JPH11241006A - Optical reflector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide at a low cost an optical reflector having a good moldability, surface property, heat resistance, adhesion and brightness after aging by directly metallizing a molded part comprising a polyester resin composition. SOLUTION: The objective reflector is obtained by directly metallizing a molded part comprising a polyester resin composition which contains, against 100 pts.wt. mixed resin comprising (a) from 95 to 50 wt.% polyalkylene terephthalate resin and (b) from 5 to 50 wt.% polycarbonate resin, (c) from 0.03 to 3 pts.wt. modified silicone oil, (d) from 0.01 to 0.5 pts.wt. organic phosphorus compound, (e) from 0.1 to 10 pts.wt. fine powder filler and (f) from 0.01 to 0.5 pts.wt. organic nucleating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a light reflector,
Specifically, the present invention relates to a light reflector made of a polyester resin composition.

[0002]

2. Description of the Related Art Light reflectors include, for example, reflectors and extensions which are members for automobile headlamps. As a material for the reflector and the extension, BMC (bulk molding compound), which is a thermosetting resin, is used instead of steel.
BMC has excellent properties such as heat resistance, rigidity, and dimensional stability, but has problems such as a long molding cycle, burrs occurring during molding, and easy volatilization of monomers during molding. .

[0003] In order to solve such problems, studies have been made to use a thermoplastic resin. For example, Japanese Patent Application Laid-Open No. 61-133234 proposes a method in which a fine powder filler is used as a reinforcing material in polyalkylene terephthalate, but the surface property is insufficient due to embossment of the filler and poor mold release. Kaihei 7-90163
In the publication, polycyclohexylene dimethylene terephthalate polyester resin and polyether amide and / or
Alternatively, a resin composition comprising a polyetherester and an organic phosphite has been proposed, but when a primer is not used on the surface of a molded article, the surface properties are not always satisfactory. The light reflector is generally subjected to a primer treatment on the surface of a molded article, and metal is deposited thereon. Therefore, even if the molded product surface has some irregularities, the surface is smoothed by the primer, and the metal deposition surface can maintain high glossiness,
When the primer treatment is performed, the process cost is greatly increased.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article made of a polyester resin composition by direct metal vapor deposition and to have excellent moldability, surface properties, heat resistance, adhesiveness and luminance after aging. It is to provide a light reflector at a low cost.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and the gist of the invention is as follows.
(A) Polyalkylene terephthalate resin 95 to 50
(C) 0.03 to 3 parts by weight of a modified silicone oil, and (d) 0.01 to 0 parts by weight of an organic phosphorus compound, based on 100 parts by weight of a mixed resin composed of 5% to 50% by weight of (b) a polycarbonate resin. 0.5 parts by weight, (e) 0.1 to 10 parts by weight of fine powder filler, and (f) 0.01 to 10 parts by weight of organic nucleating agent.
A light reflector characterized by being directly metal-deposited on a molded article comprising a polyester resin composition containing 0.5 parts by weight.

Hereinafter, the present invention will be described in detail. Examples of the (a) polyalkylene terephthalate resin in the present invention include polyalkylene terephthalate, copolyesters of alkylene terephthalate, and mixtures of polyalkylene terephthalate. The polyalkylene terephthalate comprises a diol component and terephthalic acid. As the diol component, ethylene glycol,
1,4-butanediol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, cyclohexanedimethanol, 2,2-bis (2'-hydroxyethoxyphenyl) propane, etc. And preferably polybutylene terephthalate.

[0007] The copolyester of alkylene terephthalate is a copolyester having an alkylene terephthalate structural unit as a main structural unit. Copolyesters composed of dicarboxylic acids are exemplified. As dicarboxylic acids other than terephthalic acid, isophthalic acid,
Naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylether dicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid, dimer acid and the like.

Specific examples of the copolyester of alkylene terephthalate include, for example, polybutylene terephthalate / isophthalate, polyethylene terephthalate / isophthalate and the like, preferably polybutylene terephthalate / isophthalate. As a mixture of polyalkylene terephthalate, for example,
A mixture of polybutylene terephthalate and a polyalkylene terephthalate other than polybutylene terephthalate,
Examples include a mixture of polybutylene terephthalate and a copolyester of alkylene terephthalate, and preferably, a mixture of polybutylene terephthalate and polyethylene terephthalate, and a mixture of polybutylene terephthalate and polybutylene terephthalate / isophthalate.

The intrinsic viscosity of the polyalkylene terephthalate is preferably from 0.5 to 1.5. The intrinsic viscosity of the copolyester of alkylene terephthalate is preferably from 0.5 to 1.5. The intrinsic viscosity of polybutylene terephthalate is preferably from 0.6 to 1.4.
The intrinsic viscosity of polyethylene terephthalate is preferably 0.6 to 1.0, and the intrinsic viscosity of polybutylene terephthalate / isophthalate is preferably 0.8 to 1.0.
１1.3. Intrinsic viscosity is measured in a 1: 1 (weight ratio) solvent of phenol and tetrachloroethane at a temperature of 30 ° C.

The polycarbonate resin (b) in the present invention may be an aromatic dihydroxy compound or a polycarbonate polymer which may be made by reacting an aromatic dihydroxy compound or a small amount of the polyhydroxy compound with phosgene or a diester of carbonic acid. Polymers. As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-
(Hydroxyphenyl) -P-diisopropylbenzene,
Examples thereof include hydroquinone, resorcinol, and 4,4-dihydroxydiphenyl, and preferably include bisphenol A.

In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,4
6-tri (4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-3,1,
3,5-tri (4-hydroxyphenyl) benzene,
Polyhydroxy compounds represented by 1,1,1-tri (4-hydroxyphenyl) ethane or 3,3-
Bis (4-hydroxyaryl) oxindole (=
Isatin bisphenol), 5-chlorisatin, 5,
7-dichlorisatin, 5-bromoisatin and the like may be used as a part of the aromatic dihydroxy compound,
The amount used is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

In order to control the molecular weight, a monovalent aromatic hydroxy compound may be used, and m- and p-methylphenol, m- and p-propylphenol, p-tert
-Butylphenol and p-long-chain alkyl-substituted phenol. As the aromatic polycarbonate resin, preferably, a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane,
Or a polycarbonate copolymer derived from 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound.

As the polycarbonate resin, a mixture of two or more resins may be used. The molecular weight of the polycarbonate resin is 15,000 to 30,000, preferably 16,000 to 25,000 as a viscosity average molecular weight calculated from solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. is there. The mixed resin in the present invention is a polyalkylene terephthalate resin 95
-50% by weight and 5-50% by weight of a polycarbonate resin. 95 polyalkylene terephthalate resin
If the content is more than 5% by weight, poor appearance such as a flow mark tends to occur, and if less than 5% by weight, heat resistance is insufficient and the appearance after heating is inferior. The mixed resin in the present invention preferably comprises 90 to 55% by weight of a polyalkylene terephthalate-based resin and 10 to 45% by weight of a polycarbonate resin.

Examples of the modified silicone oil (c) in the present invention include a silicone oil having an organic group introduced into the side chain of polysiloxane, and a silicone oil having an organic group introduced at both ends and / or one end of the polysiloxane. Can be As the organic group, an epoxy group, an amino group,
Examples thereof include a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group.

As the modified silicone oil, preferably, an epoxy-modified silicone oil in which an epoxy group is introduced into a side chain of polysiloxane is used. The blending amount of the modified silicone oil is 0.1 to 100 parts by weight of the mixed resin.
03 to 3 parts by weight. If the compounding amount is less than 0.03 parts by weight, surface properties are reduced due to poor mold release during injection molding,
If the amount is more than 3 parts by weight, the workability of kneading the modified silicone oil is reduced, and clouding of the surface of the molded article due to the unreacted material floating during aluminum deposition is observed. The blending amount of the modified silicone oil is preferably 0.05 to 2.5 parts by weight, more preferably 0.1 to 2 parts by weight.
Examples of the organic phosphorus compound (d) in the present invention include an organic phosphate compound, an organic phosphite compound, an organic phosphonite compound, and the like. As the organic phosphate compound, preferably,

[0016]

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(Wherein, R ¹ represents an alkyl group having 8 to 30 carbon atoms). Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triancotyl and the like. . As the organic phosphite compound, preferably,

[0018]

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(Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms or a C ⁶ to C ⁴
30 aromatic groups, and at least one of R ² , R ³ and R ⁴ is an aromatic group having 6 to 30 carbon atoms. )
The compound represented by these is mentioned. Specific examples of the organic phosphite compound include tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-
t-butylphenyl) 4,4'-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4'-butylidene-bis (3 -Methyl-6-
t-butylphenyl-di-tridecyl) phosphite,
1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite , 4,
4'-isopropylidenebis (phenyl-dialkylphosphite) and the like, and tris (2,4-di-t
-Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di- Phosphite and the like. As the organic phosphonite compound, preferably,

[0020]

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Wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms or an aromatic group having 6 to 30 carbon atoms, and R ⁵ , R ⁶ and At least one of R ⁷ is an aromatic group having 6 to 30 carbon atoms). Specific examples of the organic phosphonite compound include tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite. The organic phosphorus compound is preferably an organic phosphate compound.

The compounding amount of the organic phosphorus compound is 0.01 to 0.1.
5 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the heating stability and retention stability of the material is reduced, and if it exceeds 0.5 part by weight, other performances are adversely affected. The compounding amount of the organic phosphorus compound is 10
The amount is preferably 0.05 to 0.3 parts by weight, more preferably 0.1 to 0.2 parts by weight, based on 0 parts by weight. These organic phosphorus compounds may be used alone or in combination of two or more.

The fine powder filler (e) in the present invention includes, for example, quartz, talc, kaolin, mica, clay, hydrotalcite, mica, graphite, glass beads,
Calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, magnesium carbonate, magnesium sulfate, calcium silicate, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, calcium titanate, magnesium titanate, barium titanate, and the like. Can be used in combination of two or more. Preferably, talc is used. The fine powder filler may be subjected to a surface treatment as needed. The average particle size of the fine powder filler is preferably 20 μm or less, more preferably 10 μm or less.

The compounding amount of the fine powder filler is 10
0.1 to 10 parts by weight with respect to 0 parts by weight. If the compounding amount is less than 0.1 part by weight, the crystallization rate is low, so that the molding cycle is slow and the productivity is not sufficient. If the compounding amount exceeds 10 parts by weight, a relatively large amount of filler emerges on the surface of the molded product. The gloss after aluminum deposition is not sufficient. The compounding amount of the fine powder filler is preferably 0.2 to 8 parts by weight, more preferably 0.3 to 6 parts by weight.

In the present invention, (f) the organic nucleating agent includes
Organic alkali salts are preferred, for example, sodium benzoate, sodium montanate, calcium montanate, lithium montanate, sodium phosphate, sodium sulfonate, sodium antimonate, maleic anhydride copolymer Examples thereof include a sodium salt and a sodium borohydride salt, and two or more of these can be used in combination. The organic nucleating agent preferably includes montanic acid sodium salt.

The compounding amount of the organic nucleating agent is 0.01 to 0.5 parts by weight. If the amount is less than 0.01 part by weight, the crystallization rate is low, so that the appearance after aging is insufficient. If the amount exceeds 0.5 part by weight, the decomposition of the material is accelerated, and the performance is reduced and discoloration is caused. Bring. The compounding amount of the organic nucleating agent is preferably 0.03 to 0.3 parts by weight, more preferably,
It is 0.05 to 0.15 parts by weight.

By blending an appropriate amount of the organic nucleating agent, the crystallization speed of the molded article is further increased, and the dimensional change after aging is reduced, and the brightness of the surface gloss is maintained. The polyester resin composition in the present invention is a normal additive as long as the object of the present invention is not impaired,
For example, it may contain a coloring agent containing a dye and a pigment, a fibrous reinforcing agent, a lubricant, a flame retardant, an antistatic agent, an antibacterial agent and the like.

A molded article made of the polyester resin composition is usually molded by an injection molding method. The light reflector of the present invention can be obtained by directly depositing a metal on the surface of a molded article made of a polyester resin composition. Examples of the metal vapor deposition method include a method of evaporating a metal in a vacuum, attaching the vapor to the surface of a molded article, and solidifying the vapor to form a metal thin film.

As the metal to be deposited, for example, chromium,
Nickel, aluminum and the like can be mentioned. The metal deposition is preferably aluminum deposition. The surface of the molded article according to the present invention is smooth and good, and good gloss can be obtained even when metal is directly vapor-deposited without applying a primer treatment to the molded article. However, if the releasability of the molded article is poor during injection molding, transfer unevenness occurs, and the surface properties of the molded article are impaired. When a wax-based release agent is used to improve the releasability, the releasability is improved, but the adhesiveness to the metal deposition body is reduced.

The molded article made of the polyester resin composition according to the present invention has excellent mold release properties and excellent adhesion to a metal deposition without a primer treatment. Note that the surface of the molded article may be cleaned and degreased prior to vapor deposition in order to increase the adhesive strength. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[0031]

The following components were used in these Examples and Comparative Examples. (1) Polybutylene terephthalate: 5008AS, Mitsubishi Engineering Plastics Co., Ltd., intrinsic viscosity 0.85 (hereinafter also referred to as PBT) (2) Polycarbonate: 7022A, Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 2100
0 (hereinafter also referred to as PC) (3) Epoxy-modified silicone oil: manufactured by Shin-Etsu Silicon Co., Ltd., KF102, viscosity 4000 cST (hereinafter also referred to as modified silicone oil) (4) Organic phosphate compound: long-chain dialkyl acid phosphate

(5) Talc: manufactured by Nippon Mistron Co., Ltd.
Mistron Vapor Super Differentiator, average particle size 0.3 μm (6) Organic alkali salt: manufactured by Client Co., Ltd., sodium montanate, NaV101 (7) Pigment: manufactured by Rombic Co., gray The test method is as follows Followed. (8) Releasability: The resistance to taking out a molded product from the cavity during injection molding was judged based on the sense of hand removal.
：: The molded product can be removed without resistance. Δ: Some resistance is felt in taking out the molded product. X: A remarkable resistance is felt in taking out the molded product.

(9) Reflectance: Measured using a spectrophotometer. (10) Reflectivity after aging: 150 ° C. with hot air dryer
The reflectivity of the sample subjected to the heat treatment of × 24Hr, 160 ° C. × 24Hr was measured. (11) Tape peeling property: A scratch was made on the surface on which aluminum was deposited with a knife, a cellophane tape was stuck thereon, and the adhesiveness when the cellophane tape was peeled was evaluated.
：: Almost no peeling of the aluminum deposited film was observed. △:
Some peeling of the aluminum deposited film is observed. X: The peeling of the aluminum deposition film is remarkable.

(12) Molding cycle: A molding cycle including an injection time, a cooling time and a metering time. ○: 5
Less than 0 seconds. Δ: 50 seconds or more and less than 60 seconds. X: 60 seconds or more. (13) TC: Measured using DSC. The measurement conditions are
Starting from 30 ° C., at a heating rate of 20 ° C./min.
The temperature was raised to 0 ° C., held for 3 minutes after reaching 300 ° C., and lowered from 300 ° C. to 20 ° C./min at 30 ° C.
The crystallization temperature (TC) was measured when the temperature was lowered to the maximum. (14) The luminance of the light reflector after aging was visually evaluated. ：: Excellent whiteness with almost no whitening. △:
Some whitening is observed, but the brightness is good. X: Whitening was observed and the luminance was poor.

Example 1 70 parts by weight of PBT, 30 parts by weight of PC, 0.2 parts by weight of modified silicone oil,
0.15 parts by weight of an organic phosphate compound, 3.0 parts by weight of talc and 0.06 parts by weight of an organic alkali salt, and further, 0.3 parts by weight of a pigment are thoroughly dry-blended with a tumbler, and then 250 ° C. Was pelletized at an extrusion speed of 15 kg / hr using a twin-screw extruder set to 1. The obtained pellets were heated at 120 ° C. for 12 hours before injection molding.
r dried, using an injection molding machine with a mold clamping force of 75 tons,
Molding temperature 250 ° C, molded product shape 100mm x 100m
Molding was performed at a mold temperature of 110 ° C. using a mirror mold of m × 3 mm.

The releasability at the time of injection molding was good, and the molded product could be taken out without resistance. The molded article was subjected to aluminum vapor deposition without performing a primer treatment, and then evaluated. As for the surface properties, the surface gloss was clear and the reflectance was high. 24 hours at 150 ° C and 160 ° C
After aging for 24 hours, the surface properties hardly changed, and the brightness was excellent. The aluminum adhesion was evaluated by peeling off the tape, but almost no peeling of the aluminum vapor-deposited film was observed, and the adhesion was good.

[Examples 2 and 3] As shown in Table 1,
Except that the composition of the resin composition was changed, pelletization and molding were performed in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 1. Comparative Examples 1 and 2 Pelletization and molding were performed in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1, and various evaluations were made. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

The light reflector of the present invention is directly metal-deposited on a molded article made of a polyester resin composition, so that the production process is simplified, and a product of low cost and stable quality can be obtained. Further, the molding cycle of the molded article is short, and the productivity in the molding process is excellent. The light reflector of the present invention has excellent surface properties, heat resistance, adhesiveness, and luminance after aging, and is particularly suitable for applications such as reflectors for automobile headlamps and extension members.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83:16) (C08K 13/04 5:51 7:00 5:00) (72) Inventor Toshiyuki Furuya Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture 5-6-1, Mitsubishi Engineering Plastics Co., Ltd. Technology Center

Claims (10)

[Claims] 1. A modified silicone oil of 0.03% based on 100 parts by weight of a mixed resin consisting of (a) 95 to 50% by weight of a polyalkylene terephthalate resin and (b) 5 to 50% by weight of a polycarbonate resin. To 3 parts by weight, (d) 0.01 to 0.5 parts by weight of an organic phosphorus compound, (e) 0.1 to 10 parts by weight of a fine powder filler, and (f) 0.01 to 0.5 part by weight of an organic nucleating agent. A light reflector characterized by being directly metal-deposited on a molded article comprising a polyester resin composition. 2. The polyalkylene terephthalate-based resin (a) is polyalkylene terephthalate, a copolyester of alkylene terephthalate or a mixture of polyalkylene terephthalate.
3. The light reflector according to 1. 3. The light reflector according to claim 2, wherein the alkylene terephthalate is polybutylene terephthalate. 4. The light reflector according to claim 2, wherein the alkylene terephthalate copolyester is a polybutylene terephthalate / isophthalate copolyester. 5. The method according to claim 1, wherein (b) the polycarbonate resin is a polycarbonate polymer or a copolymer prepared by reacting bisphenol A with phosgene or a carbonic acid diester. Light reflector. 6. The light reflector according to claim 1, wherein (c) the modified silicone oil is an epoxy-modified silicone oil. 7. The method according to claim 1, wherein (d) the organic phosphorus compound is an organic phosphate compound, an organic phosphite compound or an organic phosphonite compound.
The light reflector according to any one of the above. (E) the fine powder filler has an average particle diameter of 20;
The light reflector according to any one of claims 1 to 7, wherein the light reflector is a fine powder filler having a size of not more than μm. 9. The light reflector according to claim 1, wherein (f) the organic nucleating agent is an organic alkali salt. 10. The light reflector according to claim 1, wherein the metal deposition is aluminum deposition.