin composition>
The method for obtaining the resin composition of the present invention is characterized in that a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings has an aspect ratio of 2 to 100. The whisker, white pigment, and other compounding agents used as necessary are not particularly limited. Moreover, there is no special restriction | limiting in the order of a mixing | blending. Examples of the compounding method include a method of kneading a resin in a molten state with a mixer, a single-screw kneader, a twin-screw kneader, a roll, a Brabender, an extruder, etc., a solidifying method by dissolving and dispersing in an appropriate solvent, and a casting method. Or a method of removing the solvent by a direct drying method.
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.

<Molded body>
The resin composition of the present invention is a known thermoplastic resin molding method, for example, injection molding method, extrusion molding method, cast molding method, inflation molding method, blow molding method, vacuum molding method, press molding method, compression molding method. Further, it can be molded by a rotational molding method, a calendar molding method, a rolling molding method, a cutting molding method or the like to obtain a molded body.
Especially, since the resin composition of this invention has the outstanding moldability (melt moldability), it is preferable to apply the injection molding method which is excellent in mass-productivity.
An arbitrary pattern can also be formed on the surface of the molded body molded in this manner as required 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.

Measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight (weight average molecular weight and number average molecular weight) of cyclic olefin ring-opening polymer
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was used and measured at 40 ° C. using tetrahydrofuran as a solvent to obtain a polystyrene equivalent value.
(2) Hydrogenation rate in cyclic olefin ring-opening polymer hydrogenated product It was determined by ¹ H-NMR measurement at 145 ° C. as an orthodichlorobenzene-d4 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) Initial reflectance For flat plates molded for evaluation of injection moldability, a spectroscopic color difference meter (trade name “SE-2000”) manufactured by Nippon Denshoku Industries Co., Ltd. is used and a standard white plate is used as a standard sample, and 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. .
(5) Reflectivity after heat-resistant long-term stability test (reflow) After performing heat treatment at 180 ° C. for 6 hours using an oven on the flat plate whose initial reflectivity was measured, the same method as the method for measuring initial reflectivity Was used to measure the spectral reflectance of 450 nm wavelength light.
(6) Deformation after heat-resistant long-term stability test (Reflow resistance)
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.

The hydrogenated dicyclopentadiene ring-opening polymer used in the examples and comparative examples was synthesized as follows.
After sufficiently drying, in a metal pressure-resistant reaction vessel purged with nitrogen, 154.5 parts of cyclohexane, 42.8 parts of a 70% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (as the amount of dicyclopentadiene) 30 parts) and 1.9 parts of 1-hexene were added and heated to 53 ° C. On the other hand, 0.061 part of 19% diethylaluminum ethoxide / n-hexane solution was added to a solution of 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene and stirred for 10 minutes. Then, a catalyst solution was prepared. This catalyst solution was added to the reactor to initiate a ring-opening polymerization reaction. Then, it was made to react for 4 hours, keeping 53 degreeC, and the dicyclopentadiene ring-opening polymer solution was obtained. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained dicyclopentadiene ring-opening polymer are 8,750 and 28,100, respectively, and the molecular weight distribution (Mw / Mn) obtained from these is 3.21.
To 200 parts of the resulting dicyclopentadiene ring-opening polymer solution, 0.037 part of 1,2-ethanediol was added as a terminator, heated to 60 ° C. and stirred for 1 hour to stop the polymerization reaction. Thereafter, 1 part of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts of Radiolite (registered trademark) # 1500 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid, and a PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo Co., Ltd.) was used. And the solution was filtered off. To 200 parts of the dicyclopentadiene ring-opening polymer solution after filtration (100 parts of polymer amount), 100 parts of cyclohexane is added, 0.0043 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium is added, and the hydrogen pressure is 6 MPa. The hydrogenation reaction was performed at 180 ° C. for 4 hours. The obtained hydrogenation reaction liquid is a slurry solution in which a polymer is precipitated. The polymer hydrogenation product and the solution are separated using a centrifuge and dried under reduced pressure at 60 ° C. for 24 hours to obtain crystals. 28.5 parts of a hydrogenated dicyclopentadiene ring-opening polymer having a property was obtained. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point (Tm) was 262 ° C., and the ratio of racemo dyad was 89%.

[Example 1]
100 parts of crystalline cyclic olefin ring-opening polymer hydrogenated product A, titanium oxide (trade name “PC-3”, rutile titanium oxide having an average particle size of 0.21 μm, manufactured by Ishihara Sangyo 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 Ltd.) 0.8 parts, After mixing 10 parts of whisker A (trade name “FTL-300”, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide whisker; fiber diameter 0.27 μm, fiber length 5.15 μm), a small kneader (Micro15 Compounder, manufactured by DSMXplore) was used. The resulting kneaded product was pelletized by kneading for 2 minutes at 290 ° C. and 100 rpm. Then, using a small injection molding machine (MicroInjectionMounting Machine 10 cc, manufactured by DSMXplore), the molding temperature was 290 ° C., the injection pressure was 0.7 MPa, the holding time in the mold was 10 seconds, and the mold temperature was 150 ° C. and the length was 70 mm and the width was 30 mm. A flat plate having a thickness of 3 mm was formed. Table 2 shows the composition of the composition and the evaluation results thereof.

[Examples 2 to 5 and Comparative Examples 1 to 4]
Except having changed the compounding quantity (weight part) of the composition as shown to a table | surface, it carried out similarly to Example 1, and obtained the molded object and performed the evaluation. Each evaluation result is shown in a table. In the table, whisker B is trade name “Tismo N” (potassium titanate whisker manufactured by Otsuka Chemical Co., Ltd .; fiber diameter 0.3 to 0.6 μm, fiber length 10 to 20 μm), whisker C is trade name “FPW”. ”(Wollastonite manufactured by Kinsei Matech Co., Ltd .; particle size # 150, aspect ratio 3 to 6) was used as a comparative example, whisker D was trade name“ Nichibi Alf (registered trademark) ”(manufactured by Chinibi Corporation, alumina fiber: fiber diameter 7 μm) is cut to a length of 800 μm, and the glass fiber is a trade name “CSG3PA-830” (manufactured by Nittobo Co., Ltd .; fiber diameter 13 μm, fiber length 3 mm).

From this result, the following can be understood.
A molded product made of a resin composition in which a predetermined amount of whisker having an aspect ratio of 2 or more is blended with a crystalline dicyclopentadiene ring-opening polymer hydrogenated product has a high initial reflectivity, and the reflectivity even after the reflow test The degree of decrease is small. (Examples 1-5) Moreover, the deformation | transformation of the molded article was not seen after the reflow test. (Examples 1-5)
On the other hand, when the inorganic filler was not blended (Comparative Example 1), or a part of the titanium oxide having an aspect ratio of 1 was substituted for the whisker, the same as the total of the whisker amount and the titanium oxide amount in Examples 2, 4 and 5. When the amount of titanium oxide is used, that is, when 30 parts by weight of whisker having an aspect ratio of less than 2 and 50 parts by weight of titanium oxide are used (Comparative Example 2), the amount of whisker is small (Comparative Example 5). The molded product after the reflow test was deformed.
In addition, when a filler with an aspect ratio exceeding 100 (Comparative Examples 3 and 4) or a large amount of whisker (Comparative Example 6), the initial reflectance is low and the reflectance after the reflow test is It was greatly reduced.

Claims (4)

(A) Whisker having an aspect ratio of 2 to 100 with respect to 100 parts by weight of a hydrogenated crystalline cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings A resin composition comprising 10 to 100 parts by weight and (C) 20 to 100 parts of a white pigment. The resin composition according to claim 1, wherein the white pigment is titanium oxide. The molded object which uses the resin composition of Claim 1 or 2. A light reflector comprising the resin composition according to claim 1.