JP2009283283A - Resin composition and reflector of lighting fixture for vehicle consisting of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reflector in which heat resistance and durability under conditions of high temperature and high humidity are maintained while reducing the weight of a vehicle, and which is superior in surface smoothness. <P>SOLUTION: A resin composition is obtained by blending (B) alicyclic structure-containing polymer, (C) crystalline olefin-based polymer having the melting point of 180°C or less, and (D) compatibilizer with (A) crystalline polymer having the melting point of 200°C or more. The reflector of a vehicle lighting fixture is molded using the resin composition in which the weight ratio between (A) crystalline polymer having the melting point of 200°C or more and (B) alicyclic structure-containing polymer is 10/90 to 40/60, (C) crystalline olefin-based polymer having the melting point of 180°C or less is in a range of 0.1 to 5 times with respect to (A) the crystalline polymer having the melting point of 200°C or more, and the content of compatibilizer is 1 to 20 wt.% against the summated amount of (A) the crystalline polymer having the melting point of 200°C or more, (B) the alicyclic structure-containing polymer, and (C) the crystalline olefin-based polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to reflectors (including extension reflectors) incorporated in headlamps, taillights, and other lamps used in, for example, four-wheel automobiles, two-wheel automobiles, and other vehicles. .

In JP-A-11-283423, a resin composition obtained by blending an amorphous alicyclic structure-containing polymer with a crystalline polymer has excellent heat resistance and durability under high-temperature and high-humidity conditions. It is disclosed that it is suitable for providing a reflector for a vehicle lamp.
By the way, in recent years, vehicles are required to be reduced in weight in response to demands for energy saving and fuel efficiency.
In the examples of the above publication, polybutylene terephthalate or polyphenylene sulfide mixed with glass fiber is used as the crystalline polymer.
However, glass fiber has a high specific gravity and does not meet the demand for weight reduction of vehicles. Moreover, weight reduction is achieved by reducing the material of the molded body, and the molded body is required to be thin.
JP-A-11-283423

  As a result of intensive investigations to obtain a reflector that achieves heat resistance and durability under high-temperature and high-humidity conditions while realizing weight reduction of the vehicle, the present inventors have obtained (A) a crystal having a melting point of 200 ° C. or higher. (B) an amorphous alicyclic structure-containing polymer, (C) a crystalline olefin polymer having a melting point of 180 ° C. or lower, and (D) a compatibilizing agent, and the amount of each component When blended in a predetermined ratio, it is possible to obtain a resin composition that not only has excellent heat resistance and durability under high-temperature and high-humidity conditions, but can also provide a reflector with excellent surface smoothness even in a thin molded article. As a result, the present invention has been completed.

Thus, according to the present invention, (A) a crystalline polymer having a melting point of 200 ° C. or higher, (B) an amorphous alicyclic structure-containing polymer, and (C) a crystalline olefin system having a melting point of 180 ° C. or lower. A resin composition comprising a polymer and (D) a compatibilizing agent,
(A) The weight ratio of the crystalline polymer having a melting point of 200 ° C. or higher and the (B) amorphous alicyclic structure-containing polymer is 10/90 to 40/60, and (C) the crystalline olefin The crystalline polymer (A) is in the range of 1/10 to 5 times the crystalline polymer having a melting point of 200 ° C. or higher, and the compatibilizer is (A) a crystal having a melting point of 200 ° C. or higher. Resin composition that is 1 to 20% by weight with respect to the total amount of the crystalline polymer, (B) the amorphous alicyclic structure-containing polymer, and (C) the crystalline olefin polymer having a melting point of 180 ° C. or lower. And a reflector for a vehicle lamp made of the resin composition.

  Since the resin composition of the present invention is also excellent in fluidity at the time of melting, it can be easily molded without causing molding defects even if it is thin and has a large and complicated shape. Therefore, the present invention is preferable when applied to a reflector for a vehicular lamp, which is complicated, large and lightweight. In addition, since the reflector according to the present invention is formed of the resin composition, the undercoating film is used when performing vapor deposition treatment of, for example, aluminum in order to perform mirror treatment on at least one main surface thereof. Even if it is not formed, sufficiently satisfactory surface smoothness can be obtained.

  In the present invention, “vehicle” means a vehicle in a broad sense, such as a two-wheeled vehicle, a three-wheeled vehicle, a four-wheeled vehicle, other vehicles, a railway vehicle, a forklift, and other industrial vehicles. It can be used not only for vehicles but also as a reflector used in commonly used lights.

  In addition, the “vehicle lamp” means a lamp for illumination, identification, or signage mounted on such various vehicles, and is not particularly limited, but includes a headlamp, a tail lamp, Examples include brake lights (stop lamps), direction indicator lights (so-called turn signals), vehicle width lights, and reverse lights.

  In the present invention, the reflector is not limited to the main reflector for collecting or diffusing the light from the light source of the lamp unit to obtain a desired light distribution characteristic, but also the extension reflector and a member connected or coupled to them ( For example, it is used in a concept including a sleeve and a lens holder.

  In the present invention, the “extension reflector” is provided around the lamp in the lamp chamber formed by the body of the vehicle lamp and the cover (or outer lens), and at least one main surface is subjected to mirror surface treatment. A component of a lamp that is used to improve the appearance of the lamp chamber by making it look specular when viewed from the outside, and / or to block light leaking from one lamp to the adjacent lamp. Thus, it is used for the purpose of improving the visibility of display by each lamp. As an extension reflector of an automotive lamp, it is frequently used for a headlamp and a tail lamp, but is not particularly limited in the present invention, and can be applied to other various lamps described above.

  The resin composition of the present invention comprises (A) a crystalline polymer having a melting point of 200 ° C. or higher, (B) an alicyclic structure-containing polymer, (C) a crystalline olefin polymer having a melting point of 180 ° C. or lower, and (D) It is obtained by containing a compatibilizing agent at a predetermined ratio.

<(A) Crystalline polymer having a melting point of 200 ° C. or higher>
The crystalline polymer used in the present invention has a melting point of 200 ° C. or higher, preferably 200 to 350 ° C., more preferably 220 to 300 ° C. By adding a crystalline polymer having a high melting point to the (B) alicyclic structure-containing polymer at a rate described later, the heat distortion temperature of the resulting reflector is increased, and the heat resistance is improved.
Crystalline polymers that can be used in the present invention include polymethylpentene, polysulfone, polybutylene terephthalate (PBT) polyethylene terephthalate (PET), polyphenyl sulfide (PPS), syndiotactic polystyrene, liquid crystal polymer (aromatic Polycyclic condensed polymer).
Among the crystalline polymers, polyethylene terephthalate (PET), polyphenyl sulfide (PPS), and liquid crystal polymer having a melting point of 240 ° C. or higher are preferable, and polyethylene terephthalate (PET) is particularly preferable.

  In the present invention, the crystalline polymer includes not only the crystallized polymer as a whole but also partially crystallized, and the crystallinity thereof is not particularly limited, but is generally 10 to 90. % Range.

<(B) Amorphous alicyclic structure-containing polymer>
The amorphous alicyclic structure-containing polymer used in the present invention is an amorphous resin (resin having no melting point) having an alicyclic structure in the main chain and / or side chain, mechanical strength, From the viewpoint of heat resistance and the like, those containing an alicyclic structure in the main chain are preferred.

  Examples of the alicyclic structure of the polymer include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, etc., the cycloalkane structure. And cycloalkene structures are preferred, and those having a cycloalkane structure are most preferred.

  The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and moldability are highly balanced and suitable.

  The ratio of the repeating unit having an alicyclic structure in the amorphous alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably It is 50% by weight or more, more preferably 70% by weight. If the proportion of the repeating unit having an alicyclic structure in the amorphous alicyclic structure-containing polymer is too small, the heat resistance is inferior. The remainder other than the repeating unit having an alicyclic structure in the amorphous alicyclic structure-containing polymer is not particularly limited and is appropriately selected depending on the purpose of use.

  Specific examples of the amorphous alicyclic structure-containing polymer include (1) norbornene polymer, (2) monocyclic olefin polymer, (3) cyclic conjugated diene polymer, and (4) vinyl. Examples thereof include alicyclic hydrocarbon polymers and hydrides of (1) to (4). Among these, norbornene-based polymers and hydrides thereof are preferable from the viewpoints of heat resistance, mechanical strength, and the like.

(1) Norbornene-based polymer The norbornene-based polymer is obtained by polymerizing a norbornene-based monomer that is a monomer having a norbornene skeleton, and is obtained by ring-opening polymerization or by addition polymerization. Broadly divided into things.

  As ring-opening polymerization, ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization, and hydrogens thereof. And the like. Examples of the polymers obtained by addition polymerization include addition polymers of norbornene monomers and addition polymers of norbornene monomers and other monomers copolymerizable therewith. Among these, a ring-opening polymer hydride of a norbornene-based monomer is preferable from the viewpoint of heat resistance, mechanical strength, and the like.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent in the ring), tricyclo [4.3.0 ^1,6 . 1 ^2,5 ] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name) Methanotetrahydrofluorene: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group, and the norbornene-based monomer may have two or more of these. Specifically, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers are used alone or in combination of two or more.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst. Examples of the ring-opening polymerization catalyst include a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent, or a metal halide or acetylacetone such as titanium, zirconium, tungsten, or molybdenum. A catalyst comprising a compound and an organoaluminum compound can be used.
Examples of the other monomer capable of ring-opening copolymerization with a norbornene monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.
The ring-opening polymer hydride of a norbornene-based monomer is usually obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the above-described ring-opening polymer, and then adding a carbon-carbon unsaturated bond. Can be obtained by hydrogenation.

  An addition polymer of a norbornene monomer, or an addition polymer of a norbornene monomer and another monomer copolymerizable therewith, these monomers are added to a known addition polymerization catalyst, for example, It can be obtained by polymerization using a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound.

Examples of other monomers that can be addition copolymerized with a norbornene monomer include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like. A cycloolefin such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, and derivatives thereof; 1,4-hexadiene, 4-methyl -1,4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene; and the like. Among these, α-olefins are preferable and ethylene is particularly preferable.
These other monomers capable of addition copolymerization with norbornene monomers can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer capable of addition copolymerization, other units capable of addition copolymerization with the structural unit derived from the norbornene monomer in the addition polymer. Appropriately, the ratio with the structural unit derived from the monomer is usually in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5 by weight. Selected.

(2) Monocyclic cyclic olefin polymer As the monocyclic olefin polymer, for example, an addition polymer of a monocyclic olefin monomer such as cyclohexene, cycloheptene, or cyclooctene may be used. it can.
(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and The hydride can be used.
(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinyl cyclohexene and vinyl cyclohexane and their hydrides; , Hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as α-methylstyrene; and the like, and vinyl alicyclic hydrocarbon polymers and vinyl aromatic monomers, and these Any of random copolymers with other monomers copolymerizable with monomers, copolymers such as block copolymers, and hydrides thereof may be used. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.

  The molecular weight of the amorphous alicyclic structure-containing polymer used in the present invention is appropriately selected according to the purpose of use, but gel permeation of cyclohexane solution (toluene solution when the polymer resin does not dissolve) The weight average molecular weight in terms of polystyrene measured by the chromatographic method is 5,000 or more, preferably 5,000 to 500,000, more preferably 8,000 to 200,000, and particularly preferably 10,000 to 100,000. In this range, the mechanical strength and the moldability are highly balanced and suitable.

  The glass transition temperature (Tg) of the amorphous alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C, preferably 100 to 280 ° C, Particularly preferably, when the temperature is in the range of 150 to 250 ° C., the heat resistance and the moldability are highly balanced and suitable.

  Incidentally, these amorphous alicyclic structure-containing polymers can be used alone or in combination of two or more.

  In the present invention, the blending amount of (A) a crystalline polymer having a melting point of 200 ° C. or higher and (B) an amorphous alicyclic structure-containing polymer is determined so that sufficient heat resistance is obtained. The weight ratio of the ring structure-containing polymer to the crystalline polymer having a melting point of 200 ° C. or higher is 10:90 to 40:60, preferably 10:90 to 30:70.

<(C) Crystalline Olefin Polymer Having a Melting Point of 180 ° C. or Less>
The crystalline olefin polymer used in the present invention is an olefin homopolymer or copolymer, and its melting point is 180 ° C. or lower, preferably 100 to 180 ° C., more preferably 140 ° C. to 170 ° C. Is. If the melting point is too high, the moldability will be poor and the surface smoothness will be poor. Conversely, if it is too low, the heat resistance will be low, which is not preferable.
Preferred as the crystalline olefin polymer having a melting point of 180 ° C. or lower is an α-olefin represented by ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 1-pentene and the like. Or a copolymer of α-olefins, a copolymer of the above α-olefins with vinyl ester, acrylic acid or derivatives thereof, organosilicon compounds, or the olefin resin. And graft polymers of various unsaturated monomers. In the copolymer, the proportion of structural units derived from monomers other than olefins is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, based on all structural units.
Among such crystalline olefin polymers, a hydrocarbon resin having a small specific gravity is preferable in that it has excellent surface smoothness even in thin molding and can reduce the weight of the resulting reflector. The specific gravity with respect to water at 4 ° C. is preferably 1.1 or less, more preferably 1.0 or less. Examples of the hydrocarbon resin having a small specific gravity suitably used in the present invention include α-olefin homopolymers such as polyethylene and polypropylene, and polypropylene is particularly preferable.

  In the present invention, the blending amount of (A) a crystalline polymer having a melting point of 200 ° C. or higher and (C) a crystalline olefin polymer having a melting point of 180 ° C. or lower is sufficient in heat resistance and weight reduction. (C) The crystalline olefin polymer having a melting point of 180 ° C. or lower is 1/10 times to 5 times the (A) crystalline polymer having a melting point of 200 ° C. or higher. The range is preferably 1/5 times to 3 times. (C) When the amount of the crystalline olefin polymer having a melting point of 180 ° C. or less is large, the heat resistance tends to be lowered. On the other hand, when the amount is small, the weight reduction is insufficient, which is not preferable.

  In the present invention, the crystalline olefin polymer and the crystalline olefin polymer include not only those in which the whole polymer is crystallized, but also those that are partially crystallized. Although not limited, it is generally in the range of 10 to 90%.

<(D) Compatibilizer>
The compatibilizing agent used in the present invention is a thermoplastic elastomer having a glass transition temperature of 40 ° C. or lower.
Specific examples of the compatibilizer include random or block styrene / butadiene copolymers such as emulsion-polymerized or solution-polymerized styrene / butadiene / rubber and high-styrene rubber, hydrogenated products thereof; isoprene / rubber, and hydrogen Additives; Chloroprene rubbers, hydrogenated products thereof; saturated polyolefin rubbers such as ethylene / propylene copolymers, ethylene / α-olefin copolymers, propylene / α-olefin copolymers; ethylene / propylene / diene copolymers; α-Olefin / diene copolymer, diene copolymer, isobutylene / isoprene copolymer, isobutylene / diene copolymer and other diene polymers, their halides, diene polymers, or hydrogenation of the halides thereof Products, or maleic anhydride, glycidyl methacrylate, Like those modified with carboxymethyl or the like.
Among these, since the surface smoothness of the molded article is good, hydrogenated random or block styrene / butadiene copolymers such as styrene / butadiene / rubber and high styrene rubber, and maleic anhydride and these Modified bodies such as glycidyl methacrylate and epoxy are preferred.
In addition, the compatibilizers can be used alone or in combination of two or more.
The compounding amount of the compatibilizer is (A) a crystalline polymer having a melting point of 200 ° C. or higher, (B) an amorphous alicyclic structure-containing polymer, and (C) a crystalline olefin polymer. The amount is preferably 1 to 20% by weight, more preferably 2 to 15% by weight. When a compatibilizing agent is added in this range, uniform dispersion of the crystalline resin with respect to the alicyclic structure-containing polymer is promoted, and a molded article having good surface smoothness can be obtained.

<Other ingredients>
In the resin composition of the present invention, other various compounding agents (compounding agents usually used in the resin industry) can be used alone or in admixture of two or more as required.

  Other compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials. For example, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, dyes and pigments, etc. And colorants, plasticizers, antistatic agents, fluorescent whitening agents, and the like.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants are particularly preferable. preferable. Antioxidants can be used alone or in combination of two or more. The amount of the antioxidant is appropriately selected within a range not to impair the purpose of the present invention, but is usually 0.001 to 100 parts by weight of the total amount of the crystalline polymer and the alicyclic structure-containing polymer. 5 parts by weight, preferably in the range of 0.01 to 1 part by weight.

Examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, a benzophenone ultraviolet absorber, an acrylate ultraviolet absorber, and a metal complex ultraviolet absorber.
Examples of the light stabilizer include hindered amine light stabilizers.

  Near-infrared absorbers include, for example, cyanine-based near-infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; Complex near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers; Commercially available near infrared absorbers SIR-103, SIR-114, SIR-128,

The dye is not particularly limited as long as it is uniformly dispersed / dissolved in the resin composition according to the present invention. However, since the compatibility with the polymer used in the present invention is excellent, oil-soluble dyes (various C.I. Solvent dyes) are widely used. Specific examples of oil-soluble dyes include Color Index vol. Published by The Society of Diies and Colorists. 3. Various C.I. I. Solvent dyes may be mentioned.
Examples of the pigment include diarylide pigments, azo lake pigments, condensed azo pigments, benzimidazolone pigments, quinacridone pigments, perylene pigments, and anthraquinone pigments.

As plasticizers, phosphate triester plasticizers, phthalate ester plasticizers, fatty acid monobasic ester plasticizers, dihydric alcohol ester plasticizers, oxyacid ester plasticizers, main skeletons are mainly C- Hydrocarbon polymers that are C or C = C structure and liquid at normal temperature can be used. Among these, phosphate triester plasticizers are preferable, and tricresyl phosphate and trixylyl phosphate are particularly preferable.
Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol, fatty acid esters of polyhydric alcohols such as glycerin monostearate and pentaerythritol monostearate, and stearyl alcohol and behenyl alcohol are particularly preferable.

  The compounding amount of these compounding agents is appropriately selected within the range not impairing the object of the present invention, but is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 100 parts by weight of the polymer component. Part range.

  In the present invention, an organic or inorganic filler may be blended in the resin composition according to the present invention. Examples of organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium oxide, calcium carbonate, calcium sulfate, and potassium titanate. , Minerals such as barium sulfate, calcium sulfite, talc, clay, mica, asbestos; fibers such as glass fiber, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber; glass flake, glass beads, silica Examples include calcium acid, montmorillonite, bentonite, graphite, aluminum powder, and molybdenum sulfide.

  These fillers can be added alone or in combination of two or more. The blending ratio of the filler can be appropriately determined according to each function and purpose of use within a range not impairing the object of the present invention, but from the viewpoint of weight reduction, it is preferable not to use an inorganic filler. .

<Method for producing resin composition>
In the present invention, the above-described components are mixed and used as necessary.
The compatibilizing agent and other compounding agents may be independently preliminarily blended with any of the polymers (A) to (C), or the polymers (A) to (C) are mixed. You may mix | blend.
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.

  The reflector for a vehicle lamp according to the present invention is obtained by molding the above resin composition. The molding method may be a conventionally known molding method, such as injection molding, press molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, and rotation. Examples include molding. In view of molding accuracy, injection molding and press molding are preferred. The melting temperature of the resin at the time of molding varies depending on the type of the alicyclic structure-containing polymer, but is usually 100 to 400 ° C, preferably 200 to 350 ° C. The shape of the reflector is not particularly limited, and can be appropriately designed according to the vehicle to be applied. Usually, a reflecting film layer is formed on one surface of a reflector-shaped molded product obtained by molding the above resin composition and used as a reflector.

<Formation of reflective film layer>
When the reflective film layer is formed on the reflector using a highly reflective metal such as aluminum, nickel, gold or the like, the method is not particularly limited and may follow a known method, for example, a normal vapor deposition method, That is, vacuum deposition, sputtering, ion plating, etc. are mentioned.

  The conditions for forming the reflective film are not particularly limited. For example, when the reflective film is formed by vacuum deposition of aluminum, the following conditions are preferable. That is, the degree of vacuum is in the range of 0.1 to 1,000 Pa, and preferably in the range of 1 to 100 Pa. When in this range, an aluminum film having fine texture and excellent adhesive strength can be deposited. The film may be formed while the molded product is heated, and it is preferable that the surface temperature of the molded product is in the range of room temperature to 100 ° C. to increase the adhesive force. The thickness of the reflective film is 5 to 10,000 nm, preferably 10 to 2,000 nm. If the film thickness is excessively thin, the reflectivity is too low, and sufficient reflectivity as a reflector cannot be obtained. If it is too thick, the reflectance does not increase, the film formation time becomes longer, and the productivity is lowered. When the film thickness is in the above range, a reflective film having high productivity and high reflectivity can be obtained, which is preferable.

  In order to improve the adhesion between the reflector-shaped molded product obtained by molding the above resin composition and the above-described reflective film, the reflector surface may be subjected to modification treatment and / or primer treatment. Examples of the surface modification treatment include energy ray irradiation treatment such as corona discharge treatment, plasma treatment, electron beam irradiation treatment and ultraviolet ray irradiation treatment, and chemical treatment in contact with an oxidizing agent aqueous solution such as potassium dichromate solution.

  If necessary, a protective layer may be provided so that the reflector-shaped molded product obtained by molding the resin composition and the reflective film are not scratched or stained. The method for forming the protective layer is not particularly limited. For example, there is a method in which an ultraviolet curable resin or a thermosetting resin is applied to the surface of a molded article by a method such as spin coating, spray coating, dipping, or flow coating, and then cured.

  Further, the reflector of the present invention can be applied to a vehicle lamp such as a rear lamp in addition to a headlamp.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples.
In the following examples and comparative examples, “part” or “%” is based on weight unless otherwise specified.

The measuring methods for various physical properties are as follows.
(1) The hydrogenation rate was measured by ¹ H-NMR.
(2) The glass transition temperature was measured based on JIS K7121.
(3) Specific gravity was measured based on ASTM D 792 for a molded plate on which aluminum deposition was not performed.
(4) The surface smoothness of the test piece is “◯” when the maximum height Rmax value measured using an ultra-deep shape measuring microscope: VK-8500 (manufactured by Keyence Corporation) is 10 μm or less, and 5 μm or more. Was judged as “×”.
(5) As for the appearance of the test piece, the presence or absence of sink marks, warpage, silver, burns and coloring was visually observed, and those having no defects were judged as “◯”, and those having defects were judged as “X”.
(6) In the heat resistance test, the test piece was placed on a horizontal plate and heated and held in a gear oven at 150 ° C. for 72 hours, and then the appearance change of the test piece was tested. As for the appearance change, “o” indicates that the appearance of the deposited film did not change compared to before the heat resistance test, and “x” indicates that the mirror surface fogging, poor reflection, film blistering, or discoloration occurred.

[Reference Example 1]
Bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “NB”) (120 kg) was added to a reaction vessel charged with 258 liters of cyclohexane at room temperature under a nitrogen stream and stirred for 5 minutes. . Further, triisobutylaluminum was added so that the concentration in the system was 1.0 ml / liter. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. The internal temperature of the autoclave was kept at 70 ° C. and pressurized with ethylene so that the internal pressure was 6 kg / cm ^{2 as a} gauge pressure. After stirring for 10 minutes, by adding 0.4 liter of a toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance, a copolymerization reaction of ethylene and NB Was started. The catalyst concentration at this time is 0.018 mmol / liter for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and 8.0 mmol / liter for methylalumoxane with respect to the entire system.

During the polymerization, ethylene was continuously fed into the system to maintain the temperature at 70 ° C. and the internal pressure at 6 kg / cm ² as a gauge pressure. After 60 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out, and then contacted with an aqueous solution obtained by adding 5 liters of concentrated hydrochloric acid to 1 m ^{3 of} water at a ratio of 1: 1 with vigorous stirring, and the catalyst residue was transferred to the aqueous phase. After leaving this contact liquid mixture, the aqueous phase was separated and removed, and further washed with water twice to purify and separate the polymerization liquid phase.

Next, the purified and separated polymer solution was brought into contact with 3 times the amount of acetone under strong stirring to precipitate a copolymer, and then the solid part (copolymer) was collected by filtration and sufficiently washed with acetone. Further, in order to extract unreacted monomers present in the polymer, this solid part was put into acetone so as to be 40 kg / m ^3, and then an extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow to obtain an ethylene / NB copolymer (A).

  As described above, Tg of the obtained ethylene / NB copolymer (alicyclic structure-containing polymer A) was 137 ° C., and the NB unit content was 51 mol%.

[Reference Example 2]
NB of Reference Example 1 was changed to tetracyclo [4.4.0.1 ^2,5 . The polymerization reaction was carried out in the same manner as in Reference Example 1 except that it was changed to ^{17, 10} ] dodec-3-ene (TCD). The obtained ethylene / TCD copolymer (alicyclic structure-containing polymer B) had a Tg of 144 ° C. and a TCD unit content of 32 mol%.

[Reference Example 3]
<Ring-opening polymerization>
To a reactor substituted with nitrogen, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter referred to as “MTF”) and tricyclo [4.3.0.1 ^2,5 ] dec-3- Ene (hereinafter referred to as “DCP”) and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 7 parts of a mixture of dodec-3-ene (hereinafter referred to as “TCD”) (weight ratio 50/10/40) (1% with respect to the total amount of monomers used for polymerization) and 1600 parts of cyclohexane were added. , 0.57 part of tri-i-butylaluminum and 0.21 part of isobutyl alcohol, 0.85 part of diisopropyl ether as a reaction regulator and 4.86 parts of 1-hexene as a molecular weight regulator. To this, 24.3 parts of a 0.65% tungsten hexachloride solution dissolved in cyclohexane was added and stirred at 55 ° C. for 10 minutes. Subsequently, while maintaining the reaction system at 55 ° C., 48.9 parts of a 0.65% tungsten hexachloride solution in which 693 parts of a mixture of MTF, DCP, and TCD (weight ratio 50/10/40) were dissolved in cyclohexane. Were continuously dropped into the system over 150 minutes. Thereafter, the reaction was continued for 30 minutes to complete the polymerization.
After completion of the polymerization, the polymerization conversion rate of the monomer measured by gas chromatography was 100% at the end of the polymerization.
<Hydrogenation>
The obtained ring-opening polymerization reaction liquid was transferred to a pressure-resistant hydrogenation reactor, and diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Co., Ltd., product name “T8400RL”, nickel support rate 57%) 1.4 parts and cyclohexane 167 Part was added and reacted at 180 ° C. and hydrogen pressure 4.6 MPa for 6 hours. The reaction solution was filtered under pressure with Radiolite # 500 as a filter bed at a pressure of 0.25 MPa (Ishikawajima-Harima Heavy Industries Co., Ltd., product name “Funda filter”) to remove the hydrogenation catalyst, and a colorless transparent solution was obtained. Obtained. Subsequently, 0.5 parts of antioxidant per 100 parts of the hydrogenated product: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, The product name “Irganox 1010”) was added to the resulting solution and dissolved. Next, it is sequentially filtered through a Zeta Plus filter 30H (Cuneau filter, pore size 0.5 to 1 μm), and further filtered through another metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Corp.). Minutes removed. The hydrogen conversion rate of the ring-opening polymer hydrogenated product was 99.9%.
Next, using a cylindrical concentrator / dryer (manufactured by Hitachi, Ltd.), at a temperature of 270 ° C. and a pressure of 1 kPa or less, cyclohexane and other volatile components as solvents are removed from the solution and directly connected to a concentrator. The molten die was extruded into a strand in a molten state, and after cooling, a hydrogenated ring-opening polymer (alicyclic structure-containing polymer C) was obtained. Tg was 154 ° C.
In addition, since the polymerization conversion rate during the synthesis of the ring-opening polymer is 100% and the hydrogen conversion rate is also a high level of 99.9%, the structural unit derived from MTF in the hydrogenated ring-opening polymer ( MTF units), DCP-derived structural units (DCP units), and TCD-derived structural units (TCD units) are estimated to be equal to the amount of monomers used in the production of the ring-opening polymer.

[Example 1]
Antioxidant (manufactured by Ciba Geigy; Irganox 1010, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4 ′) was added to 65 parts by weight of the ethylene / NB copolymer prepared in Reference Example 1. -Hydroxyphenyl) propionate] methane) 0.1 part by weight, compatibilizer (product name “Toughtech M1911” manufactured by Asahi Kasei Chemicals Corporation) 15.75 parts, polyethylene terephthalate (melting point 255 ° C., specific gravity 1.40) 35 parts by weight 5 parts by weight of polypropylene (melting point: 160 ° C., specific gravity: 0.90, melt mass flow rate at a test temperature of 230 ° C .: 0.3 g / 10 min) was kneaded with a biaxial kneader to be pelletized. This pellet was injection-molded at a resin temperature of 280 ° C. and a mold temperature of 120 ° C. using a mold having a thickness of 0.5 mm, a length of 200 mm, and a width of 100 mm. Furthermore, an aluminum reflective film having a thickness of 400 nm was formed on the mirror surface side of the test piece by a vacuum vapor deposition method to prepare a test piece.

[Examples 2-3, Comparative Examples 1-7]
Except having changed the compounding quantity of (A)-(D) component, it pelletized like Example 1, the injection molding and vapor deposition of the aluminum film were performed, and the test piece was created.

  Table 1 shows the results of the smoothness and appearance of the test article surface using the test pieces molded in Examples 1 to 3 and Comparative Examples 1 to 7.

From this result, the following can be understood.
A molded body using the resin composition of the present invention has high heat resistance and excellent surface smoothness (Example 1-3).
On the other hand, when (A) the blending ratio of the crystalline polymer having a melting point of 200 ° C. or higher is low, the heat resistance is low (Comparative Example 1), and when the blending ratio is high, the surface smoothness is poor. (Comparative example 2).
(C) When the blending ratio of the crystalline olefin having a melting point of 180 ° C. or lower is high, the heat resistance is low (Comparative Example 4), and when the blending ratio is low, the surface smoothness is inferior. (Comparative Example 3).
(D) When the compounding quantity of the compatibilizing agent is large, it was found that heat resistance is inferior (Comparative Example 6), and when it is small, heat resistance and surface smoothness are inferior (Comparative Example 5).

Claims (2)

(A) a crystalline polymer having a melting point of 200 ° C. or higher, (B) an amorphous alicyclic structure-containing polymer, (C) a crystalline olefin polymer having a melting point of 180 ° C. or lower, (D ) A resin composition comprising a compatibilizing agent,
(A) The weight ratio of the crystalline polymer having a melting point of 200 ° C. or higher and the (B) amorphous alicyclic structure-containing polymer is 10/90 to 40/60, and (C) 180 ° C. or lower. The crystalline olefin polymer having a melting point is (A) in the range of 1/10 to 5 times the crystalline polymer having a melting point of 200 ° C. or higher, and the compatibilizer is the above (A) 200. With respect to the total amount of the crystalline polymer having a melting point of ℃ or higher, (B) the amorphous alicyclic structure-containing polymer, and (C) the crystalline olefin polymer having a melting point of 180 ° C. or lower, 1 to A resin composition which is 20% by weight.   The reflector of the vehicle lamp which consists of a resin composition of Claim 1.