JPH05320506A - Lamp reflector - Google Patents

Abstract

PURPOSE:To obtain a lamp reflector made of a resin, excellent in heat resistance, high-temperature rigidity, surface smoothness and adhesion of resin surfaces, especially the adhesion at high temperatures and high humidities with hardly any warpage and deformation in injection molding and capable of reducing the weight. CONSTITUTION:The objective lamp reflector is obtained by molding a resin composition comprising (A) a polyphenylene sulfide and (B) a polyphenylene ether(PPE) or a functionalized PPE resin functionalized with a styrenic resin and/or maleic anhydride, etc., at 280-330 deg.C, as necessary, coating the surface to be a reflecting surface of the resultant molding with a primer, baking the primer and subsequently forming an aluminum metallic film by a vacuum deposition method, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention molds a resin composition containing a poly (arylene sulfide) resin and a poly (arylene ether) resin, and a metal film is provided on the surface of the molded product which is to be the reflecting surface. The present invention relates to a lamp reflector and a manufacturing method thereof. 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 it is manufactured through a number of steps such as fixing, the cost is high. Therefore, it has been attempted in recent years to manufacture it by integral molding with a 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, the productivity was poor, the recyclability of the material was poor, and the heat resistance and surface smoothness were poor. 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,
Further, the surface smoothness of the resin surface was insufficient, and even if the primer was applied to the resin surface, the adhesion on the resin surface was poor. Furthermore, in these lamp reflectors, P
Due to the low glass transition point of AS resin, the rigidity at high temperature is not sufficient. For example, the lamp reflector deforms under its own weight in a high temperature atmosphere exceeding 150 ° C, which is assumed for halogen lamps, and the light distribution performance (luminance ) Is reduced, the optical axis is displaced, etc., and practical performance as a lamp (for example,
Problems such as not meeting JIS D 5500) have occurred. Also P
Due to the anisotropy of the AS resin itself, the lamp reflector is warped and deformed during injection molding, causing abnormalities in the light distribution performance, optical axis, etc., as described above, as well as the lamp mounting process and screwing process during assembly. There is a possibility that the production efficiency will be significantly reduced due to such problems.

[0006]

The present invention solves the problems of the prior art and has a high degree of freedom in designing.
Superior in productivity (including warpage and deformation characteristics) and cost during manufacturing, excellent in heat resistance, excellent in rigidity at high temperature, lightweight, excellent in surface smoothness of resin surface,
It is an object of the present invention to provide a lamp reflector having various characteristics such as excellent adhesion on the resin surface.

[0007]

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

That is, the present invention is a composition in which a reinforcing material and / or an inorganic filler, a fatty acid metal salt or the like is further added, if necessary, to a specific resin composition containing a polyarylene sulfide resin and a polyarylene ether resin. In order to provide a lamp reflector used for indoor / outdoor lighting, automobile headlights, work lights, etc.

The first feature of the lamp reflector of the present invention formed by using a specific resin composition containing the PAS resin (A) and the polyarylene ether resin (B) is as follows.
(1) Good resin surface smoothness, (2) Resin surface is extremely rich in adhesion, which means good adhesion between the resin surface and the primer, especially at high temperature / humidity. In addition to being extremely excellent, it is possible to directly provide a metal film on the surface of a resin, which has been completely impossible up to now, and in addition, (3) it is possible to significantly reduce the weight.

The second feature of the lamp reflector of the present invention is that it has excellent rigidity at high temperatures, and that the reflector itself undergoes little warpage / deformation during injection molding of the lamp reflector.

The resin composition used in the lamp reflector of the present invention comprises a PAS resin (A) and a polyarylene ether resin (B).

As the PAS resin in the present invention, a resin containing 70 mol% or more of the structural unit represented by the following general formula 1 is preferable because it provides a lamp reflector having excellent characteristics. Especially polyphenylene sulfide (PPS)
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.

P used in the lamp reflector of the present invention
If a PAS resin that is not crosslinked or has a small degree of crosslinkage is used as the AS resin, it is particularly preferable to use JP-A No.
High molecular weight PAS resins known from 0-84698 and JP-A-51-144495 can be preferably used. Among these non-crosslinked or low-crosslinked, high molecular weight PPS resins, particularly according to ASTM D1238 under a load of 316 ° C./5000 g (orifice; 0.08
25 ± 0.002 inch diameter x 0.315 ± 0.00
Melt flow rate at 1 inch length) is 800g / 1
PAS resins of 0 minutes or less are preferred.

On the other hand, a PAS resin having a high degree of crosslinking is used as the PAS resin used in the lamp reflector of the present invention. Among these PAS resins having a high degree of crosslinking, a load of 316 ° C./5000 g according to ASTM D1238 is used. A PAS resin having a lower melt flow rate (orifice; 0.0825 ± 0.002 inch diameter × 0.315 ± 0.001 inch length) of 800 g / 10 minutes or less is preferable.

Polyphenylene ether resin can be used as the polyarylene ether resin (B) of the resin composition used in the lamp reflector of the present invention.

The polyphenylene ether resin that can be used in the present invention is a generic term for homopolymers or copolymers containing, for example, one or more units represented by the following general formula 10.

[0030]

[Chemical 10]

Wherein R 2, R 3, R 4, and R 5 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbons, halohydrocarbons, hydrocarbonoxy and halohydrocarbonoxy, and l is a monomer It represents the total number of units and is an integer of 20 or more.)

The method for producing the above polyphenylene ether resin is not particularly limited, but US Pat. Nos. 3,306,874, 3,306,875, and 325.
It can be produced by the reaction of phenols by the method described in Nos. 7357 and 3257358. As these phenols, 2,6-dimethylphenol, 2,
6-diethylphenol, 2,6-dibutylphenol, 2,6-dilaurylphenol, 2,6-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6-ethylphenol, 2-methyl-6- Cyclohexylphenol, 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and 2, Includes, but is not limited to, 6-diethoxyphenol.

The polyphenylene ether resin of the present invention may be a copolymer obtained by grafting a styrene compound on the homopolymer or copolymer shown by the chemical formula 10. As the styrene compound-grafted polyphenylene ether resin, a homopolymer or a copolymer represented by the chemical formula 10 can be used as a styrene compound.
For example, it is a copolymer obtained by graft-polymerizing styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like. A preferred polyphenylene ether resin that can be used in the present invention is poly (2,6-dimethyl-
1,4-phenylene) ether.

The polyarylene ether resin (B) of the resin composition used in the lamp reflector of the present invention includes
It may contain a styrene resin.

The styrenic resin which can be contained in the present invention contains a repeating structural unit derived from a vinyl aromatic compound represented by the following general formula 11 in its polymer.
Must have at least 5% by weight.

[0036]

[Chemical 11]

(In the formula, R ₆ is hydrogen or a carbon atom number of 1 to
4 is an alkyl group, Z is halogen or a substituent which is an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5. )

Examples of such styrenic polymers include homopolymers of styrene and its derivatives and polybutadiene, polyisoprene, butyl rubber and EPD.
M, ethylene-propylene copolymer, natural rubber, a mixture of natural or synthetic elastomeric substances such as epichlorohydrin, or a styrene-based polymer modified with these, and a styrene-containing copolymer such as styrene-acrylonitrile copolymer, styrene -Butadiene copolymer, acid modified styrene-hydrogenated butadiene copolymer, epoxy modified styrene-hydrogenated butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene copolymer can be mentioned. .

Preferred styrenic resins that can be contained in the present invention are homopolystyrene, rubber-reinforced polystyrene, acid-modified styrene-hydrogenated butadiene copolymer and epoxy-modified styrene-hydrogenated butadiene copolymer.

The content ratio of the styrene resin to the polyarylen ether resin (B) is as follows: polyarylen ether resin (B) / styrene resin = 100/0 to 20 /
A range of 80 is preferred.

As a method for preparing a resin composition comprising a PAS resin (A) and a polyarylene ether resin (B) when the polyarylene ether resin (B) contains a styrene resin Is preferably a method in which the polyarylene ether resin and the styrene resin are melt-kneaded in advance, and then the melt-kneaded product and the PAS resin (A) are melt-kneaded, but the method is not limited thereto. .

The polyarylene ether resin (B) of the resin composition used in the lamp reflector of the present invention includes
Functionalization with a functionalizing agent selected from organic compounds having simultaneously (a) an ethylenic double bond and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and an epoxy group in the molecule. The resulting functionalized polyphenylene ether resin can be included.

The functionalized polyphenylene ether resin which can be contained in the present invention is the polyphenylene ether resin described above.
It can be obtained by functionalizing a tell resin with a specific functionalizing agent.

The functionalizing agent used for preparing the functionalized polyphenylene ether resin is composed of (a) an ethylenic double bond and (b) a carboxyl group, an acid anhydride group, a hydroxyl group and an epoxy group in the molecule. An organic compound having simultaneously a functional group selected from the group, specifically, maleic acid,
Α, β-unsaturated dicarboxylic acids exemplified by fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, etc .; exemplified by acrylic acid, planic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentenoic acid, angelic acid, etc. Unsaturated monocarboxylic acids; anhydrides of these α, β-unsaturated dicarboxylic acids and unsaturated monocarboxylic acids; 1 mol of the above α, β-unsaturated dicarboxylic acids and ethylene glycol, propylene glycol, tri Methylene glycol, butane-1,
Aliphatic diols such as 4-diol, tetramethylene glycol, pentaethylene glycol, etc., and hydroquinone, resorcin, catechol, m-xylylene diol
, P-xylylene diol, 4,4'-dihydroxybiphenyl ether, bisphenol A, bisphenol
Dihydroxy-α, β-unsaturated dicarboxylic acid ester having a structure derived from 2 moles of an aromatic diol such as sulfur S and bisphenol F; α, β-unsaturated dicarboxylic acid 1
Hydroxy-α having a structure derived from 1 mol of an aliphatic diol or an aromatic dihydroxy compound,
β-unsaturated dicarboxylic acid ester; derived from α, β-unsaturated dicarboxylic acid and aliphatic polyvalent alcohol such as glycerol, pentaerythritol or aromatic polyphenol such as pyrogallol A hydroxy ester having a structure represented by the formula; a hydroxy unsaturated monocarboxylic acid ester having a structure derived from 1 mol of the above unsaturated monocarboxylic acid and 1 mol of the above aliphatic diol or an aromatic dihydroxy compound; Hydroxypolyunsaturated monocarboxylic acid esters having a structure derived from a saturated monocarboxylic acid and the aforementioned aliphatic polyhydric alcohol or aromatic polyhydric phenol; the aforementioned α, β-unsaturated dicarboxylic acid or Reaction products of unsaturated monocarboxylic acids with epichlorohydrin, which are glycidyl maleates, glycidyl acrylates, glycidyl methates Unsaturated epoxy compounds exemplified by tacrylate and the like can be mentioned.

The functionalized polyphenylene ether resin that can be contained in the present invention is prepared by the following method, but is not particularly limited thereto. For example, as the functionalized polyphenylene ether resin, the polyphenylene ether resin and the functionalizing agent described above are used at 150 to 350 ° C. using a roll mill, a Banbury mixer, an extruder or the like.
Even when prepared by melt-kneading and reacting at a temperature of benzene, toluene, heating the polyphenylene ether resin and the functionalizing agent in a solvent exemplified by xylene,
It may be prepared by reacting.

In order to facilitate the functionalization reaction, organic peroxides and azo compounds such as benzoylperoxide, di-t-butylperoxide, dicumylperoxide, t-butylperoxybenzoate, etc. are used in the reaction system. The presence of a radical initiator represented by an azo compound exemplified by bisisobutyronitrile and azobisisovaleronitrile is effective. A more practical functionalization method is melt-kneading in the presence of a radical initiator.

The content of the functionalized polyphenylene ether resin in the polyarylene ether resin (B) of the resin composition used for the lamp reflector of the present invention is not limited to a specific range. In the lamp reflector made of the resin composition comprising the PAS resin (A) and the polyarylene ether resin (B), any range may be used as long as it exhibits excellent characteristics.

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

The resin composition used in the lamp reflector of the present invention may contain a phosphoric acid ester compound. Examples of the phosphate ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate,
Tritoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, phosphates obtained from a mixture of isopropylphenol and phenol, such as benzohydroquinone or bisphenol A. Mention may be made of phosphates and aromatic polyphosphates obtained from bifunctional phenols and other alcohols or phenols. A particularly preferred phosphoric acid ester compound is aromatic polyphosphate. The aromatic polyphosphate has a structure represented by the following general formula 12.

[0050]

[Chemical 12]

(Wherein R7, R8, R9, R10, R1
1 and R12 each represent a hydrogen atom or a lower alkyl group, and n represents a positive integer. )

Specific examples of the aromatic polyphosphate include cresyl resorcin polyphosphate,
Phenyl / cresyl / resorcin / polyphosphate, xylyl / resorcin / polyphosphate, phenyl / isopropylphenyl / resorcin / polyphosphate, cresyl / xylyl / resorcin / polyphosphate, phenyl / isopropylphenyl / diisopropylphenylresorcin A derivative thereof in which a substituent is introduced can be mentioned.

The phosphoric acid ester compound which can be contained in the present invention is preferably added when preparing a resin composition for a lamp reflector from the PAS resin (A) and the polyarylene ether resin (B). .

The amount of the phosphoric acid ester compound added in the present invention is the sum of the components (A) and (B) of the resin composition used in the lamp reflector of the present invention (A) + (B); 100.
It is 0.01 to 40 parts by weight, preferably 0.1 to 10 parts by weight, based on 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 Al vapor deposition film, and preferably the fatty acid Has a carbon number of 18 or more, more preferably 24 or more. When the fatty acid metal salt has less than 18 carbon atoms, the heat resistance of the metal salt itself is inferior, the effect of addition is not achieved, the strength of the lamp reflector is reduced, and the like. 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 the lamp reflector from the PAS resin (A) and the polyarylene ether 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 are used when preparing a resin composition for a lamp reflector from a PAS resin (A) and a polyarylene ether resin (B). Is preferably added to.

The resin composition used for the lamp reflector of the present invention can be used by mixing the following polymers in a range not impairing the object of the present invention. These polymers include ethylene, butylene, pentene, butadiene, isoprene,
Homopolymers or copolymers of monomers such as chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) acrylonitrile, polyurethane, polyamide,
Polybutylene terephthalate, polyesters such as polyethylene terephthalate, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyetherketone,
Polyether ether ketone, polyimide, polyamide imide, polyether imide, silicone resin, phenoxy resin, fluororesin, liquid crystal polymer, homopolymer such as polyaryl ether, random copolymer or block copolymer , Graft copolymers and the like.

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 for the lamp reflector of the present invention can be prepared by a known method. For example, PA
S resin (A) and polyarylene ether resin (B),
Furthermore, if necessary, other raw materials are uniformly mixed with a tumbler or a mixer such as a Henschel mixer,
Supply to a single-screw or twin-screw extrusion kneader and 200 ° C to 350 ° C
There is a method in which the resin composition used in the lamp reflector of the present invention is obtained as pellets by melt-kneading in the temperature range of.

However, when the poly (arylene ether) resin (B) contains a styrene resin, the poly (arylene ether) resin and the styrene resin are previously melted at 200 to 300 ° C. as described above. It is preferable that after kneading to prepare the poly (arylene ether) resin (B), the poly (arylene ether) resin (B) and the PAS resin (A) are melt-kneaded.

A molded product for a lamp reflector is molded at a molding temperature of 280 to 330 ° C. using the above-mentioned resin composition, and then a metal film is provided on the reflection surface of the molded product.

As a method for providing the metal film, there is a "dry plating" (so-called dry metal plating method), and specifically, a vacuum vapor deposition method, an ion plating method (ion plating method) or an intermediate method between them. A sputtering method, which is a technique, can be exemplified.

The vacuum vapor deposition method will be described below as an example, and its specific production method 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 to 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, since the resin surface is easily adhered to the metal film, a primer (undercoat) is not particularly required, but when the primer is not used, the ion adhesion to the substrate is excellent. It is preferable to adopt a plating method (ion plating method).

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.

[0070]

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 then 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 an autoclave of 50 liter scale in a molar ratio of 70 and sodium sulfide nonahydrate was adjusted to 0.
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 (Polyphenylene ether resin:
Production of PPE-1) 32.2 g of cupric bromide, di-n were charged in a reactor equipped with an oxygen suction device, a cooling coil, and a stirrer, which had been replaced with nitrogen.
-Butylamine (666 g) and toluene (24 liters), in which 5.25 kg of 2,6-xylenol was dissolved, were mixed and added, and the mixture was uniformly dissolved. Then, while rapidly absorbing oxygen, the inside of the reaction vessel was kept at 30 ° C for 90 minutes. Polymerized. After the polymerization was completed, 18 liters of toluene was added,
Furthermore, the reaction was stopped by adding a 20% aqueous solution of ethylenediaminetetraacetic acid. The resulting product mixture was centrifuged, the polymerized solution phase was taken out, and methanol was gradually added while stirring. After fractionation, it was dried to obtain a polyphenylene ether resin having an intrinsic viscosity of “0.50” (measured at 30 ° C. with chloroform as a solvent). This is called PPE-1.

Reference Example 4 (Production of functionalized polyphenylene ether resin: FPPE-1) Polyphenylene ether resin synthesized in Reference Example 3: "P
PE-1 ”To 3 kg of maleic acid, 90 g of maleic anhydride was added and mixed by a Henschel mixer, and then melt-kneaded at a temperature of 300 to 320 ° C. with a twin-screw extruder to form pellets. This is called FPPE-1. Obtained FPPE-1
The pellet (2 g) was dissolved in 50 ml of chloroform, and the solution was added to 500 ml of methanol to precipitate the polymer. The obtained polymer was filtered and dried (under reduced pressure, 80 ° C./10 hours).

The obtained sample was subjected to infrared spectroscopic analysis, and polyphenylene ether was prepared using a calibration curve prepared in advance from the polyphenylene ether resin and maleic anhydride.
The weight% of maleic anhydride bound to the telluric resin was calculated and used as the amount of maleic anhydride bound. As a result, FPP
The amount of maleic anhydride bound in E-1 was 1.1% by weight.

Reference Example 5 (Production of functionalized polyphenylene ether resin: FPPE-2) Polyphenylene ether resin synthesized in Reference Example 3: "P
PE-1 "3 kg of glycidyl methacrylate 90
g and 15 g of dicumylperoxide were added and mixed by a Henschel mixer, and then 300-
It was melt-kneaded and pelletized at a temperature of 320 ° C. This is F
It is called PPE-2.

2 g of the obtained FPPE-2 pellet was dissolved in 50 ml of chloroform, and this solution was added to 50 ml.
The polymer was precipitated in addition to 0 ml of methanol.
The obtained polymer was separated by filtration and dried (under reduced pressure, 80 ° C /
10 hours).

Infrared spectroscopic analysis of the obtained sample was carried out to bond it to the polyphenylene ether resin by using a calibration curve prepared in advance from the polyphenylene ether resin and glycidyl methacrylate. The weight% of glycidyl methacrylate was calculated and used as the amount of glycidyl methacrylate bound. As a result, the amount of glycidyl methacrylate bonded in FPPE-2 was 1.3% by weight.

Examples 1 to 5 and Comparative Examples 1 to 3 PAS resin (A) synthesized in Reference Example, polyphenylene ether resin, functionalized polyphenylene ether resin, and other raw materials (fibrous reinforcing material) shown in the table below. , Inorganic filler, fatty acid metal salt, etc.) in the proportions shown in the table (numerical values are parts by weight) and uniformly mixed, and then melt-kneaded and pelletized at 290 ° C. in a 35 mmφ twin-screw extruder. Got

However, the polyarylene ether resin (B) is a polyphenylene ether resin ("PPE-1").
) And a styrenic resin in the case of Example 2, a polyphenylene ether resin (“PPE-
1 ”) and a styrene resin are melt-kneaded at 260 ° C. with a 35 mmφ twin-screw extruder to prepare a polyarylenene ether resin (B), and then the polyarylen ether resin (B) is prepared. ) And PAS resin (A) were melt-kneaded by the above-mentioned method to obtain pellets (two-step production method).

Furthermore, in Example 5, polyary
The len ether resin (B) contains a polyphenylene ether resin (“PPE-1”), a styrene resin and a functionalized polyphenylene ether resin. In this case, the polyphenylene ether resin (“ PPE-
1 ") and a styrene resin are melt-kneaded at 260 ° C. in a 35 mmφ twin-screw extruder to prepare a partial intermediate of the polyarylen ether resin (B), and then the polyarylenene resin is prepared. The ter resin (B) partial intermediate, the functionalized polyphenylene ether resin (“FPPE-2”), and the PAS resin (A) were kneaded by the above-mentioned method to obtain pellets (two-step production method).

Pellets of the PAS resin (A) and the polyarylene ether resin (B) were used to form a cylinder temperature of 290 ° C. and a mold temperature of 135 ° C. using an inline screw type 3 ounce injection molding machine. Injection pressure 1000kg
Lamp reflector (mold surface roughness: 0.02 μm or less) and 100 mm × at f / cm ² , injection speed medium speed
100 mm x 2 mm (thickness) sheet (mold surface roughness:
0.02 μm or less), resin composition mechanical characteristics (including specific gravity) and warp / deformation characteristic test pieces for evaluation were molded, and various characteristics were evaluated. The results are shown in the table.

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 was vacuum-deposited to a thickness of 0.01 to 0.5 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)> Molded 100 mm ×
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 bending property measurement according to ASTM D-792 (2) Rigidity: According to ASTM D-790 Flexural strength / flexural modulus at 23 ° C and 150 ° C is 1/8 "(thickness) ×
Measured with a 1/2 "(width) x 5" (length) test piece (3) Izod impact strength: 1/8 "(thickness) x 1 / notch impact strength according to ASTM D-256 Measured with 2 "(width) x 2 1/2" (long) test piece

<Warp / Deformation Characteristics of Resin Composition> The L-shaped inclination angle; θ of a molded article formed by using the “L-shaped” warp / deformation measuring die shown in FIG. 1 was measured with a tool microscope.

The components blended in the table are as follows. 1) Styrenic resin is PST: polystyrene, trade name Dick Styrene "C
R-3500 ", manufactured by Dainippon Ink and Chemicals, Inc. AHSBR: acid-modified hydrogenated styrene butadiene rubber, trade name Tuftec" M-1913 ", manufactured by Asahi Kasei Kogyo Co., Ltd. 2) : 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-3) Inorganic filler is filler-A: Kisuma 5B, magnesium hydroxide, filler manufactured by Kyowa Chemical Industry Co., Ltd.-B: Heavy calcium carbonate, average particle size 1.6 μm filler-C: Aluminum silicate bar. − (SiO ₂ 52 wt.%,
Al ₂ O ₃ 33 wt.%, Specific gravity 2.1, average particle diameter 10 μm), manufactured by Zeelan Co. 4) Phosphate ester compound is APP-1: aromatic polyphosphate, “cresyl.
Resorcin Polyphosphate "APP-2: Aromatic Polyphosphate, Phenyl
Isopropylphenyl resorcin polyphosphate "

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

Example 6 Al was vacuum-deposited directly on a reflecting surface of a lamp reflector molded from a resin composition having the same composition as in Example 2 without applying a primer, and Al was vapor-deposited by a cross-cut peeling test. When the film adhesiveness (initial adhesiveness) was evaluated, it was 80/100. 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.

[0097]

Effect of the Invention PAS resin (A) and polyarylenene
The lamp reflector of the present invention, which is formed from a specific resin composition containing a telluric resin (B) and has a metal film on the surface serving as the reflection surface of the molded article, has good surface smoothness and high temperature at high temperature. In addition to having rigidity, it also has excellent adhesion to the resin surface, especially at high temperatures / humidity, excellent warpage / deformation characteristics during injection molding, and can be made lighter. It retains a high level of practicality / functionality.

[Brief description of drawings]

FIG. 1 shows an “L-shaped” measuring mold for evaluating the warp / deformation characteristics of a resin composition used in the lamp reflector of the present invention.

FIG. 2 shows measurement points of L-shaped inclination angle; θ of a molded product molded using a “L-shaped” warp / deformation measurement mold.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // B32B 27/00 A 7344-4F 103 N 7344-4F

Claims (14)

[Claims] 1. A resin composition containing a poly (arylene sulfide) resin (A) and a poly (arylene ether) resin (B) is molded, and a metal film is formed on the surface of the molded product to be the reflection surface. A lamp reflector characterized by being provided. 2. A resin composition containing a polyarylenylene sulfide resin (A) and a polyarylenene ether resin (B) is molded, and a primer is applied to the reflection surface of the molded product. The lamp reflector is characterized by being provided with a metal film. 3. The lamp reflector according to claim 1, wherein the polyarylene ether resin (B) is a polyphenylene ether resin. 4. The polyarylene ether resin (B) further contains a styrene resin.
The described lamp reflector. 5. The lamp reflector according to claim 4, wherein the resin composition is obtained by melt-kneading a melt-kneaded product of a polyarylene ether resin and a styrene resin and (A). 6. A polyarylene ether resin (B)
Is a functionalizing agent selected from an organic compound having at least one functional group selected from the group consisting of (a) ethylenic double bond and (b) carboxyl group, acid anhydride group, hydroxyl group and epoxy group in the molecule. A lamp reflector according to claim 1, 2, 3, 4 or 5, containing a functionalized polyphenylene ether resin obtained by functionalization. 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 lamp reflector according to claim 1, further comprising a phosphoric acid ester compound. 13. A resin composition containing a polyarylene sulfide resin (A) and a polyarylene ether resin (B) is molded, and a metal film is formed on the surface of the molded product which is to be the reflecting surface. A method for manufacturing a lamp reflector, which is characterized by being provided. 14. A resin composition containing a poly (arylene sulfide) resin (A) and a poly (arylene ether) resin (B) is molded, and a primer is applied to the surface of the molded product to be the reflection surface. And then providing a metal film.