JPH11297102A - Lighting fixture reflector for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To hardly generate breakage, enhance surface smoothness and light reflecting characteristics, and easily form a thin, large reflector by with a resin composition prepared by mixing a soft polymer having a glass transition temperature of the specific value or less to a polymer resin containing alicyclic structure. SOLUTION: As a polymer resin containing alicyclic structure, the resin having the alicyclic structure in a principal chain and/or the side chain is used, as a soft polymer to be mixed, a soft polymer component which develops mechanical strength and flexibility by mixing to the polymer resin containing alicyclic structure is used. Concretely, a soft polymer having a glass transition temperature of 30 deg.C or less is used. One example is a soft resin having an amorphous domain having rubber-like elasticity which easily deforms at room temperature under fixed stress and recovers to the original state when the stress is removed. Concretely, a norbornane family polymer, a single cycle cyclic olefin polymer, a cycle conjugated diene polymer, or the like is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reflector (including an extension reflector) incorporated in a headlight, a taillight, and other lamps used for, for example, four-wheeled vehicles, two-wheeled vehicles, and other vehicles. The present invention relates to a reflector that is unlikely to be cracked due to a stop.

[0002]

2. Description of the Related Art A vehicular lamp mainly comprises a lamp body formed in a container shape having a front opening, a lamp unit having a light source (lamp) attached to the lamp body, and a lamp unit attached to a front opening of the lamp body. Lamp cover (or outer lens).

A lamp unit is provided with a reflector for condensing or diffusing light from a light source to obtain a desired light distribution characteristic, but a large space is provided between the lamp unit and a lamp body. Therefore, there is a problem in appearance that when the lamp is observed from the outside, the lamp can be seen through to the aiming mechanism behind.

[0004] For this reason, in order to make the entire lighting room look like a mirror surface and improve the appearance, an extension reflector (Extension R) which has been subjected to mirror finishing is provided in a range from around the reflector of the lamp unit to the front opening of the lamp body.
eflector).

In combination lamps such as a front combination lamp in which a headlamp and a direction indicator lamp are integrated, and a rear combination lamp in which a stop lamp and a direction indicator lamp are integrated, light from one lamp is adjacent. An extension reflector is provided which also has a function of shielding the lamp from leaking to the lamp side.

[0006] Such reflectors (including extension reflectors) are designed to increase the productivity and reduce the weight, and to sufficiently cope with complicated shapes, so as to be able to sufficiently cope with complicated shapes, such as addition copolymers of norbornene and ethylene. The use of a plastic resin has been studied. For example, German Patent Publication No. 19540414 discloses a reflector made of a thermoplastic resin, such as an addition copolymer of norbornene and ethylene, which is not used for vehicles.

[0007]

By the way, the reflector of the vehicular lamp including the extension reflector is often attached to the vehicular lamp with screws or bolts.

However, if the reflector of such a vehicular lamp is made of a thermoplastic resin such as an addition copolymer of norbornene and ethylene as described above, the reflector may be broken when screws are fixed. , There was a risk of cracking.

Further, since the above addition copolymer of norbornene and ethylene has low impact strength, if it is used as a reflector of a vehicular lamp, there is a possibility that cracks may occur during transportation, assembly, or after mounting on a vehicle. Was.

When the reflector is made of resin, it is necessary to form a reflection surface on the surface by vapor deposition of aluminum or the like. To suppress scattering of reflected light as much as possible,
A substrate having excellent surface smoothness is desired. Further, it is desired that the reflectivity of the resin-made reflector having the reflecting surface is also good.

The present invention has been made in view of the above-mentioned problems of the prior art, and it is difficult for cracks and the like to occur, easy to screw in, and excellent in surface smoothness and light reflection characteristics. It is another object of the present invention to provide a reflector for a vehicular lamp that can be easily formed into a thin and large one.

[0012]

In order to achieve the above-mentioned object, a reflector according to the present invention is provided in a reflector of a vehicular lamp provided in the vehicular lamp, wherein the alicyclic structure-containing polymer resin has a glass transition temperature. Comprises a resin composition containing a soft polymer having a temperature of 30 ° C. or lower.

The alicyclic structure-containing polymer resin according to the present invention has excellent heat resistance, can be molded without decomposition even at high temperatures, and has excellent fluidity upon melting, so that it is thin, large, and complicated. Even with a simple shape, molding can be easily performed without causing molding failure. In addition, in order to perform a mirror surface treatment on at least one principal surface thereof, it is possible to obtain a sufficiently satisfactory surface smoothness without forming an undercoating film when performing an evaporation treatment of, for example, aluminum.

Further, the alicyclic structure-containing polymer resin constituting the reflector according to the present invention has a glass transition temperature of 3
Since a soft polymer having a temperature of 0 ° C. or less is blended, no cracks or cracks occur even when screws are used during assembly. Therefore, it is preferable to be applied to a reflector of a vehicular lamp for which a complicated, large, and lightweight vehicle is desired.

[0015] In the reflector present invention, the term "vehicle", the two-wheeled motor vehicles, three-wheeled motor vehicles, four-wheeled motor vehicles and other motor vehicles, railway vehicles, a forklift for the vehicle and so on other industries, meaning the broad sense of the vehicle.
The invention can be used not only for vehicles but also as a reflector used in commonly used lights.

The term "vehicle lamp" means a lamp for lighting, identification, or signage mounted on such various vehicles, and is not particularly limited, but includes a headlight (headlamp), a taillight (taillight). Tail lamps, brake lights (stop lamps), direction indicators (so-called turn signals), vehicle width lights, reverse lights, and the like are applicable.

In the present invention, the reflector is not limited to the main reflector for condensing or diffusing light from the light source of the lamp unit to obtain a desired light distribution characteristic, but is also an extension reflector and connected or connected thereto. Used in a concept that also includes members such as sleeves and lens holders.

In the present invention, an "extension reflector" is provided around a lamp in a lamp room formed by a body of a vehicle lamp and a cover (or an outer lens), and at least one principal surface is mirror-finished. The lamp is a component part of the lamp, and is used for the purpose of improving the appearance by showing the entire lamp chamber to a mirror color when the lamp is observed from the outside, and / or leaking from one lamp to an adjacent lamp. It is used for the purpose of blocking light and increasing the visibility of display by each lamp. Extension reflectors for automotive lighting are often used for headlights and taillights, but are not particularly limited in the present invention, and can be applied to the various other lightings described above.

The alicyclic structure-containing polymer resin The alicyclic structure-containing polymer resin used in the present invention has an alicyclic structure in a main chain and / or a side chain.
From the viewpoints of mechanical strength and heat resistance, 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 viewpoints of mechanical strength, heat resistance and the like, A cycloalkane structure and a cycloalkene structure are preferred, and among them, 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.
When the number is in the range of 5 pieces, more preferably 5 to 15, the properties of mechanical strength, heat resistance and moldability are highly balanced and suitable.

The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin used in the present invention may be appropriately selected according to the purpose of use, but is usually at least 30% by weight. Preferably at least 50% by weight, more preferably 7% by weight.
0% by weight. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin is too small, the heat resistance is poor, which is not preferable. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin is not particularly limited, and is appropriately selected depending on the purpose of use.

Specific examples of the polymer resin having an alicyclic structure include (1) a norbornene-based polymer, (2) a monocyclic olefin-based polymer, and (3) a cyclic conjugated diene-based polymer. Polymers, (4) vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof.

Among these, preferred are norbornene-based polymers and hydrogenated products thereof, cyclic conjugated diene-based polymers and hydrogenated products thereof, and more preferred are norbornene-based polymers and hydrogenated products thereof.

(1) Norbornene-based polymer The norbornene-based polymer is not particularly limited. For example, JP-A-3-14882 and JP-A-3-122.
137 is a known resin disclosed in, for example,
Specific examples include ring-opening polymers of norbornene-based monomers and hydrogenated products thereof, addition polymers of norbornene-based monomers, and addition-type polymers of norbornene-based monomers and vinyl compounds.

Among them, hydrogenated ring-opening polymer of norbornene-based monomer, addition-type polymer of norbornene-based monomer, and copolymer with norbornene-based monomer can be used in order to highly balance heat resistance and dielectric properties. An addition type polymer of a vinyl compound is preferred, and a hydrogenated open polymer of a norbornene-based monomer is particularly preferred.

Examples of the norbornene monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.2.1] hepta-2.
-Ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1]
Hept-2-ene, 5-butyl-bicyclo [2.2.
1] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-octyl-
Bicyclo [2.2.1] hepta-2-ene, 5-octadecyl-bicyclo [2.2.1] hepta-2-ene, 5
-Ethylidene-bicyclo [2.2.1] hepta-2-ene, 5-methylidene-bicyclo [2.2.1] hepta-
2-ene, 5-vinyl-bicyclo [2.2.1] hepta-2-ene, 5-propenyl-bicyclo [2.2.1]
Hept-2-ene, 5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Methoxycarbonyl-bicyclo [2.2.1] hept-2-ene; 5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.
2.1] Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-
Methyl octanate, bicyclo [2.2.1] hept-
2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5,6-di (hydroxymethyl) bicyclo [2.2.
1] Hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene;
5-Cyanobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6
-Dicarboxylic acid imide; tricyclo [4.3.1 ^2,5 .
0 ^1,6 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] dec-3-ene; tricyclo [4.4.1 ^2,5 . 0 ^1,6 ]
Undeca-3,7-diene or tricyclo [4.
4.1 ^2,5 . [ ^1,6 ] undeca-3,8-diene or a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene), ie, tricyclo [4.4.
^12.5 . 0 ^1,6 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5
-Cyclohexyl-bicyclo [2.2.1] hept-2
-Ene, 5-cyclohexenylbicyclo [2.2.1]
Hept-2-ene, 5-phenyl-bicyclo [2.2.
1] hept-2-ene; tetracyclo [4.4.1
^2,5 . ^17,10 . 0] - dodeca-3-ene (also simply referred to as tetracyclododecene), 8-methyl tetracyclo [4.4.1 ^{2,5. 17,10} . 0] -dodec-3-ene,
8-ethyltetracyclo [4.4.1 ^2,5 . ^17,10 .
0] -dodec-3-ene, 8-methylidenetetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-ethylidenetetracyclo [4.4.1 ^2,5 .
1 ^{7, 10.} 0] -dodec-3-ene, 8-vinyltetracyclo [[4.4.1 ^2,5 . ^17,10 . 0] -dodeca-3-
Ene, 8-propenyl-tetracyclo [4.4.
1 ^{2, 5. 17,10} . 0] -dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . ^17,10 .
0] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0]
-Dodeca-3-ene, 8-hydroxymethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-carboxytetracyclo [4.4.1 ^2,5 . 1
^7,10 . 0] -dodec-3-ene; 8-cyclopentyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-cyclohexenyl-tetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.1 ^2,5 .
^17,10 . 0] -dodec-3-ene; tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] trideca-2,
4,6,11-tetraene (1,4-methano-1,4,4)
4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^11,14 . 0 ^1,10 . 0 ^3,8] tetradec -3,5,7,12- tetraene (1,4-methano -1,4,4a, also referred to as a 5,10,10a- hexahydrophthalic anthracene), pentacyclo [6.5.1 ^{1 , 8} .
1 ^{3, 6.} 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.1 ^3,6. 1 ^10,13 .
0 ^1,9 . 0 ^2,7 ] pentadeca-4,11-diene; cyclopentadiene tetramer; and the like. These norbornene monomers may be used alone or in combination of two or more.

The polymerization method and the hydrogenation method of the norbornene monomer or the vinyl compound which can be copolymerized with the norbornene monomer are not particularly limited, and can be carried out according to known methods.

Examples of the copolymerizable vinyl compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,
4-dimethyl-1-hexene, 4,4-dimethyl-1-
Pentene, 4-ethyl-1-hexene, 3-ethyl-1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, ethylene or α-olefin having 2 to 20 carbon atoms; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a,
5,6,7a-tetrahydro-4,7-methano-1H-
Cycloolefins such as indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

The ring-opening (co) polymer of a norbornene-based monomer can be obtained by using a norbornene-based monomer as a ring-opening polymerization catalyst in ruthenium, rhodium, palladium, osmium,
Iridium, a metal halide such as platinum, a nitrate or acetylacetone compound and a catalyst system comprising a reducing agent, or titanium, vanadium, zirconium, tungsten, a metal halide such as molybdenum or an acetylacetone compound, and an organic aluminum compound Using a catalyst system consisting of: in a solvent or without solvent, usually at a polymerization temperature of -50 ° C to 100 ° C, 0 to 50 kg / c
It can be obtained by ring-opening (co) polymerization at a polymerization pressure of m ² .

The catalyst system includes molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride,
By adding a third component such as an ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, or other Lewis acid, the polymerization activity and the selectivity of ring-opening polymerization can be increased.

The hydrogenated norbornene-based polymer can be obtained by a conventional method in which a ring-opened (co) polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst.

The addition copolymer of a norbornene-based monomer and a vinyl-based compound can be prepared, for example, by adding a monomer component in a solvent or without a solvent in the presence of a catalyst system comprising a titanium, zirconium, or vanadium compound and an organoaluminum compound. At a polymerization temperature of -50 ° C to 100 ° C,
It can be obtained by a method of copolymerizing at a polymerization pressure of ５０50 kg / cm ² .

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cyclic olefin polymer include, for example, cyclolohexene, cycloheptene, cyclooctene and the like disclosed in JP-A-64-66216. An addition polymer of a monocyclic cyclic olefin monomer can be used.

(3) Cyclic conjugated diene-based polymer The cyclic conjugated diene-based polymer is described in, for example,
The cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-A-136057 and JP-A-7-258318 are used as 1,2- or 1,2-
4-Polymerized polymers and hydrogenated products thereof can be used.

(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59,989. Polymers of vinyl alicyclic hydrocarbon monomers and hydrogenated products thereof, JP-A-63-43910, JP-A-64-1,706
For example, a hydrogenated product of an aromatic ring portion of a polymer of a vinyl aromatic monomer such as styrene or α-methylstyrene disclosed in Japanese Patent Application Laid-Open Publication No. H10-15095 can be used.

The molecular weight of the alicyclic structure-containing polymer resin used in the present invention is appropriately selected according to the purpose of use.
Weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of cyclohexane solution (toluene solution if polymer resin does not dissolve)
5,000 or more, preferably 5,000 to 500,00
When it is in the range of 0, more preferably in the range of 8,000 to 200,000, particularly preferably in the range of 10,000 to 100,000, the mechanical strength and the formability are highly balanced and suitable.

The glass transition temperature (Tg) of the alicyclic structure-containing polymer resin 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. ° C, particularly preferably 150-250 ° C
When it is within the range, heat resistance and moldability are highly balanced and suitable.

JIS of the alicyclic structure-containing polymer resin used in the present invention at 280 ° C. under a load of 2.16 kgf
The melt flow rate measured by K6719 may be appropriately selected depending on the purpose of use.
g / 10 min. , Preferably 10 to 50 g / 10 mi
n. Is suitable. If the melt flow rate is too low, the temperature at which the molding material is heated at the time of molding becomes higher, so that processing may be difficult. If it is too high, molding defects such as burrs may occur at the time of molding.

By the way, these alicyclic structure-containing polymer resins can be used alone or in combination of two or more.

Soft Polymer In the present invention, the soft polymer to be incorporated in the alicyclic structure-containing polymer resin constituting the reflector may be, when incorporated into the alicyclic structure-containing polymer resin, mechanical strength and flexibility. There is no particular limitation as long as it is a soft polymer component capable of imparting properties, but specifically refers to a polymer having a glass transition temperature of 30 ° C. or less. For example, it is easily deformed by a constant stress at room temperature. A soft polymer having an amorphous (amorphous) domain having a property of recovering the original shape when the stress is removed, that is, having a rubber-like elasticity. Even in the case of a polymer having a plurality of Tg or a polymer having both Tg and melting point (Tm), if the lowest Tg is 30 ° C. or lower, it is included in the soft polymer.

Examples of such a soft polymer include (a) an olefin-based soft polymer mainly composed of α-olefins such as ethylene and propylene, (b) an isobutylene-based soft polymer mainly composed of isobutylene, and (c) butadiene. , A diene-based soft polymer mainly composed of a conjugated diene such as isoprene, (d) a cyclic olefin-based ring-opened polymer mainly composed of a cyclic olefin such as norbornene and cyclopentene, and (e) a soft weight having a silicon-oxygen bond as a skeleton. Coalescing (organic polysiloxane), (f) α, β-
A soft polymer mainly composed of unsaturated acids and their derivatives,
(G) a soft polymer mainly composed of an unsaturated alcohol and an amine or an acyl derivative or acetal thereof,
(H) a polymer of an epoxy compound; and (i) other soft polymers.

Specific examples of these soft polymers include, for example, (a) liquid polyethylene, atactic polypropylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene and 1-octene. A homopolymer such as decene; an ethylene / α-olefin copolymer,
Copolymers such as propylene / α-olefin copolymer, ethylene / propylene / diene copolymer (EPDM), ethylene / cyclic olefin copolymer and ethylene / propylene / styrene copolymer are exemplified. Examples of (b) include polyisobutylene, isobutylene / isoprene rubber, and isobutylene / styrene copolymer. (C) is a homopolymer of a conjugated diene such as polybutadiene or polyisoprene; hydrogen of butadiene / styrene random copolymer, isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, or acrylonitrile / butadiene copolymer Additives, random copolymers of conjugated dienes such as acrylonitrile / butadiene / styrene copolymers; butadiene / styrene / block copolymers, styrene / butadiene / styrene / block copolymers, isoprene / styrene / block copolymers, Examples include block copolymers of conjugated dienes such as styrene / isoprene / styrene / block copolymers and aromatic vinyl hydrocarbons, and hydrogenated products of these block copolymers. Examples of (d) include norbornene-based monomers such as norbornene, vinylnorbornene, and ethylidene norbornene, and metathesis ring-opened polymers of monocyclic olefins such as cyclobutene, cyclopentene, and cyclooctene, and hydrogenated products thereof. Examples of (e) include silicone rubbers such as dimethylpolysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane. As (f), a homopolymer of an acrylic monomer such as polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, or polyacrylonitrile; a mixture of an acrylic monomer such as a butyl acrylate / styrene copolymer and another monomer And copolymers. Examples of (g) include homopolymers of (esterified) unsaturated alcohols such as polyvinyl alcohol, polyvinyl acetate, polyvinyl polystearate, polyvinyl benzoate, and polyvinyl maleate; and vinyl acetate-styrene copolymers. Esterification) Copolymers of unsaturated alcohols with other monomers. Examples of (h) include polyethylene oxide, polypropylene oxide, epichlorohydrin rubber, and the like. (I) includes natural rubber, polypeptides, proteins, and the like.

These soft polymers may have a crosslinked structure or may have a functional group introduced by modification.

In the present invention, from the viewpoint of preventing cracks caused by screwing, among the above soft polymers, (a)
(B) and (c) the soft polymers are particularly excellent in rubber elasticity,
It is preferable because of excellent mechanical strength and flexibility. Above all, soft polymers corresponding to these (a), (b) and (c), and further having an aromatic vinyl monomer in a polymer repeating unit, are heat-resistant, phase-resistant. Specific examples of such a soft polymer are more preferable because of its excellent solubility, and examples thereof include a random copolymer such as an ethylene-propylene-styrene copolymer and an isobutylene-styrene copolymer, and hydrogenation of the copolymer. Thing; butadiene
Styrene block copolymer, styrene butadiene
Block copolymers such as styrene-block copolymer, isoprene-styrene-block copolymer, styrene-isoprene-styrene-block copolymer, and hydrogenated products of the copolymer; Further, among these, from the viewpoint of heat resistance and weather resistance, a polymer containing no or only a small amount of a double bond in the main chain (a hydrogenated product of the above polymer) is most preferable.

In the present invention, the blending amount of the soft polymer in the alicyclic structure-containing polymer resin is determined so that cracks are not easily generated by screwing. The weight ratio with the soft polymer is preferably 5:95 to
95: 5, more preferably 10:90 to 90:10.

Filler In the reflector of the present invention, by further adding a filler in addition to the above soft polymer, the strength against screw cracking can be further improved.

The filler that can be used in the present invention is not particularly limited as long as it is generally used in the polymer industry, but those used as reinforcing agents, reinforcing agents and the like are preferable. . Specific examples of such a filler include an organic filler and an inorganic filler.

The inorganic filler is not particularly limited,
For example, calcium carbonate powder such as light calcium carbonate, heavy or finely divided calcium, and special calcium-based filler; clay (aluminum silicate powder) such as nepheline syenite fine powder, calcined clay, and silane-modified clay; talc;
Silica (silicon dioxide) powders such as fused silica and crystalline silica; silicate-containing compounds such as diatomaceous earth and silica sand; pulverized powder of natural minerals such as pumice powder, pumice balloon, slate powder and mica powder; asbestos (asbestos) Alumina-containing compounds such as alumina, alumina colloid (alumina sol), alumina white, and aluminum sulfate;
Minerals such as barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, and graphite (graphite); glass-based compounds such as glass fiber, glass beads, glass flakes and foamed glass beads; fly ash spheres, volcanic glass hollow bodies, synthetic inorganic hollows Body, single crystal potassium titanate, carbon fiber, carbon hollow sphere, anthracite powder, artificial cryolite (cryolite), titanium oxide, magnesium oxide, basic magnesium carbonate, dowamite, potassium titanate,
Examples include calcium sulfite, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber and the like.

Among these inorganic fillers, fibrous fillers having high elasticity, high strength and excellent reinforcing properties are preferable, and specific examples thereof include glass fibers (glass fibers), carbon fibers (carbon fibers), and boron fibers. , Silicon carbide fibers, single crystal potassium titanate and the like.

Examples of the organic filler include polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, fluorine fiber, ebonite powder, thermosetting resin hollow sphere, thermosetting resin filler, epoxy resin filler, silicone filler, Saran hollow spheres, shellac, wood flour, cork powder, polyvinyl alcohol fiber, cellulose powder, wood pulp, and the like.

Among these, epoxy resin fillers, silicone fillers, thermosetting resin hollow spheres, fluorine fibers, and the like are preferable because of their excellent heat resistance, mechanical properties, and the like, and thermosetting resins having a small linear expansion coefficient. Fillers are more preferred.

These fillers are used for the purpose of improving wettability and adhesion between the alicyclic structure-containing polymer resin and the filler and improving the adhesion between the silanes such as epoxysilane, aminosilane, titanate, aluminum chelate and zircoaluminate. Surface treatment may be performed with a coupling agent, silicon oil, or the like.

These fillers may be used alone or in combination of two or more. The amount of these fillers is usually 1 to 300 parts by weight, preferably 2 to 2 parts by weight, per 100 parts by weight of the alicyclic structure polymer resin.
When the amount is 00 parts by weight, most preferably 5 to 100 parts by weight, the strength of the reflector against screw cracks and the surface smoothness are highly balanced and suitable.

Other Components In the reflector of the present invention, if necessary, the above-mentioned alicyclic structure-containing polymer resin may contain other polymers, other compounding agents (compounding agents generally used in the resin industry), The agents can be used alone or in combination of two or more.

The other compounding agents are not particularly limited as long as they are commonly used in thermoplastic resin materials, and include, for example, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, dyes And colorants such as pigments and the like, compounding agents such as lubricants, plasticizers, antistatic agents and optical brighteners.

Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant and a sulfur-based antioxidant. Among these, a phenol-based antioxidant is preferable, and an alkyl-substituted phenol-based antioxidant is preferable. Agents are particularly preferred.

As the phenolic antioxidant, conventionally known phenolic antioxidants can be used. For example, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-
t-Amyl-6- (1- (3,5-di-t-amyl-2)
-Hydroxyphenyl) ethyl) phenyl acrylate and the like.
Acrylate compounds described in 68643;
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-t-butylphenol),
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenylpropionate) methane [namely, pentaerythrimethyl-tetrakis (3- (3,5 -Di-t
-Butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3- (3-t
Alkyl-substituted phenolic compounds such as -butyl-4-hydroxy-5-methylphenyl) propionate);
6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1,3,5-triazine, 2- Octylthio-4,6-bis- (3,5-di-
triazine group-containing phenolic compounds such as t-butyl-4-oxyanilino) -1,3,5-triazine;

The phosphorus-based antioxidant is not particularly limited as long as it is generally used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris ( Nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, 10- (3,5-di-
t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-
Monophosphite compounds such as 10-oxide;
4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,
Diphosphite compounds such as 4 ′ isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); Among these, monophosphite compounds are preferred, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferred.

Examples of the sulfur-based antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl
3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,2
4,8,10-tetraoxaspiro [5,5] undecane and the like.

Each of these antioxidants is used alone,
Alternatively, two or more kinds can be used in combination.
The compounding amount of the antioxidant is appropriately selected within a range not to impair the purpose of the present invention, and is usually 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polymer component.
The range is 1 part by weight.

As the ultraviolet absorber, for example, 2- (2
-Hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5)
-Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di -T-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2
-(3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-
benzotriazole ultraviolet absorbers such as t-amyl-2-hydroxyphenyl) -2H-benzotriazole; 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4
-Di-t-butylphenyl-3,5-di-t-butyl-
4-hydroxybenzoate, hexadecyl-3,5-
Di-tert-butyl-4-hydroxybenzoate, 2-
(2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H -Benzotriazole, 2-
Bezoate UV absorbers such as (2-hydroxy-4-octylphenyl) -2H-benzotriazole;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonic acid trihydrate, 2
-Hydroxy-4-octyloxybenzophenone, 4-
Dodecaloxy-2-fodroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
Benzophenone ultraviolet absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; ethyl-2-cyano-3,3-diphenylacrylate, 2 '
Acrylate UV absorbers such as -ethylhexyl-2-cyano-3,3-diphenylacrylate; [2,
2'-thiobis (4-t-octylphenolate)]-
Metal complex UV absorbers such as 2-ethylhexylamine nickel are exemplified.

As the light stabilizer, for example, 2,2,6
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-
4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-
Hindered amine light stabilizers such as tetramethylpiperidine can be mentioned.

The near-infrared absorber includes, for example, a cyanine-based near-infrared absorber; a pyrylium-based infrared absorber; a squarylium-based near-infrared absorber; a croconium-based infrared absorber;
Azurenium-based near-infrared absorber; phthalocyanine-based near-infrared absorber; dithiol metal complex-based near-infrared absorber;
Naphthoquinone-based near-infrared absorber; anthraquinone-based near-infrared absorber; indophenol-based near-infrared absorber; azimuth-based near-infrared absorber; In addition, commercially available near-infrared absorbers SIR-103, SIR-114, SIR
-128, SIR-130, SIR-132, SIR-
152, SIR-159, SIR-162 (manufactured by Mitsui Toatsu Dye), Kayasorb IR-750, Ka
yasorb IRG-002, Kayasorb I
RG-003, IR-820B, Kayasorb I
RG-022, Kayasorb IRG-023, Ka
yasorb CY-2, Kayasorb CY-
4, Kayasorb CY-9 (Nippon Kayaku)
And the like.

The dye is not particularly limited as long as it can be uniformly dispersed and dissolved in the alicyclic structure-containing polymer.
Oil-soluble dyes (various CI solvent dyes) are widely used because of their excellent compatibility with the alicyclic structure-containing polymer used in the present invention. Specific examples of oil-soluble dyes include The The
Society of Diyes and Colo
Urists, Color Index vol. 3
Various C. described in C. I. Solvent dyes.

Examples of the pigment include diarylide pigments such as Pigment Red 38; Pigment Red 48:
2, Pigment Red 53, Pigment Red 57: 1
Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 248, etc .; Condensed Azo Lake Pigments; Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 1
85, penzimidazolone pigments such as Pigment Red 208; quinacridone pigments such as Pigment Red 122; Pigment Red 149, Pigment Red 17
8, perylene pigments such as Pigment Red 179; and anthraquinone pigments such as Pigment Red 177.

When the reflector of the present invention needs to be colored, any of dyes and pigments can be used within the scope of the present invention, and is not limited.

As the lubricant, an organic compound such as an ester of an aliphatic alcohol, an ester of a polyhydric alcohol or a partial ester, or inorganic fine particles can be used. Examples of the organic compound include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.

In general, inorganic particles can be used as the other lubricant. Here, the inorganic fine particles include oxides, sulfides, hydroxides, nitrides, halides, carbonates, sulfates, and acetates of elements belonging to Groups 1, 2, 4, and 6 to 14 of the periodic table. And particles of phosphate, phosphite, organic carboxylate, silicate, titanate, borate and hydrates thereof, composite compounds mainly containing them, and natural compounds.

As the plasticizer, for example, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethyl phenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, diphenyl monoxylenyl phosphate Phosphate triester plasticizers such as phosphate, monophenyldixylenyl phosphate, tributyl phosphate and triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-phthalate 2-ethylhexyl, diisononyl phthalate, octyldecyl phthalate,
Phthalate ester plasticizers such as butyl benzyl phthalate; fatty acid monobasic ester plasticizers such as butyl oleate and glycerin monooleate; dihydric alcohol ester plasticizers; oxy acid ester plasticizers
Among them, a phosphoric acid triester plasticizer is preferable, and tricresyl phosphate and tricillyl phosphate are particularly preferable.

Further, as a softening agent or a plasticizer, a hydrocarbon polymer which is liquid at room temperature and whose main skeleton is mainly a CC or C = C structure is preferably used. Among the liquid hydrocarbon polymers, a linear or branched liquid hydrocarbon polymer having no hydrocarbon ring in the main chain is preferable. Further, it is preferable that the molded article (reflector) obtained does not substantially have a C = C structure because of excellent weather resistance. The weight average molecular weight of the liquid hydrocarbon polymer is preferably 10,000 or less, more preferably 20 or less.
The range is from 0 to 8,000, particularly preferably from 300 to 4,000. Specific examples of the liquid hydrocarbon polymer include:
Squalane (C30H62, Mw = 422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO specified in JIS K2231)
VG32, ISO VG68, ISO VG100,
VG8 and VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like. Among them, squalane, liquid paraffin and polyisobutene are preferred.

Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol, and fatty acid esters of polyhydric alcohols such as glycerin monostearate and pentaerythritol monostearate. Stearyl alcohol and behenyl alcohol are particularly preferable. preferable.

These other compounding agents can be used alone or as a mixture of two or more kinds, and the ratio is appropriately selected within a range not to impair the object of the present invention. The amount is appropriately selected within a range that does not impair the object of the present invention.
To 5 parts by weight, preferably 0.01 to 1 part by weight.

Molding Material and Molding Method In the present invention, the alicyclic structure-containing polymer is used by mixing the above components as necessary. The mixing method is not particularly limited as long as these compounding agents are sufficiently dispersed in the alicyclic structure-containing polymer. For example, a method in which a resin is kneaded 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 coagulation method, a casting method, or a direct drying method in which the resin is dissolved and dispersed in an appropriate solvent. There is a method of removing the solvent by a method.

In the case of using a twin-screw kneader, after kneading, the mixture is usually extruded into a rod in a molten state, cut into an appropriate length by a strand cutter, and pelletized.

The reflector of the vehicular lamp according to the present invention comprises:
It is obtained by molding the above molding material. The molding method may be in accordance with a conventionally known molding method. 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, rotational molding and the like can be mentioned. Injection molding and press molding are preferred from the molding accuracy. 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.

Formation of Reflection Film Layer When a reflection film layer is formed on the above-mentioned reflector by using a metal having high reflectivity such as aluminum, nickel and gold, the method is not particularly limited, and a known method may be used. For example, a normal vapor deposition method, that is, vacuum vapor deposition, sputtering, ion plating, or the like can be used.

The conditions for forming the reflective film are not particularly limited. For example, when aluminum is vacuum-deposited to form a reflective film, the following conditions are preferable. That is, the degree of vacuum is in the range of 0.1 to 1,000 Pa, preferably 1 to 100 Pa, and when it is in this range, an aluminum film having fine texture and excellent adhesion can be deposited. The film may be formed while heating the molded article.
It is preferable to form the film in the temperature range of 00 ° C. because the adhesive strength is increased. The thickness of the reflective film is 5 to 10,000 nm, preferably 10 to
If the film thickness is too thin, the reflectance is too low, and a sufficient reflectance as a reflector cannot be obtained. And productivity decreases. When the film thickness is in the above range, a reflective film having high reflectivity and high productivity can be obtained, which is preferable.

In order to improve the adhesion between the reflector and the above-mentioned reflecting film, the surface of the reflector is subjected to a modification treatment and / or
Alternatively, a primer treatment may be performed. Examples of the surface modification treatment include an energy beam irradiation treatment such as a corona discharge treatment, a plasma treatment, an electron beam irradiation treatment, and an ultraviolet irradiation treatment, and a chemical treatment brought into contact with an oxidizing agent aqueous solution such as a potassium dichromate solution.

If necessary, a protective layer may be provided to prevent the reflector and the reflection film from being 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.

[0081]

Embodiments of the present invention will be described below. The vehicle lamp of the present embodiment is a headlamp for a passenger car, and includes a lamp body (a body according to the present invention), a unit-type lamp, an extension reflector, and an outer lens (a cover according to the present invention).

The lamp body is formed of a resin that does not transmit light. A first unit type lamp constituting a high beam lamp of a head lamp is provided inside the lamp body, and a low beam lamp is provided outside the vehicle. A second unit-type lamp to be configured is provided.

In these unit type lamps, a light bulb (bulb) is supported by a connector socket on the bottom surface of an elliptical main reflector. On the front edge of this main reflector,
A substantially cylindrical sleeve (lens holder) is attached, and a condenser lens is held on the front side edge of the sleeve by bonding.

The first and second unit-type lamps can obtain required light distribution characteristics by the lamps alone by the reflection characteristics of the main reflector and the light-collecting characteristics of the condenser lens. The gap between the connector socket of each unit type lamp and the opening of the lamp body is sealed by a socket cover.

An extension reflector is provided in the lamp body and between the first and second unit-type lamps and the inner surface of the lamp body, and an extension reflector is provided between the unit-type lamp and the inner surface of the lamp body. Hiding the gap between them, preventing the inner surface of the lamp body located behind when seeing the lamp from outside, and improving the appearance by showing the entire lamp room with a single mirror surface color Has a function to enhance product appeal.

The external shape of the extension reflector is designed to be housed in the lamp body, and has a back portion, and upper and lower portions projecting upward and downward from the front.

A fixed portion protruding rearward is formed on each of the left and right sides on the rear surface, and a bolt is inserted through the fixed portion and a nut is screwed into the fixed portion to fix the extension reflector to the lamp body. Is done. Two holes are formed in the rear part of the extension reflector, and the condenser lens of the unit type lamp is exposed to the front side of the lamp through these holes.

An outer lens is attached to the front opening of the lamp body. That is, a sealing leg is formed at the peripheral edge of the outer lens, and the sealing leg is inserted into a sealing groove formed at the opening edge of the lamp body, and is sealed in an airtight state using a sealing agent such as hot melt. Fixed.

In this embodiment, the main reflector, the sleeve and the extension reflector are respectively referred to as a norbornene-based polymer, a monocyclic cycloolefin-based polymer, a cyclic conjugated diene-based polymer, and a vinyl alicyclic hydrocarbon polymer. , And a hydrogenated product thereof, such as an alicyclic structure-containing polymer resin, and the surface thereof (the inner surface of the lamp and the inner lens surface and the outer lens surface) is evaporated with aluminum to form a reflective surface. ing.

As described above, the main reflector according to the present embodiment,
The sleeve and extension reflector are each
Since it is formed of the alicyclic structure-containing polymer resin described above, it is possible to obtain a sufficiently satisfactory surface smoothness without forming an undercoating film when performing an aluminum vapor deposition treatment.

The alicyclic structure-containing polymer resin constituting these main reflector, sleeve and extension reflector has excellent heat resistance, can be molded without decomposition even at high temperature, and has excellent fluidity at the time of melting. Therefore, even a thin, large, and complicated shape can be easily molded without causing molding failure. Therefore, even if the structure of the main reflector, the sleeve, and the extension reflector is complicated, large, and thin, the molding can be easily performed without causing molding failure.

Further, the main reflector according to the present embodiment,
The alicyclic structure-containing polymer resin constituting the sleeve and the extension reflector has a glass transition temperature of 30.
Since a soft polymer having a temperature of not more than ℃ is blended, it has excellent durability especially under high temperature and high humidity, and does not generate cracks or cracks even if screws are used during assembly.

The present invention is not limited to the above-described embodiment, but can be variously modified within the scope of the present invention.

For example, in the above-described embodiment, the main reflector, the sleeve, and the extension reflector are connected by fasteners such as screws and bolts, respectively. May be integrally molded with the alicyclic structure-containing polymer resin containing the soft polymer. Also, the condenser lens may be formed integrally with the extension reflector or the sleeve and the alicyclic structure-containing polymer resin containing the specific soft polymer described above. However, in this case, since the condenser lens is required to be transparent, it is necessary to mask this lens portion and deposit aluminum or the like on the inner surface of the extension reflector or the sleeve to form a reflection surface. The type of condenser lens is
There is no particular limitation, and a Fresnel lens may be used.

By integrally forming the condenser lens, a step of assembling the separate condenser lens to the extension reflector or the sleeve becomes unnecessary. In addition, by forming the condensing lens from the alicyclic structure-containing polymer resin blended with the above-mentioned specific soft polymer, the birefringence is smaller than that of a normal resin lens, and the environment changes. Can be expected to have a small deformation. Moreover, the moldability is good and the surface accuracy is excellent.

Further, in the above-described embodiment, the extension reflector is fixed to the lamp body side, but the mounting structure of the extension reflector is not particularly limited, and may be mounted to the outer lens side.

Further, the specific structure of the vehicular lamp to which the reflector according to the present invention is applied can be variously modified. For example, a shade which is a member for forming a cut-off line of the low beam may be mounted on the front surface of the main reflector and / or the front surface.

The reflector of the present invention can be applied to a rear lamp and other vehicular lamps in addition to a headlamp.

[0099]

The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to only these examples. In the following Examples and Comparative Examples, parts and% are based on weight unless otherwise specified.

In the following Examples and Comparative Examples, methods for measuring various physical properties are as follows. (1) The hydrogenation rate was measured by ¹ H-NMR. (2) The glass transition temperature is a value measured based on JIS K7121.

(3) The accuracy of the test piece surface is the maximum height Rm
Those with an ax value of 10 μm or less were judged as “○”, and those with an ax value of 10 μm or more were judged as “x”. (4) The appearance of the test piece was visually observed for sink, warp, silver, burn, and coloring, and those having no defect were judged as “「 ”, and those having a defect were judged as“ x ”. (5) In the heat resistance test, the test piece was placed on a horizontal plate, and 12
After heating and holding in a gear oven at 0 ° C. for 48 hours, the test pieces were tested for warpage, change in appearance, and adhesion of the film.
(A) The warpage of the test piece after heating was 0.3 mm or less as compared with before the heating, and was evaluated as “「 ”, and the test piece was 0.3 mm or more as“ X ”. (B) The change in appearance is indicated by “」 ”when there is no change in the appearance of the deposited film as compared with before the heat resistance test, and“ × ”when the mirror surface is fogged, poor reflection, film blistering, discoloration, etc. did. (C) The adhesion of the deposited film after the heat resistance test was determined by a cross-cut peel test. The cross-cut peeling test is performed by making 11 vertical and horizontal cuts at 1 mm intervals from the top of the vapor-deposited film formed on the surface of the molded product with a cutter to make 100 1-mm square cross-cuts, and use cellophane tape (Sekisui Chemical) Was peeled off vigorously and the number of peeled deposited films was counted. The number of less than 10 was evaluated as good (○), and the number of 10 or more was evaluated as unacceptable (x). (6) Screw resistance test is 4mm in outer diameter and 28m in length
A screw having an m screw was attached to the test piece B, and cracking of the test piece was observed. A sample without cracks was marked with “○” and one with cracks was marked with “×”.

Reference Example 1 A reaction vessel charged with 258 liters of cyclohexane was charged with bicyclo at room temperature under a nitrogen stream.
[2.2.1] Hept-2-ene (hereinafter abbreviated as NB) (1
18 kg) and stirred for 5 minutes. Further, triisobutylaluminum was added so that the concentration in the system became 1.0 ml / liter. Subsequently, ethylene was circulated at normal pressure while stirring to make the inside of the system an ethylene atmosphere. The internal temperature of the autoclave was maintained at 70 ° C., and pressure was applied with ethylene so that the internal pressure became 6 kg / cm ^{2 as a} gauge pressure. 1
After stirring for 0 minutes, a copolymerization reaction of ethylene and NB was performed by adding 5.0 liter of a toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance to the system. Was started. At this time, the concentration of the catalyst was 0.1% for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride with respect to the whole system.
015 mmol / l and methylalumoxane 7.5 mmol / l.

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

Then, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and sufficiently washed with acetone. did. Further, in order to extract unreacted monomers present in the polymer, this solid portion was reduced to 40 kg / m
After pouring into acetone so as to be ³ , an extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration, and at 130 ° C. and 350 mmH under nitrogen flow.
g and dried for 12 hours to obtain an ethylene / NB copolymer.

The ethylene / N obtained as described above
The B copolymer has an intrinsic viscosity [η] in a decalin solution of 130 ° C., 0.60 dl / g, and a Tg of 140 ° C.
The B content was 53 mol%.

REFERENCE EXAMPLE 2 A cyclohexane solution of tetracyclododecene (TCD) was fed from the top of a 1 m ³ polymerization vessel equipped with stirring blades to a TCD supply concentration of 60 k in the polymerization vessel.
g / m ³ was supplied continuously. As catalyst from the polymerization vessel top, VO and (O · C ₂ H ₅₎ of Cl ₂ cyclohexane-based solution, as vanadium concentration in the polymerization vessel is 0.9 mol / m ^3, ethylaluminum cough disk chloride de (Al ( A cyclohexane solution of C ₂ H ₅ ) _1.5 Cl _1.5 ) was continuously supplied into the polymerization vessel such that the aluminum concentration in the polymerization vessel was 7.2 mol / m ³ . Also, using a bubbling tube for the polymerization system, ethylene was 85 m ³ / hour, nitrogen was 45 m ³ / hour,
Hydrogen was supplied in an amount of 6 m ³ / hour.

A copolymerization reaction was carried out while maintaining the polymerization system in which a heating medium was circulated in a jacket attached to the outside of the polymerization vessel at 10 ° C. The polymerization solution of the copolymer produced by the above-mentioned copolymerization reaction was poured from the top of the polymerization vessel so that the polymerization liquid in the polymerization vessel was always 1 m ³ (that is, the average residence time was 0.1 m ³⁾ .
Withdrawn continuously (5 hours). To the extracted polymerization solution, a cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to stop the polymerization reaction.
Thereafter, the mixture was brought into contact with an aqueous solution obtained by adding 5 liters of concentrated hydrochloric acid to 1 m ^{3 of} water under a strong stirring at a ratio of 1: 1 to transfer a catalyst residue to an aqueous phase. After allowing this contact mixture to stand,
The aqueous phase was separated and removed, followed by washing twice with water, and the polymerization liquid phase was purified and separated.

Next, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and sufficiently washed with acetone. did. Further, in order to extract unreacted monomers present in the polymer, this solid portion was reduced to 40 kg / m
After pouring into acetone so as to be ³ , an extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration, and at 130 ° C. and 350 mmH under nitrogen flow.
g for 12 hours.

As described above, the obtained ethylene / T
The CD copolymer has an intrinsic viscosity [η] in a decalin solution of 130 ° C .; 0.42 dl / g, Tg;
The CD content was 31 mol%.

Reference Example 3 (Polymerization) Dehydrated cyclohexane 500 in a nitrogen atmosphere
To the parts by weight, 0.56 parts by weight of 1-hexene, 0.11 parts by weight of dibutyl ether, and 0.1 part by weight of triisobutylaluminum.
After mixing 22 parts by weight in a reactor at room temperature and mixing at 45 ° C., 8-methyl-tetracyclo [4.4.0.1
^2,5 . [ ^7,10 ] dodeca-3-ene (200 parts by weight) and tungsten hexachloride (0.70% by weight) in a toluene solution (30 parts by weight) were continuously added over 2 hours to carry out polymerization. The number average molecular weight (Mn) of the obtained polymer was 18,000, and the weight average molecular weight (Mw) was determined by high performance liquid chromatography (in terms of polystyrene) using cyclohexane as a moving bed.
Is 36,200 and the molecular weight distribution (Mw / Mn) is 2.0
It was one.

(Hydrogenation) The adjusted polymerization reaction solution was transferred to a pressure-resistant hydrogenation reactor, and 10 parts by weight and 200 parts by weight of a diatomaceous earth-supported nickel catalyst (manufactured by Nissan Gardler Co .; G-96D, nickel loading rate 58% by weight). Then, the mixture was reacted at 180 ° C. and a hydrogen pressure of 45 kgf / cm ² for 10 hours. This solution was filtered using a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst. The obtained reaction solution was poured into 3000 parts by weight of isopropyl alcohol with stirring to precipitate a hydrogenated product, which was collected by filtration. Further, after washing with 500 parts by weight of acetone, 1 t
The product was dried for 48 hours in a reduced pressure drier set at 100 ° C. or lower to obtain 190 parts by weight of a hydrogenated ring-opening polymer.

(Polymer Properties) The hydrogenation rate of the main chain of the obtained hydrogenated ring-opened polymer was 99.9%, and the number average molecular weight (M
n) is 20,400 and the weight average molecular weight (Mw) is 4
Its molecular weight distribution (Mw / Mn) was 1,200. The melt flow rate at 280 ° C. is 20 g
/ 10 min. The glass transition temperature was 140 ° C. and the specific gravity was 1.01.

Example 1 Ethylene prepared in Reference Example 1
Antioxidant (manufactured by Ciba Geigy; Irganox 1010, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane) (100 parts by weight of NB copolymer) 0.1 parts by weight and 20 parts by weight of a hydrogenated styrene-isoprene-styrene block copolymer (manufactured by Kuraray Co., Ltd .; Septon 4055) were added, kneaded with a twin-screw kneader, and pelletized. This pellet is mirror-polished on one side, 1 mm thick x 200 mm long
Using a mold having a width of 100 mm, injection molding was performed at a resin temperature of 320 ° C. and a mold temperature of 120 ° C. to prepare a test piece A. Further, the test piece A has a thickness of 400 n on the mirror side by vacuum evaporation.
An aluminum reflective film having a thickness of m was formed, and a test piece B was prepared.

Example 2 Pelletization, injection molding and injection molding were carried out in the same manner as in Example 1 except that the ethylene / NB copolymer was replaced by the ethylene / TCD copolymer prepared in Reference Example 2. Aluminum films were deposited and test pieces A and B
Was prepared.

Example 3 Test pieces A and B were prepared by pelletizing, injection molding and depositing an aluminum film on the hydrogenated ring-opening polymer prepared in Reference Example 3 in the same manner as in Example 1. .

[Example 4] In place of the hydrogenated styrene-isoprene-styrene block copolymer of Example 1, 20 parts by weight of polyethylene were blended. Test pieces A and B were prepared by depositing an aluminum film.

Example 5 Test pieces A and B were prepared in the same manner as in Example 1 except that 30 parts by weight of PAN-based carbon fiber (trade name, manufactured by Toray Industries, Inc.) was added.

Comparative Example 1 Ethylene prepared in Reference Example 1
Antioxidant (manufactured by Ciba Geigy; Irganox 1010, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane) (100 parts by weight of NB copolymer) Test pieces A and B were prepared by blending only 0.1 part by weight and pelletizing, injection molding and vapor deposition of an aluminum film in the same manner as in Example 1.

Table 1 shows the test pieces A produced in Examples 1 to 5 and Comparative Example 1, the smoothness and appearance of the test article surface, and the results of the heat resistance test measured using the test piece B.

[0120]

[Table 1] Table 2 shows the results of the screw resistance test measured using the test piece B molded in Examples 1 to 5 and Comparative Example 1.

[0121]

[Table 2] Evaluation of the moldability shown in Table 1 confirmed that there was no difference in moldability and heat resistance in Examples 1 to 5 and Comparative Example 1 regardless of the presence or absence of the soft polymer. In the evaluation of the screw-fastening test shown in Table 2, in Comparative Example 1, cracks occurred due to the screw-fastening. From the results shown in Tables 1 and 2, the reflector composed of the alicyclic structure-containing polymer resin in which the soft polymer of the present invention is blended has the same moldability, surface accuracy and heat resistance as those of the unblended one. It was confirmed that the molded article had cracking and cracking even when the molded article was screwed.

[0122]

As described above, according to the present invention, the surface smoothness and heat resistance are excellent, the durability under high temperature and high humidity is excellent, the screw resistance is excellent, and the screw can be easily fixed. Thus, it is possible to provide a reflector for a vehicle lamp which is excellent in assembling workability and can be easily formed into a thin and large one.

Claims (1)

[Claims] 1. A reflector for a vehicular lamp provided in a vehicular lamp, wherein the alicyclic structure-containing polymer resin has a glass transition temperature of 30 ° C.
A reflector for a vehicular lamp, comprising a resin composition containing the following soft polymer.