JPH05325612A - Lamp reflector - Google Patents

Abstract

PURPOSE:To provide a resin lamp reflector having good surface smoothness, very excellent in the adhesion of the resin surface, the adhesion under high temperature/high humidity in particular, and capable of being made light-weight. CONSTITUTION:A resin composition containing polyphynylene sulfide (A) and polyamide resin (B) containing polyamide such as nylon, acid-denatured polyolefin, and/or ionomer resin is molded at 280-320 deg.C. A primer is coated and baked as required on the face of this molding serving as a reflecting surface, and an aluminum metal film is applied by vacuum deposition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lamp reflector in which a resin film containing a polyarylene sulfide resin and a polyamide resin is molded, and a metal film is provided on the surface serving as the reflecting surface of the molded article, and the production thereof. Concerning the law. The lamp reflector is used for indoor and outdoor lighting, automobile headlights, work lights, and the like.

[0002]

2. Description of the Related Art Conventionally, lamp reflectors used for lighting of theaters, headlights of automobiles, etc.
Aluminum (hereinafter abbreviated as Al) material has been often used. However, in order to manufacture a lamp reflector using an Al material, a rolled Al plate is pressed to form the shape of the lamp reflector, then Al is vapor-deposited on the reflecting surface, and then spot welding or caulking is used to form the lamp mounting portion. Since a number of steps such as fixing are required and the cost is high, it has been attempted in recent years to manufacture them by integral molding with synthetic resin.

For example, it is known to manufacture a lamp reflector by using a bulk molding compound (BMC). With this lamp reflector, although the manufacturing process is somewhat simplified, the compound is thermosetting. Since it was a resin, it was inferior in productivity, was poor in recyclability of the material, and was inferior in heat resistance and surface smoothness. Further, in addition to the material having a high specific gravity, there is a problem that the lamp reflector itself becomes extremely heavy because a slide made of a metal is required due to its structure.

On the other hand, a lamp reflector made of a thermoplastic resin, for example, a polyarylene sulfide (hereinafter referred to as PAS) resin is also known. PAS resins have recently attracted attention as engineering plastics having excellent heat resistance and chemical resistance. Advantages of manufacturing a lamp reflector from PAS resin include increased flexibility in designing the lamp reflector and improved productivity, improved heat resistance, and reduced weight due to the possibility of injection molding. As a lamp reflector made of such PAS resin,
A lamp reflector using a PAS resin composition filled with a specific fine hollow granular filler for the purpose of lowering the specific gravity of the material and avoiding an increase in cost in consideration of strength, rigidity, and deformation resistance (JP-A-2-8247). )It has been known.

However, in this lamp reflector,
Due to the filled filler, the original advantage that the specific gravity of the material is low and the cost advantage is rather lost,
The surface smoothness of the resin surface was also insufficient.

Furthermore, in the above-mentioned lamp reflector made of PAS resin, even if a primer is applied, the adhesion to the resin surface is inferior, and in a particularly severe environment, for example, at a high temperature of 150 ° C. or higher assuming a halogen lamp or under high humidity. Since the adhesiveness is remarkably deteriorated when exposed to light for a long time, A provided on the reflecting surface of the reflector by a vacuum deposition method or the like.
The film does not have practical durability as a lamp reflector including optical performance due to peeling and swelling of the film.

[0007]

The present invention solves the problems of the prior art and has a high degree of freedom in designing.
We provide lamp reflectors with various features such as superior productivity and cost in manufacturing, excellent heat resistance, light weight, excellent surface smoothness of resin surface, and excellent adhesion on resin surface. To do.

[0008]

The present inventors have completed the present invention as a result of intensive studies to achieve the above-mentioned object.

That is, according to the present invention, a fatty acid metal salt, a silane coupling agent, a reinforcing material, and / or an inorganic filler are further added to a specific resin composition containing a polyarylene sulfide resin and a polyamide resin, if necessary. Another object of the present invention is to provide a lamp reflector used for indoor / outdoor lighting, automobile headlights, work lights, etc. by molding the compounded product and providing a metal film on the surface of the molded product, which serves as the reflection surface.

The lamp reflector of the present invention is molded by using a specific resin composition containing the PAS resin (A) and the polyamide resin (B), thereby making it possible to obtain a thermosetting resin ( BMC) and PAS resin can significantly reduce weight, which is not seen in lamp reflectors. Furthermore, the resin surface has good smoothness and excellent adhesion, and particularly excellent adhesion even under high temperature / humidity.
It retains high practicability / functionality as a lamp reflector.

That is, the most significant features of the lamp reflector of the present invention are (1) excellent smoothness of the resin surface, and (2) extremely excellent adhesion on the resin surface, which means that the resin surface and the primer are Not only does it have good adhesion, but it also means that it is possible to directly provide a metal film on the resin surface, which was previously impossible, and in addition (3) significant weight reduction is possible, etc. Is achieved and high utility / functionality as a lamp reflector can be maintained.

The resin composition used in the lamp reflector of the present invention is a PAS resin (A) and a polyamide resin (B).
It contains. As the PAS resin in the present invention,
A compound containing 70 mol% or more of the structural unit represented by the following general formula 1 is preferable because it provides a lamp reflector with excellent characteristics. Especially polyphenylene sulfide (PP
S) resins are preferably used.

[0013]

[Chemical 1]

The polymer can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and water in a polar solvent. A method of polymerizing in the presence of sodium oxide, a self-condensation of p-chlorothiophenol and the like can be mentioned. However, sodium sulfide and p-
A method of reacting dichlorobenzene is suitable. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to control the degree of polymerization.

If it is less than 30 mol% as a copolymerization component, for example, a meta bond, an ether bond,
Even if it contains a sulfone bond, a sulfide ketone bond, a biphenyl bond, a substituted phenyl sulfide bond, a trifunctional phenyl sulfide bond, a naphthyl bond, etc., it does not matter as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is It is preferably 10 mol% or less.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

Particularly, when a phenyl bond, a biphenyl bond, a naphthyl sulfide bond or the like having three or more functional groups is selected for the copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

Such PAS resin is produced by a general method, for example, (1) reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 2,513,188, etc., JP-B-44).
-27671 and Japanese Patent Publication No. 45-3368)
(2) Condensation reaction in the presence of an alkali catalyst of thiophenols or copper salts (see US Pat. No. 3,274,615 and British Patent No. 1160660) (3) Lewis acid catalyst of aromatic compound with sulfur chloride It is synthesized by a condensation reaction in the coexistence (see Japanese Examined Patent Publication No. 46-27255, Belgian Patent No. 29437) and the like, and can be arbitrarily selected according to the purpose.

If a PAS resin which is not crosslinked or has a small degree of crosslinking is used as the PAS resin used in the reflector of the present invention, it is particularly preferable to use JP-A-50-8.
High molecular weight PAS resins known from JP-A-4698 and JP-A-51-144495 can be preferably used. These non-crosslinked or low-crosslinked high molecular weight P
Among PS resins, especially according to ASTM D1238 31
Under 6 ℃ / 5000g load (orifice; 0.0825 ±
A PAS resin having a melt flow rate of 0.002 inch diameter × 0.315 ± 0.001 inch length) of 800 g / 10 minutes or less is preferable.

On the other hand, P used in the reflector of the present invention
As the AS resin, a PAS resin having a high degree of crosslinking is used, and among these PAS resins having a high degree of crosslinking, AS is particularly preferable.
TMD1238 under 316 ° C / 5000g load (orifice; 0.0825 ± 0.002 inch diameter x
0.315 ± 0.001 inch length) melt flow
A PAS resin having a rate of 800 g / 10 minutes or less is suitable.

The polyamide resin (B), which is one component of the resin composition used in the lamp reflector of the present invention, comprises a polyamide resin or a resin containing a polyamide resin and a polyolefin resin.

As the polyamide resin which can be used in the lamp reflector of the present invention, various known ones can be mentioned. For example, oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid,
Dicarboxylic acids such as 1,4-cyclohexyldicarboxylic acid and ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine,
Polyamide obtained by polycondensation with metaxylylenediamine; polyamide obtained by polymerizing cyclic lactam such as caprolactam and laurolactam; or obtained by copolymerizing cyclic lactam with a salt of dicarboxylic acid and diamine Polyamide etc. can be mentioned. Of these polyamides, 6-nylon and 6-6- are preferred.
Nylon, 4 / 6-nylon, 6 / 10-nylon, 6
・ 6/6 ・ 10-Nylon, 6/6 ・ 6-Nylon, 1
2-nylon, 11-nylon and the like can be mentioned, and particularly preferred are 6-nylon and 6.6-nylon.

Examples of the polyolefin resin which can be contained in the polyamide resin (B) of the present invention include acid-modified polyolefin and / or ionomer resin.

The acid-modified polyolefin which can be used includes direct copolymerization of α, β-unsaturated carboxylic acid comonomer and olefin, and α, β-unsaturated carboxylic acid comonomer in polyolefin and polyolefin copolymer. Those produced by a method such as graft copolymerization of at least 50 mol%, preferably 70 mol%.
1-olefin such as ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1, decene-1,4-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1, Those containing vinylcyclohexane, styrene, α-methylstyrene, styrene substituted with lower alkyl substituents or the like are preferred, and it is also possible to use mixtures of the abovementioned olefins.

Among them, polyolefins and / or polyolefin copolymers graft-copolymerized with α, β-unsaturated carboxylic acid comonomers, for example, α, β-copolymers obtained from ethylene and butene-1 or propylene.
A graft copolymer of an unsaturated carboxylic acid comonomer is preferable.

Examples of commercially available products of the polyolefin and / or polyolefin copolymer used herein include Tuffmer A series such as Tuffmer A4085, Tuffmer A4090, Tuffmer A20090 (ethylene-butene-1 copolymer, Mitsui Petrochemical Co., Ltd. Industrial Co., Ltd. products) and Toughmer P series (ethylene-propylene copolymer, Mitsui Petrochemical Industrial Co., Ltd. product) such as Tuffmer P0280, Tuffmer P0480, Tuffmer P0680, and Tuffmer P0880.

Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid,
Examples thereof include (anhydrous) maleic acid, fumaric acid and monoesters of the above-mentioned carboxylic acids, and acrylic acid, methacrylic acid and (anhydrous) maleic acid are preferred.
Among them, (anhydrous) maleic acid is particularly preferable because a sufficient acid modification effect can be obtained by adding a small amount as compared with other acids.

Suitable acid-modified polyolefins include ethylene-butene-1- (anhydrous) maleic acid copolymers and ethylene-propylene- (anhydrous) maleic acid copolymers.

Examples of the ionomer resin that can be used in the present invention include those obtained by neutralizing a part or all of the above acid-modified polyolefin with a metal ion, and among them, α, β-unsaturated carboxylic acid. It is preferable that some or all of the carboxyl groups in the direct copolymer of the comonomer and the olefin are neutralized with a metal ion having a valence of 1 to 3.

The copolymer used to obtain the above-mentioned ionomer resin is, for example, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / itaconic acid copolymer, ethylene / methyl hydrogen maleate copolymer. Polymers, ethylene / maleic acid copolymers, ethylene / acrylic acid / methyl methacrylate copolymers, ethylene / methacrylic acid / ethyl acrylate copolymers, ethylene / itaconic acid / methyl methacrylate copolymers, ethylene / maleic Methyl hydrogen acrylate / ethyl acrylate copolymer, ethylene / methacrylic acid / vinyl acetate copolymer, ethylene / acrylic acid / vinyl alcohol copolymer, ethylene / propylene / acrylic acid copolymer, ethylene / styrene / acrylic acid Copolymer, ethylene / methacrylic acid / acrylonitrile copolymer Ethylene / fumaric acid / Binirumechirue - ether copolymers, ethylene / vinyl chloride / acrylic acid copolymer, ethylene / vinylidene chloride / acrylic acid copolymer, ethylene / vinyl fluoride / methacrylic acid copolymer,
Ethylene / chlorotrifluoroethylene / methacrylic acid copolymer, polyethylene / acrylic acid graft copolymer, polyethylene / methacrylic acid graft copolymer, polymerized ethylene / propylene acrylic acid graft copolymer, polymerized ethylene / butene-1 Methacrylic acid graft copolymer, polymerized ethylene / vinyl acetate methacrylate graft copolymer, polypropylene / acrylic acid graft copolymer, polypropylene / methacrylic acid graft copolymer, polybutene / acrylic acid graft copolymer, poly-3 -Methylbutene / acrylic acid graft copolymer, polyethylene / acrylic acid / ethyl acrylate graft copolymer, styrene / maleic acid copolymer,
Styrene / acrylonitrile / maleic acid copolymer, styrene / α-methylstyrene / maleic acid copolymer,
There are styrene / acrylic acid copolymers, styrene / methyl methacrylate / itaconic acid copolymers, etc., but not limited to these.

The monovalent metal ions for neutralizing the carboxylic acid in these copolymers include Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Cu ⁺ , as monovalent metal ions. Hg ⁺
As the divalent metal ion, Be ²⁺ , Mg ²⁺ , C
a ²⁺ , Sr ²⁺ , Ba ²⁺ , Cu ² , Cd ²⁺ , Hg ²⁺ , Sn
²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ^2+, Zn ^2+, etc.
As trivalent metal ions, Al ³⁺ , Sc ³⁺ , Fe ³⁺ , Yt
³⁺ etc. are mentioned respectively.

Specific examples of these ionomer resins include, but are not limited to, ionomer resins marketed by Mitsui-DuPont Polychemical under the name of "HIMILAN".

The mixing ratio of the PAS resin (A) and the polyamide resin (B) of the resin composition used for the lamp reflector of the present invention is not limited to a specific ratio,
PAS resin (A) / polyamide resin (B) = 5/95
The range of ˜95 / 5 is preferable in order to obtain a lamp reflector having excellent characteristics.

When the polyamide resin (B) contains a polyamide resin and a polyolefin resin, the mixing ratio of the polyamide resin and the polyolefin resin is not limited to a specific ratio. Polyamide resin / polyolefin resin = 20/80 to 95 /
The range of 5 is preferable in order to obtain a lamp reflector having excellent characteristics.

As a method of using a polyamide resin (B) containing a polyolefin resin and preparing a resin composition comprising this and a PAS resin (A), a polyamide resin (B) and a polyamide resin are previously prepared. A method of melt-kneading the polyolefin-based resin and then melt-kneading the polyamide-based resin (B) and the PAS resin (A) is preferable, but the method is not limited thereto.

One or more specific silane compounds may be added to the resin composition used in the lamp reflector of the present invention. The silane compound that can be added is specifically one or more of aminoalkoxysilane, epoxyalkoxysilane, and vinylalkoxysilane.

As the aminoalkoxysilane, any silane compound having one or more amino groups and two or three alkoxy groups in one molecule is effective. For example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ-
Examples thereof include aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

As the epoxyalkoxysilane, any silane compound having one or more epoxy groups and two or three alkoxy groups in one molecule is effective. For example, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like can be mentioned.

As the vinylalkoxysilane, any silane compound having one or more vinyl groups in one molecule and two or three alkoxy groups is effective. Examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane and the like.

Preferred examples of the specific silane compound that can be added in the present invention include aminoalkoxysilane.

The specific silane compound which can be added in the present invention is preferably added when preparing the resin composition for a lamp reflector from the PAS resin (A) and the polyamide resin (B).

The addition amount of the specific silane compound that can be added is the sum of the components (A) and (B) of the resin composition used in the lamp reflector of the present invention (A) + (B);
The amount is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight.

The resin composition used in the lamp reflector of the present invention may contain a fatty acid metal salt. The fatty acid metal salt that can be added in the present invention is added for the purpose of further improving the adhesion between the resin surface of the lamp reflector of the present invention and the primer or the metal film. Considering the heat resistance of the metal salt itself and the strength of the lamp reflector after addition, the carbon number of the fatty acid is 18 or more, more preferably 24 or more. Zinc montanate can be mentioned as an example of a preferable fatty acid metal salt.

The fatty acid metal salt which can be added in the present invention is preferably added when preparing the resin composition for a lamp reflector from the PAS resin (A) and the polyamide resin (B).

The amount of the fatty acid metal salt added in the present invention is
The total of components (A) and (B) of the resin composition used for the lamp reflector of the present invention (A) + (B); 0.01 to 10 parts by weight, preferably 0.1 to 100 parts by weight.
~ 3 parts by weight.

Further, the resin composition used in the lamp reflector of the present invention includes a fibrous reinforcing material and / or an inorganic filler.
Can be included. As the fibrous reinforcing material, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, further stainless steel, aluminum, titanium, copper,
Examples thereof include inorganic fibrous substances such as brass and other metallic fibrous substances, organic fibrous substances such as aramid fibers, and the like, and any form such as chopped fiber and milled fiber can be used. Polyamide,
High melting point organic fibrous substances such as fluororesin and acrylic resin can also be used. A particularly representative fibrous reinforcing material is glass fiber or carbon fiber.

The fiber diameter of the fibrous reinforcing material that can be used in the present invention is preferably 8 μm or less in consideration of the surface smoothness of the lamp reflector.

As the inorganic filler, silicon carbide, boron nitride, various metal powders, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, nepheline sinite, talc, Atarupulgite, wollastonite,
PMF, ferrite, aluminum silicate, calcium silicate, calcium carbonate, magnesium carbonate, dolomite,
Antimony trioxide, zinc oxide, titanium oxide, alumina,
Examples thereof include magnesium oxide, magnesium hydroxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balun, quartz, silica and quartz glass. Particularly preferred inorganic fillers include calcium carbonate and / or magnesium hydroxide.

The fibrous reinforcing material and / or the inorganic filler which can be added in the present invention should be added when preparing the resin composition for the lamp reflector from the PAS resin (A) and the polyamide resin (B). Is preferred.

The resin composition used for the lamp reflector of the present invention may further be mixed with the following polymers within a range not impairing the object of the present invention. Examples of these polymers include ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, and (meth) acrylonitrile. Polyesters such as polymer or copolymer, polyurethane, polybutylene terephthalate, polyethylene terephthalate, etc., polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate , Homopolymers such as polyphenylene ether, polyether ketone, polyether ether ketone, polyimide, polyamide imide, polyether imide, silicone resin, phenoxy resin, fluororesin, liquid crystal polymer, polyaryl ether, etc. , Randa Copolymers or block copolymers, may be mentioned a graft copolymer.

The resin composition used in the lamp reflector of the present invention includes a plasticizer, a small amount of a release agent, a coloring agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, a rust preventive agent, a flame retardant agent. Etc. may be added.

The resin composition used in the lamp reflector of the present invention can be prepared by a known method. For example, PA
After uniformly mixing the S resin (A), the polyamide resin (B), and optionally other raw materials with a mixer such as a tumbler or a Henschel mixer, a uniaxial or biaxial extrusion kneader And the mixture is melt-kneaded in the temperature range of 200 ° C. to 350 ° C. to obtain a resin composition used as a pellet for the lamp reflector of the present invention. However, when the polyamide-based resin (B) contains a polyamide resin and a polyolefin-based resin, the polyamide resin and the polyolefin-based resin are previously mixed at 200 ° C. to 3 ° C. as described above.
After melt-kneading at 00 ° C. to prepare a polyamide resin (B), the polyamide resin (B) and the PAS resin (A)
It is preferable to melt-knead and.

A molded product for a lamp reflector is molded using the above resin composition at a molding temperature of 280 to 320 ° C., and then a metal film is provided on the surface serving as the reflection surface of the molded product. "Dry plating" is a method for providing a metal film.
(A so-called dry metal plating method), and specifically, a vacuum deposition method, an ion plating method (ion plating method), and a sputtering method which is an intermediate technique between them can be exemplified.

A vacuum vapor deposition method, which is more common in producing a lamp reflector, is taken as an example, and a specific production method thereof will be described below. (1) Immerse the injection-molded lamp reflector molded product in a solvent such as isopropyl alcohol (Dipping)
Degreasing by, for example, 6 if necessary
Dry at 0 to 120 ° C. (2) Apply a primer (undercoat) if necessary on the surface of the lamp reflector molded product after degreasing and cure it, (3) attach the molded product to a supporting jig, After being inserted into a vacuum container, the chamber is evacuated and the evaporation of evaporated metal such as metallic aluminum evaporated under a predetermined pressure is started. At this time, the attached jig is rotated or revolved above the evaporation source as required. The thickness of the metal film is 0.05 to 0.1 μm. (4) After vapor deposition, if necessary, top coating is applied to protect the vapor deposition surface.

In the lamp reflector molded product of the present invention, the resin surface easily adheres to the metal film, and thus a primer (undercoat) is not always necessary. When the primer is not used, it is preferable to adopt the ion plating method (ion plating method), which has excellent adhesion to the substrate. Al
The ion plating method is useful for making the lamp reflector of the present invention.

The primer applied to the reflecting surface of the lamp reflector molded product is used for the purpose of (1) improving the surface smoothness of the reflecting surface and (2) improving the adhesion between the metal film and the surface of the molded product. Be seen. The film thickness is about 10 to 50 μm. As the primer coating, melamine alkyd type, urethane type and acrylic type are generally used. The acrylic type is mainly UV curable type and the other type is mainly heat curable type. The preferred primer for use in the lamp reflector of the present invention is a urethane-based one that can provide a cured film having excellent heat resistance. In particular, a reaction between a long-chain diol having polybutadiene as a main chain and a blocking isocyanate blocked with phenol or the like (the curing and baking conditions are 1
Heating at 50 ° C. or higher, preferably 180 ° C. or higher for 1 hour or longer) is preferable.

[0064]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, the part in an example means a weight part.

Reference Example 1 (Production of PPS- (1)) 1993 parts of N-methylpyrrolidone and 2.7 hydrate of sodium sulfide were added to a 5-liter autoclave equipped with a stirrer.
7 parts (4.1 mol), 1.6 parts (0.04 mol) of sodium hydroxide and 144 parts (1.0 mol) of sodium acetate were charged and stirred under a nitrogen atmosphere up to 200 ° C. over about 2 hours. While gradually raising the temperature 102
ml of water was distilled off.

Then, the reaction system was cooled to 150 ° C., and then 603 parts (4.1 mol) of p-dichlorobenzene and 1,
1.8 parts (0.01 mol) of 2,4-trichlorobenzene and 310 parts of N-methylpyrrolidone were added and 2
The reaction was carried out at 30 ° C for 2 hours and further at 260 ° C for 3 hours, during which the internal pressure at the end of the polymerization reaction was 9.0 kg / cm.
^{Was 2} .

Thereafter, the autoclave was cooled, the contents were filtered off, and the cake was washed with hot water three times, further with acetone twice, and then dried at 120 ° C. 394 parts of light grayish brown granular PPS was obtained (yield = 89%).

The PPS obtained here has a logarithmic viscosity [η].
It was 0.20 and the melt flow rate was 550 g / 10 minutes. This is called PPS- (1). The logarithmic viscosity [η] of PPS is 206 ° C. (40%) of the α-methylchlornaphthalene solution of PPS (PPS concentration 0.4 g / 100 ml).
The relative viscosity value at 0 ° F.) was measured and calculated by the following formula. [Η] = ln (relative viscosity value) / PPS concentration

Reference Example 2 (Production of PPS- (2)) N-methylpyrrolidone was added to a 50 liter scale autoclave at a molar ratio of 70, and sodium sulfide nonahydrate was added to 0.2%.
99, sodium benzoate at 0.60 and sodium hydroxide at a ratio of 0.15 mol (50 mol scale),
The temperature was raised to 210 ° C. in a nitrogen stream and dehydration was performed to a dehydration rate of 110%. The system was cooled to 160 ° C., charged with P-dichlorobenzene at a molar ratio of 1.0, sealed, and then pressurized with nitrogen to an internal pressure of 2.5 kg / cm ² . The temperature was controlled in consideration of the heat generated by the polymerization, the temperature was raised to 270 ° C., and the polymerization was carried out with stirring for 5 hours. Internal pressure is 17 kg
It was rising to / cm ² . Next, after cooling the system, the pressure was released, and the contents were poured into a large amount of water to recover a flake-shaped polymer. The polymer was repeatedly washed with hot water and acetone, and finally was a white flake with a yield of 70%. This white flaky PPS polymer (logarithmic viscosity [η]
0.19, melt flow rate 1500 g / 10 min) was charged into a ribbon blender, stirred while blowing air at 245 ° C., heat-treated for 4 hours, cross-linked, and finally logarithmic viscosity [η] 0 .20, melt flow rate 550
A g / 10 min PPS polymer was obtained. This is PPS-
It is called (2).

Reference Example 3 (Acid-modified polyolefin- (1)
Production: APO-1) Ethylene-propylene copolymer (Tufmer P-028
0) 100 parts of toluene was dissolved in 400 parts of toluene under heating with stirring at 80 ° C., and then 5 parts of maleic anhydride was added and dissolved. Then, after heating the content to 110 ° C., a solution of 0.15 parts of tertiary butyl peroxybenzoate (NOF, perbutyl Z) / 20 parts of toluene was added dropwise over 1 hour,
Polymerization was carried out at 0 ° C for 10 hours. The obtained graft polymer solution was diluted with toluene to a concentration of 5%, then added little by little to an equivalent amount or more of methanol at 45 to 55 ° C. to precipitate the graft polymer, which was washed and dried. This graft polymer is used as an acid-modified polyolefin- (1) (AP in the table)
O-1).

When the acid value was measured, maleic anhydride was 4.7
It was found to be% grafted.

Examples 1 to 4 and Comparative Examples 1 to 3 PAS resins (A) and polyamide resins (B) synthesized in Reference Examples and other raw materials (fibrous reinforcing material, inorganic filler, fatty acid metal salt, Silane coupling agent, etc.) in the proportions shown in the table (numerical values are parts by weight) and uniformly mixed, and then 290 ° C. in a 35 mmφ twin-screw extruder.
And melt-kneaded to obtain pellets. However, when the polyamide resin (B) contains a polyamide resin and a polyolefin resin, after uniformly mixing the polyamide resin and the polyolefin resin, a cylinder temperature of 270 ° C. is obtained using a 40 mmφ uniaxial extruder. Then, the polyamide resin (B) was prepared in advance by melt-kneading, and then the polyamide resin (B) and the PAS resin (A) were melt-kneaded by the above-mentioned method to obtain pellets (two-step production method).

These pellets consisting of the PAS resin (A) and the polyamide resin (B) were fed to an inline screw type 3 ounce injection molding machine, and the cylinder temperature was 290 ° C., the mold temperature was 135 ° C., and the injection pressure was. 1000 kgf
/ Cm ² , at injection speed medium speed, lamp reflector (mold surface roughness: 0.02 μm or less), 100 mm × 1
00 mm x 2 mm (thickness) sheet (mold surface roughness:
Test pieces for evaluating the mechanical properties (including specific gravity) of the resin composition (0.02 μm or less), and various properties were evaluated. The results are shown in Tables 1 and 2.

The evaluated items are as follows. <Primer with lamp reflector / Al vapor deposition film adhesion (cross-section peeling test)> After degreasing the reflective surface of the molded lamp reflector with isopropyl alcohol, the primer
(Blocking isocyanate type urethane-based paint: Toyo Kogyo Paint Co., Ltd., "BP-50")
C./hour for 1 hour to cure. Immediately after curing the primer, Al is vacuum-deposited to a thickness of 0.05 to 0.1 μm,
After leaving for 24 hours, check the cross-section peeling test for primer / Al
The vapor deposition film adhesion (initial adhesion) was evaluated. Furthermore, the lamp reflector after Al deposition was placed in an oven at 150 ° C / 1
After heating for 00 hours, the adhesion of the primer / Al deposited film after heat aging (adhesion after aging) was evaluated by a cross-cut peeling test as in the case of initial adhesion.

<Surface smoothness (unit: μm)> Molded 1
The surface roughness (resin surface roughness) of a sheet of 00 mm x 100 mm x 2 mm (thickness) was measured by a surface roughness meter (trade name: s
urfcom, manufactured by Tokyo Seimitsu Co., Ltd.).

(Measurement items: Rmax: maximum height / JIS standard, Rz: 10-point average roughness / JIS standard, measuring distance: 2.5
(0 mm, magnification: 10,000 times) Further, the surface roughness (primer surface roughness) of the sheet coated with a primer on the sheet was measured in the same manner as the above lamp reflector.

<Image clarity (C value)> 100 mm molded
Using a sheet of 100 mm × 2 mm (thickness), an optical comb width:
The image clarity (C value) was measured under the conditions of 1.0 mm and a reflection angle of 45 °.

<Mechanical Properties of Resin Composition> (1) Specific Gravity: Measured with a test piece used for measuring bending properties in accordance with ASTM D-792.

(2) Bending property: Bending strength (unit: Kg / cm ² ) and bending elastic modulus (unit: Kg) according to ASTM D-790.
/ cm ² ) measured with a 1/8 "(thickness) x 1/2" (width) x 5 "(long) test piece.

(3) Izod impact strength: Notch impact strength (unit: Kg · cm / cm) is 1/8 ″ (thickness) according to ASTM D-256.
Measured with a test piece of x 1/2 "(width) x 2 1/2" (length).

The contents of each of the blended components are as follows. (1) Polyamide resin is nylon 66 (Leona 130
0, Asahi Kasei Kogyo Co., Ltd. (2) The polyolefin resin is an acid-modified polyolefin: APO-1 ionomer resin of Synthesis Example 3 described above: Himiran 1856, manufactured by Mitsui DuPont Polychemical Co., Ltd. (3) Fibrous reinforcing material Reinforcement A: Fiber diameter 6 μm, average fiber length 60 μm, milled glass fiber-Reinforcement material B: Fiber diameter 6 μm, 3 mm length, chopped strand glass fiber Reinforcement material C: Fiber diameter 13 μm, 3 mm length Chopped strand glass fiber- (4) Inorganic fillers are filler A: Kisuma 5B, magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd. Filler B: heavy calcium carbonate, average particle size 1.6μ.
m Filler-C: Aluminum silicate balloon (SiO ₂ 52 wt.%
, Al ₂ O ₃ 33 wt.%, Specific gravity 2.1 average particle size 10 μm),
(5) Silane coupling agent: γ-aminopropyltriethoxysilane

[0082]

[Table 1]

[0083]

[Table 2]

Example 5 Al was vacuum-deposited directly on a reflecting surface of a lamp reflector formed of a resin composition having the same composition as in Example 1 without applying a primer on the reflective surface thereof by a cross-cut peeling test. When the film adhesion (initial adhesion) was evaluated, it was 85/100. Furthermore, after heating the lamp reflector after Al vapor deposition in an oven at 150 ° C./100 hours, the adhesiveness of the Al vapor deposition film after heating and aging (after aging) by a cross-cut peeling test similar to the initial adhesiveness. The adhesiveness) was evaluated to be 70/100.

[0085]

The lamp reflector of the present invention is obtained by molding a specific resin composition containing a PAS resin (A) and a polyamide resin (B), and providing a metal film on the reflection surface of the molded product. In addition to having good surface smoothness, it also has excellent adhesion to the resin surface, especially at high temperatures / humidity, and can be made lighter, and is highly practical / functions as a lamp reflector. It retains sex.

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Claims (14)

[Claims] 1. A resin composition containing a polyarylenylene sulfide resin (A) and a polyamide resin (B) is molded, and a metal film is provided on the surface of the molded product to be the reflection surface. And a lamp reflector. 2. A resin composition containing a polyarylenylene sulfide resin (A) and a polyamide resin (B) is molded, a primer is applied to the reflection surface of the molded product, and then a metal is used. A lamp reflector comprising a film. 3. The lamp reflector according to claim 1, wherein the polyamide resin (B) is a polyamide resin. 4. The lamp reflector according to claim 1, wherein the polyamide resin (B) contains a polyamide resin and a polyolefin resin. 5. The lamp reflector according to claim 4, wherein the polyolefin resin is an acid-modified polyolefin and / or an ionomer resin. 6. The lamp reflector according to claim 4, wherein the resin composition is obtained by melt-kneading a melt-kneaded product of a polyamide resin and a polyolefin resin and (A). 7. The lamp reflector according to claim 1, further comprising a reinforcing material and / or an inorganic filler. 8. The lamp reflector according to claim 7, wherein the reinforcing material is a fibrous reinforcing material having a fiber diameter of 8 μm or less. 9. The lamp reflector according to claim 7, wherein the inorganic filler is calcium carbonate and / or magnesium hydroxide. 10. The method according to claim 1, further comprising a fatty acid metal salt.
The lamp reflector according to 2, 3, 4, 5, 6, 7, 8 or 9. 11. The lamp reflector according to claim 10, wherein the fatty acid metal salt is zinc montanate. 12. The method according to claim 1, further comprising a silane coupling agent.
The lamp reflector according to 1. 13. A resin composition containing a polyarylene sulfide resin (A) and a polyamide resin (B) is molded, and a metal film is provided on the surface of the molded product, which is the reflective surface. And lamp reflector manufacturing method. 14. A resin composition containing a polyarylene sulfide resin (A) and a polyamide resin (B) is molded, a primer is applied to the reflection surface of the molded product, and then a metal is used. A method of manufacturing a lamp reflector, which comprises providing a film.