JP5316716B2 - Thermoplastic polyester resin composition and light reflector using the same - Google Patents

Description

  The present invention relates to, for example, a thermoplastic polyester resin composition used for a light reflector part in which a light reflecting layer is provided on the surface of a part constituting an automotive lamp or a lighting fixture, and a light reflection formed by molding the thermoplastic polyester resin composition. The present invention relates to a body part and a light reflector in which a light reflecting metal layer is directly formed on a part or the whole of the light reflector part.

  Conventionally, light reflectors such as extensions and reflectors used in automobile lamps and lighting fixtures have high luminance appearance (smoothness), uniform reflectivity, and heat resistance against heat generated by light from the light source. Etc. are required. Conventionally, such products have been provided with a metal thin film on the surface of a bulk molding compound (hereinafter abbreviated as BMC) which is a thermosetting resin.

  Although BMC is excellent in heat resistance, dimensional stability, etc., the molding cycle is long, and it takes time to process burrs during molding. There was a problem. As means for improving these problems, studies using thermoplastic resins have been conducted.

  As an example of using a thermoplastic resin, a composition in which various reinforcing materials are blended with a crystalline resin typified by a polyester resin such as polybutylene terephthalate or polyethylene terephthalate, or an amorphous resin typified by a polycarbonate resin. Has been proposed. In particular, for light reflectors that require mechanical properties, electrical properties, heat resistance, good moldability, etc., various reinforcing materials are applied to polybutylene terephthalate resin alone or a mixture of polybutylene terephthalate and other resins. The blended composition is widely adopted.

  As a technique for forming a metal thin film or the like to give a performance as a light reflector to a molded article made of the thermoplastic resin composition described above, pretreatment by undercoat treatment before forming a light reflective metal layer on the molded article The method of performing is mentioned. In the conventional method for performing the undercoat treatment, since an organic solvent is used in the undercoat, the burden on the environment is large. Further, the organic solvent volatilizes and the coat needs time to be cured. The cost for the process is high, and the total cost is a problem. Therefore, there is a need for a thermoplastic resin composition for a light reflector that does not require a pretreatment step and that can be directly formed by directly forming a metal layer.

  When performing direct vapor deposition by the direct method, it is necessary that the resin molded product itself has good surface smoothness, high glossiness, and brightness. In addition, it is necessary to highly control the heat resistance of the resin and the suppression of gas generation (low gasity) at the time of molding from the application. For example, Patent Documents 1 and 2 propose resin compositions that can be vapor-deposited by the direct method. However, Patent Document 1 has very high levels in all of the material surface, the mold surface, and the molding surface. Since it is necessary, the present situation is that it has not yet been widely adopted in molded products having very complicated shapes.

  In particular, the blending of inorganic fillers has been studied in order to improve the heat resistance described above, but this causes the filler to float on the resin surface and impairs the smoothness of the surface. For example, in Patent Document 3, surface smoothness is maintained by blending about 10 parts by mass of finely divided spherical inorganic fillers such as calcined kaolin, barium sulfate, and titanium oxide. However, there is a problem that the heat resistance is reduced due to the aggregation of fillers and the amount of resin with a slow crystallization rate for maintaining good appearance, such as polyethylene terephthalate, increases.

  On the other hand, automotive lamp parts, etc., are often complicated in shape, and in particular, direct vapor deposition molds have mirror molds that have been polished at a level of # 10000 or higher for the purpose of obtaining a smooth surface. In particular, there is a high possibility that mold release defects will occur during molding. Therefore, a release agent is always blended in the resin. Of course, although the mold release property is improved by adding a mold release agent, the mold becomes dirty due to the mold release agent itself becoming a gas and bleeding out, and the range of 100 ° C. to 200 ° C. In such a temperature environment, there are problems that adhesive gas is generated from the light reflector and the lens cover or mirror is fogged (fogging), or the glossiness is lowered by bleeding out of the additive.

  In addition, a long-chain fatty acid ester-based release agent composed of montanic acid, which is a long-chain fatty acid having a chain length of about C28, is effective for release and has been generally used as a release agent. However, montanic acid is a fatty acid that uses natural resources extracted from mines as a raw material, and there is always the danger of depletion. On the other hand, fatty acids such as behenic acid, stearic acid, lauric acid and the like having a short fatty acid chain length are plant-derived fatty acids and can be supplied at low cost and stably. Therefore, a shift to a release agent different from the montanic acid type release agent has been screamed recently.

JP 2008-280498 A JP 2009-102581 A JP 2009-235156 A JP 2005-97563 A

  In the above-mentioned prior literature, a mold release agent has been studied. However, Documents 1 and 2 have been examined especially for mold dirt and gas. Due to the effect of using a highly controlled mold release agent, the mold release agent is used. In some cases, the properties were insufficient. Moreover, about literature 3, there exists a concern about the contamination to a metal mold | die by the influence which uses the fatty-acid metal salt. Furthermore, for Reference 4, a fatty acid ester in which a fatty acid is ester-bonded to only one of the hydroxyl groups of glycerin is blended, but this additive is very volatile because there are many remaining hydroxyl groups, and gas, mold contamination The impact on is great. Therefore, the direct method has not been studied at a very high level with respect to releasability, low mold contamination, fogging property, and bleed-out property. The object of the present invention is to not only have good releasability when molding resin light reflector parts by injection molding or the like, but also to reduce mold contamination by suppressing gas generation and molding It is an object of the present invention to provide a resin composition capable of obtaining a resin molded body that highly suppresses bleed-out to the product surface and also has good heat resistance. It is another object of the present invention to provide a light reflector that has low fogging performance and can maintain a high luminance feeling even when exposed to a high temperature atmosphere.

  As a result of intensive studies, the present inventors have used a release agent and a carbodiimide compound having a specific structure in order to satisfy many properties such as releasability and low gasity as properties necessary for the light reflector. As a result, the inventors have found that the object can be achieved and completed the present invention.

That is, the present invention is as follows.
[1] (C) All hydroxyl groups of (C) polyglycerol with respect to 100 parts by mass of polyester resin containing (B) 0-50 parts by mass of polyethylene terephthalate resin with respect to 100-50 parts by mass of polybutylene terephthalate resin the polyglycerol fatty acid ester 0.05 to 5 parts by mass formed by fatty acid binding, (D) an aliphatic or alicyclic polycarbodiimide compounds 0.05 to 5 parts by mass of (E) free machine filler 0-20 A thermoplastic polyester resin composition , which contains part by mass and contains an inorganic filler, the inorganic filler being an inorganic filler having an average particle size of 3.0 μm or less .
[2] The thermoplastic polyester resin composition according to [1], wherein the polyglycerol which is a constituent component of the (C) polyglycerol fatty acid ester is triglycerol and the fatty acid is behenic acid.
[3] The thermoplastic polyester resin composition according to [1] or [2], wherein the (D) aliphatic or alicyclic polycarbodiimide compound has an isocyanate group at the terminal.
[4] The thermoplastic polyester resin composition according to any one of [1] to [3], wherein (E) the inorganic filler contains two or more of talc, barium sulfate, calcium carbonate, and titanium dioxide.
[5] A light reflector part molded using the thermoplastic polyester resin composition according to any one of [1] to [4].
[6] A light reflector in which a light-reflecting metal layer is directly formed on at least a part of the surface of the component for light reflector according to [5].

  According to the resin composition of the present invention, excellent mold releasability and heat resistance can be achieved while reducing mold contamination by suppressing gas generation when molding a light reflector part made of resin by injection molding or the like. Therefore, it is possible to obtain a resin molded body that has high performance and highly suppresses bleed-out to the surface of the molded product, so that a high brightness feeling can be maintained even when exposed to a high temperature atmosphere.

Hereinafter, the present invention will be described in detail.
The (A) polybutylene terephthalate resin used in the present invention is a general polycondensation reaction mainly composed of terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. It is a polymer obtained by a polymerization method. The butylene terephthalate repeating unit is preferably a polymer having 80 mol% or more, the butylene terephthalate repeating unit is more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol%. Other copolymer components may be included in a range that does not impair the characteristics, for example, about 20% by mass or less. Examples of copolymers include polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), poly (butylene) / Ethylene) terephthalate, etc., may be used alone or in combination of two or more.

  The (A) polybutylene terephthalate resin used in the present invention preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when an o-chlorophenol solution is measured at 25 ° C. It is more preferred that it is in the range of .52 to 1.25 dl / g, more preferred is that in the range of 0.58 to 1.12 dl / g, and 0.62 to 1.02 dl / g. Are most preferred. When the intrinsic viscosity of (A) is 0.36 to 1.60 dl / g, the mechanical properties and moldability of the thermoplastic polyester resin composition of the present invention are improved.

  The (B) polyethylene terephthalate resin used in the present invention is a polymer obtained by an ordinary polymerization method such as a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and ethylene glycol or an ester-forming derivative thereof. It is a coalescence. The ethylene terephthalate repeating unit is preferably a polymer having 80 mol% or more, and the ethylene terephthalate repeating unit is more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol%. Other copolymer components may be included in a range that does not impair the characteristics, for example, about 20% by mass or less. Examples of copolymers include polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polyethylene (terephthalate / decanedicarboxylate), polyethylene (terephthalate / naphthalate), poly (ethylene) / Cyclohexanedimethyl) / terephthalate, poly (butylene / ethylene) terephthalate, and the like, and may be used alone or in combination of two or more. By using the (B) polyethylene terephthalate resin, the moldability and the direct metal vapor deposition property can be made higher compatible.

  The (B) polyethylene terephthalate resin used in the present invention preferably has an intrinsic viscosity of 0.30 to 1.60 dl / g when an o-chlorophenol solution is measured at 25 ° C., 0.45 to 1 Those in the range of .35 dl / g are more preferred, those in the range of 0.50 to 1.20 dl / g are more preferred, and those in the range of 0.55 to 1.05 dl / g are preferred. Most preferred. When the intrinsic viscosity of (B) is 0.30 to 1.60 dl / g, the mechanical properties and moldability of the thermoplastic polyester resin composition of the present invention are improved.

The blending amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin in the present invention is 0 to 50 parts by mass of (B) polyethylene terephthalate resin with respect to 100 to 50 parts by mass of (A) polybutylene terephthalate resin. Preferably, (A) 100 to 60 parts by mass, (B) 0 to 40 parts by mass, more preferably (A) 90 to 70 parts by mass, and (B) 10 to 30 parts by mass, more preferably Is (B) 15-25 parts by mass with respect to (A) 85-75 parts by mass. (B) Although it is possible to improve the surface appearance of the resin composition by blending the polyethylene terephthalate resin, if the blending amount exceeds 50 parts by mass, the releasability at the time of injection molding of the resin composition is poor and molding high cycle The heat resistance of the resin tends to decrease.
In the present invention, the total amount of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin in the polyester resin is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. 100 mass%.

  (C) Polyglycerin fatty acid ester in which fatty acids are bonded to all hydroxyl groups of polyglycerin used in the present invention acts as a release agent, and forms a slippery film on the surface of the molded product during molding. As a result, good releasability is exhibited.

  The polyglycerol fatty acid ester is composed of a polyglycerol component and a fatty acid component. Examples of the polyglycerol component include diglycerol, triglycerol, and tetraglycerol. Polyglycerin higher than tetraglycerin does not exhibit sufficient releasability due to the increased molecular weight. Among diglycerin and triglycerin, triglycerin is superior in volatility and bleed-out resistance.

  Examples of fatty acid components constituting the polyglycerin fatty acid ester include linear higher fatty acids such as stearic acid (carbon number 18), behenic acid (carbon number 22), and montanic acid (carbon number 28). Of these, long chain fatty acids of behenic acid or higher are preferable from the viewpoints of releasability, mold contamination, and molecular weight of the release agent, and behenic acid is more preferable because of its excellent supply stability.

  The configuration of the polyglycerol fatty acid ester varies depending on the number of fatty acids bonded to the hydroxyl group of the polyglycerol. For example, diglycerin is diglycerin monoester, diglycerin diester, diglycerin triester, diglycerin tetraester (diglycerin full ester). When fatty acids are not bonded to all the hydroxyl groups of polyglycerol, since the hydroxyl groups remain, the volatility of the polyglycerol fatty acid ester becomes very large, increasing mold contamination and deteriorating fogging performance. Polyglycerin fatty acid ester (polyglycerin fatty acid full ester) in which fatty acids are bonded to all hydroxyl groups of polyglycerin has low volatility, does not cause mold contamination, and improves fogging performance.

In the present invention, when a triglycerin pentabehenate ester in which behenic acid is bonded to all hydroxyl groups of triglycerin is used, the resulting resin composition has excellent releasability, and at the same time, low fogging property, Low mold contamination and bleed-out resistance.
The content of the (C) polyglycerin fatty acid ester is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts per 100 parts by mass of the polyester resin containing (A) and (B). Part by mass, more preferably 0.1 to 1 part by mass. If it is less than 0.05 parts by mass, sufficient releasability cannot be exhibited, and if it exceeds 5 parts by mass, bleeding out and gas generation increase, and the object of the present invention cannot be achieved.

  As described above, the polyglycerin fatty acid ester in which (C) a fatty acid is bonded to all the hydroxyl groups of polyglycerin has excellent release properties, low gas properties, and bleed-out resistance even when used alone. It is also extremely effective to use a release agent other than (C) in combination with the thermoplastic polyester resin composition in a range that does not adversely affect the properties required for the light reflector produced by the direct vapor deposition method. is there.

The (D) aliphatic or alicyclic polycarbodiimide compound used in the present invention is one of compounds having a carbodiimide group which is a carboxylic acid reactive group in one molecule, and promotes the reduction of gas in the resin composition. .
(D) The aliphatic or alicyclic polycarbodiimide compound is preferably a compound having a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule. Such a compound having a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule can exhibit the property of capturing a carboxylic acid compound or a hydroxyl group-containing compound produced during the decomposition of the fatty acid ester.

  Since free carboxylic acid compounds such as fatty acids and hydroxyl group-containing compounds generated by the decomposition of the fatty acid ester compound greatly affect the generation of gas, the compound to be added is preferably a compound that reacts rapidly with the carboxylic acid and the hydroxyl group. The main purpose of adding these is to immediately supplement the free acid and free hydroxyl group-containing compound contained in the fatty acid ester compound, the free acid and free hydroxyl group-containing compound generated during the subsequent heat treatment and use at high temperatures, and volatilize. Is to prevent. In particular, free carboxylic acid volatilizes at a relatively low temperature, and the volatiles crystallize, so that it often causes fogging. Therefore, capture of free carboxylic acid is extremely important.

  Examples of the functional group that reacts with the carboxylic acid include a glycidyl group, an oxazoline group, an oxetane group, and a carbodiimide group. However, general glycidyl group-containing compounds, oxazoline group-containing compounds, and oxetane group-containing compounds do not react quickly, and it may be difficult to coexist with a functional group that reacts with a hydroxyl group. Due to the intense nature, it is often difficult to use for this purpose. On the other hand, carbodiimide compounds have a faster reaction than glycidyl groups, oxazoline groups, and oxetane groups, and are highly preferred for use in capturing free carboxylic acids. The functional group that reacts with a hydroxyl group is different from the functional group that reacts with a carboxylic acid, and examples thereof include an isocyanate group and an acid anhydride group, and an isocyanate group is particularly preferred from the viewpoint of reactivity. As a result of extensive studies, the compound having a carboxylic acid group-reactive group and a hydroxyl group-reactive group in one molecule is most preferably a compound having a carbodiimide group and an isocyanate group in one molecule. In addition, the purpose of containing a carboxylic acid group reactive group and a hydroxyl group reactive group in one molecule is that these functional groups can easily react with both a thermoplastic resin and a fatty acid ester decomposition product, and have a large molecular weight. This is because the volatilization of the fatty acid ester decomposition product can be significantly reduced by connecting the plastic resin and the decomposition product with a reactive compound. Therefore, in the case of a thermoplastic polyester resin containing a carboxylic acid as in the present invention, effects such as hydrolysis inhibition and thickening can be imparted, and effects such as processability improvement and durability improvement as a resin composition are exhibited. It is also possible.

  Polycarbodiimide is a compound having two or more structures of —N═C═N— in one molecule, and a known one produced by decarbonation reaction of a diisocyanate compound can be used (US Pat. No. 2,941,956, (See Japanese Patent Publication No. 47-3279, J. Org. Chem., 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81, No. 4, 619-621).

  Examples of the diisocyanate compound include 4,4-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Isocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 1,3,5-tri Isopropylphenylene-2,4-diisocyanate or the like may be used alone or in combination of two or more. Come. Moreover, you may introduce | transduce a branched structure and functional groups other than a carbodiimide group and an isocyanate group by copolymerization. Furthermore, the degree of polymerization can be controlled and the terminal isocyanate can be blocked by blocking part or all of the terminal isocyanate. As the end-capping agent, monoisocyanate compounds such as phenyl isocyanate, tris isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, -OH group, -COOH group, -SH group, -NH-R (R is hydrogen) A compound having an atom or an alkyl group) can be used. When all the terminal isocyanates are blocked, it is necessary to introduce a hydroxyl-reactive group different from the isocyanate group. Examples of commercially available products include Rhein Chemie's Starbucksol series, Nisshinbo's Carbodilite series, Mitsui Takeda Chemical Cosmonate LK, Cosmonate LL, BASF INOAC Polyurethane Lupranate MM-103, and the like. It is done. Especially, it is preferable to use the polycarbodiimide which consists of an aliphatic or alicyclic structure from a compatible viewpoint with a C12 or more fatty acid. If it is an aromatic polycarbodiimide, the compatibility with a fatty acid having 12 or more carbon atoms is poor, and the carbodiimide group and the fatty acid cannot react efficiently, and the effect is reduced. In the above-mentioned commercial products, the Nisshinbo Carbodilite series has an aliphatic or alicyclic structure and is preferably used.

  Moreover, regarding content of polycarbodiimide, it is 0.05-5 mass parts with respect to polyester resin from a system stability, Preferably it is 0.05-3 mass parts, More preferably, it is 0.1-1 mass part. is there. When the amount is less than 0.05 parts by mass, the capture ability of the fatty acid ester decomposition product is not sufficient. On the other hand, when the amount exceeds 5 parts by mass, the functional group is excessive and the thermoplastic resin may be gelled. Theoretically, the decomposition product of the fatty acid ester compound only needs to be captured. Therefore, the ester group amount a (equivalent / ton) of the fatty acid ester compound, the added amount b part by mass, and the carboxylic acid group reaction in one molecule. When the sum c (equivalent / ton) of the functional group amount of the compound having a reactive group and a hydroxyl group-reactive group and its added amount d are mass parts, 100 ≧ c × d / a × b ≧ 0.1 Is preferred. If c × d / a × b <0.1, the amount of reactive compound is too small compared to the fatty acid ester compound, so that the reaction with the free acid generated from the fatty acid ester compound does not proceed sufficiently, and the effect of suppressing gas generation is achieved. It does not appear. On the other hand, if c × d / a × b> 100, an excessive reactive compound is contained in the thermoplastic resin, resulting in a decrease in thermal stability. From the above viewpoint, the capture rate of the fatty acid ester decomposition product is fast, and the polycarbodiimide which is a high molecular weight is most preferable. In particular, the number average molecular weight is 500 to 10,000 and the carbodiimide group amount is 100 to 10,000 equivalent / Are preferred.

  In the present invention, the (E) inorganic filler can be used to improve the heat resistance and rigidity required as a light reflector of the resin composition. When the average particle diameter of the inorganic filler exceeds 3.0 μm, the surface smoothness of the resin composition is lowered and the direct vapor deposition property is lowered, which is not preferable. Moreover, 1 mass part or more is preferable with respect to 100 mass parts of polyester resins containing (A) and (B), and, as for content of an inorganic filler, 5 mass parts or more is more preferable, and 8 mass parts or more is further more preferable. . However, from the surface smoothness of the resin composition, the content of the inorganic filler needs to be 20 parts by mass or less, particularly 15 parts by mass with respect to 100 parts by mass of the polyester resin containing (A) and (B). The following is preferred. When the amount exceeds 20 parts by mass, the direct vapor deposition property is lowered due to the relief of the filler.

  (E) It is preferable to contain 2 or more types of inorganic fillers among talc, barium sulfate, calcium carbonate, and titanium dioxide. Among the above inorganic fillers, talc has a crystal nucleating agent effect on the polyester resin, and can improve the heat resistance of the polyester resin with a small amount of addition. However, since the particle diameter of talc is relatively large, if it is added in a large amount, the surface smoothness is lowered due to the embossing on the resin surface, and the direct vapor deposition property is lowered. On the other hand, although barium sulfate, calcium carbonate, and titanium dioxide do not have a crystal nucleating agent effect, since the particle diameter is smaller than that of talc, the surface smoothness is easily maintained even if the addition amount is large. That is, when a small amount of talc is used in combination with at least one member of the group consisting of barium sulfate, calcium carbonate, and titanium dioxide, the crystal nucleating agent effect and the reinforcing effect of the filler while maintaining the surface smoothness. Can be obtained simultaneously, and the heat resistance can be greatly improved. When the total inorganic filler is 100% by mass, the total of at least one of the group consisting of barium sulfate, calcium carbonate, and titanium dioxide is 99.5 to 85% by mass with respect to 0.5 to 15% by mass of talc. % Is preferred.

(E) The inorganic filler may be surface-treated in order to improve compatibility and dispersibility. Good surface smoothness and direct vapor deposition can be exhibited even if the inorganic filler is not surface-treated. In the case of surface treatment, it is preferable to perform the surface treatment to such an extent that gas generation does not affect other characteristics such as fogging.
Examples of the surface treatment include treatment with a surface treatment agent, treatment with a fatty acid, treatment with SiO ₂ —Al ₂ O ₃ , and the like. Examples of the surface treatment agent include amino silane coupling agents, epoxy silane coupling agents, titanate coupling agents, and aluminate coupling agents.

In addition, the thermoplastic polyester resin composition of the present invention can contain various additives in a known range as long as the characteristics of the present invention are not impaired, if necessary. Examples of known additives include colorants such as pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, modifiers, antistatic agents, flame retardants, and dyes.
The thermoplastic polyester resin composition of the present invention preferably occupies 85% by mass or more, and 90% by mass or more in total of the components (A), (B), (C), (D), and (E). It is more preferable to occupy 95% by mass or more.

  As a method for producing the thermoplastic polyester resin composition of the present invention, it can be produced by mixing the above-described components and, if necessary, various stabilizers and pigments, and melt-kneading them. As the melt-kneading method, any method known to those skilled in the art can be used, and a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury mixer, and the like can be used. Among these, it is preferable to use a twin screw extruder. As general melt kneading conditions, in a twin screw extruder, the cylinder temperature is 220 to 270 ° C., and the kneading time is 2 to 15 minutes.

  The component for light reflectors of the present invention is formed using the thermoplastic polyester resin composition of the present invention. It does not restrict | limit especially as a shaping | molding method, Well-known methods, such as injection molding, extrusion molding, and blow molding, can be used. Among these, an injection molding method is preferably used from the viewpoint of versatility.

  The light reflector of the present invention is obtained by directly forming (depositing) a light reflective metal layer on at least a part of the surface of the light reflector component of the present invention. It does not restrict | limit especially regarding vapor deposition, A well-known method can be used.

  Examples of the light reflector thus obtained include light reflectors (extensions, reflectors, housings, etc.) of automobile lamps (headlamps, etc.), and light reflectors such as lighting fixtures.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measured value described in the Example is measured by the following method.

(1) Mold release resistance The mold release resistance value obtained at the time of mold release of a resin molded product was used as a method for evaluating mold release properties.
Using an injection molding machine SG-125 (manufactured by Sumitomo Heavy Industries, Ltd.), with a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., a cooling time of 30 seconds, and a cycle time of 60 seconds, a maximum inner diameter of 143 mm, a height of 60 mm, meat A cup-shaped product having a thickness of 3 to 4 mm and a draft angle of 2 ° was molded, and the resistance pressure (mold release resistance) applied to the ejector pin at the time of mold release was measured using a pressure sensor. The smaller the release resistance value, the better the release property from the mold.
In addition, when this mold release resistance value is 10 Mpa or less, it has favorable mold release property when shape | molding as components of various lamps. When the mold release resistance value exceeds 10 MPa, the moldability is difficult, and the productivity may be lowered, or there may be a problem when molding a molded product having a complicated shape or a large molded product.

(2) HAZE
A small piece having a size of about 10 mm × 10 mm is cut out from the molded product, and a total of 10 g is put in a glass tube (φ65 × 80 mm) covered with aluminum foil to form a bottom, and a hot plate (Neo Hot Plate HT-1000, ASONE Set). Furthermore, after the glass tube was covered with a slide glass, heat treatment was performed at 180 ° C. for 20 hours. As a result of this heat treatment, deposits due to decomposition products sublimated from the resin composition were deposited on the inner wall of the slide glass. The HAZE value (cloudiness) of these slide glasses was measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
In addition, when the HAZE of the slide glass after heating at 180 ° C. for 20 hours exceeds 5%, there is a practical problem of fogging as various lamp parts.

(3) Mold Stain Using an injection molding machine EC100N (manufactured by Toshiba Machine Co., Ltd.), a stepped (three-stage) molded product having a thickness of 95 mm × 50 mm × 2 to 3 mm was molded continuously 500 shots, and then adhered to the mold. Dirt was evaluated visually. Molding was performed under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and a cycle time of 40 seconds.
A: There is no white cloudy or iridescent oil film on the mold surface.
A: A white cloudiness or a rainbow-colored oil film is slightly observed on the mold surface depending on the visual angle, but is practically satisfactory.
Δ: White cloudiness or iridescent oil film is observed on the mold surface.
X: White cloudy or iridescent oil film is very conspicuous on the mold surface.

(4) Bleed-out resistance Using an injection molding machine EC100N (manufactured by Toshiba Machine Co., Ltd.), a 100 mm × 100 mm × 2 mm thick flat plate molded product having a mirror surface polished on a # 6000 file on one side was injection molded. Molding was performed under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and a cycle time of 40 seconds.
The molded product was heat-treated at 130 ° C. for 20 hours using a shelf dryer, and the mirror surface of the molded product was visually evaluated under sunlight irradiation for the presence of additive bleed out.
A: There is no white or iridescent pattern or oil film due to bleeding out.
○: A white or iridescent pattern or oil film due to bleed-out is slightly recognized depending on the viewing angle, but is practically satisfactory.
Δ: White or iridescent pattern or oil film due to bleed-out is observed.
X: A white or iridescent pattern or oil film due to bleed out is extremely noticeable.

(5) Appearance Using an injection molding machine EC100N (manufactured by Toshiba Machine Co., Ltd.), a 100 mm × 100 mm × 2 mm thick flat plate molded product having a mirror surface polished on the # 6000 file on one side was injection molded. Molding was carried out at a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., a cycle time of 40 seconds, and a low injection speed at which filler floating easily occurred on the surface. The mirror surface of the molded product was visually evaluated for defects (whitening, rough surface) due to floating of the filler.
A: There is no whitening or rough surface.
○: Whitening and surface roughness are slightly observed depending on the visual angle, but are practically acceptable.
Δ: Whitening and rough surface are observed.
X: Whitening and surface roughness are extremely noticeable.

(6) Appearance after annealing The flat molded product used in (5) Appearance evaluation described above was annealed for 4 hours in a shelf-type constant temperature dryer set at 130 ° C., and then the mirror surface of the molded product was used as a filler. Visual observation evaluated whether there was any defect (whitening, rough surface) due to the floating of the surface.
A: There is no whitening or rough surface.
○: Whitening and surface roughness are slightly observed depending on the visual angle, but are practically acceptable.
Δ: Whitening and rough surface are observed.
X: Whitening and surface roughness are extremely noticeable.

(6) HDT (Load: 0.45 MPa)
The deflection temperature under load (HDT) was used as an index of heat resistance of the resin composition. A multipurpose test piece of ISO-3167 was molded using an injection molding machine EC100N (manufactured by Toshiba Machine Co., Ltd.), and HDT was measured at a load of 0.45 MPa according to ISO-75. In particular, for light reflector applications requiring heat resistance, if the HDT is 130 ° C. or higher, the resin composition satisfies the heat resistance as a resin for a light reflector, but if it is 140 ° C. or higher, it is more highly satisfactory. And when it is 145 ° C. or higher, it can be said that it is more highly satisfactory.

The compounding components used in Examples and Comparative Examples are shown below.
(A) polybutylene terephthalate resin;
(A-1) Polybutylene terephthalate resin: IV = 0.83 dl / g, acid value = 30 eq / t
(B) polyethylene terephthalate resin;
(B-1) Polyethylene terephthalate resin: IV = 0.62 dl / g, acid value = 30 eq / t

(C) mold release agent;
(C-1) Triglycerin flubehenate: Poem TR-FB (manufactured by Riken Vitamin Co., Ltd.)
(C-2) Diglycerin flubehenate ester: L-7640 (manufactured by Riken Vitamin Co., Ltd.)
(C-3) Diglycerin flustearate: Riquemar S-74 (manufactured by Riken Vitamin Co.)
(C-4) Glycerin monostearate: S-100A (manufactured by Riken Vitamin Co., Ltd.)
(C-5) Glycerin monobehenate ester: B-100 (manufactured by Riken Vitamin Co., Ltd.)
(C-6) Montanic acid complex ester: Recolbe WE40 (manufactured by Clariant)

(D) a polycarbodiimide compound;
(D-1) Polycarbodiimide having an isocyanate at the terminal: Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.)
(D-2) Polycarbodiimide with all terminal isocyanates blocked: Carbodilite HMV-8CA (Nisshinbo Chemical Co., Ltd.)

(E) inorganic filler;
Catalog values etc. were adopted for the following average particle diameter.
(E-1) Talc (average particle size: 2.5 μm [laser diffraction method]): Microace SG-95 (manufactured by Nippon Talc Co., Ltd.)
(E-2) Talc (average particle size: 11.0 μm [precipitation method]): Talcan PK-C (manufactured by Hayashi Kasei Co., Ltd.)
(E-3) Precipitated barium sulfate (average particle diameter: 1.2 μm [observation by electron microscope]): B-54 (manufactured by Sakai Chemical Industry Co., Ltd.)
(E-4) Barium sulfate (average particle size: 10 μm [observation by electron microscope]): BMH-100 (manufactured by Sakai Chemical Industry Co., Ltd.)
(E-5) Calcium carbonate (average particle size: 1.8 μm [laser diffraction method]): SCP E- # 2010 (manufactured by Hayashi Kasei Co., Ltd.)
(E-6) Calcium carbonate (average particle diameter: 12.5 μm [laser diffraction method]): SCP E- # 45 (manufactured by Hayashi Kasei Co., Ltd.)
(E-7) Titanium dioxide (average particle size: 0.25 μm [observation by electron microscope]): PF-739 (Ishihara Sangyo Co., Ltd.)

[Examples 1 to 10, Comparative Examples 1 to 6]
First, the mixing ratio of (A) PBT and (B) PET, (C) release agent component, and (D) polycarbodiimide were examined. The blended components blended in the combinations shown in Table 1 were compounded with a co-directional twin-screw extruder set at a cylinder temperature of 260 ° C., and the resulting strand was cooled with water and pelletized. Each of the obtained pellets was dried at 130 ° C. for 4 hours and used for each of the above-described evaluation tests. The results are shown in Table 1.

  In Examples 1 to 5 and Comparative Examples 1 to 5, the addition amount and type of the fatty acid ester of the release agent are changed, and the effects of various release agents on release properties, fogging properties, mold stains, and the like can be compared. . For example, in Comparative Example 1, the release property is very good because the amount of the release agent is large, but the amount of gas generated by the release agent after molding and at the time of molding is large, and fogging and mold contamination are not good. In Comparative Examples 2 and 3, a release agent in which a hydroxyl group remains is used, and gas generation is extremely large. In Comparative Example 4, a release agent having a large molecular weight is used, and it is thought that it is difficult to deposit on the resin surface. Therefore, fogging, mold contamination, and bleed-out resistance are good, but release properties are extremely low compared to others. I understand that. In Comparative Example 5, fogging and mold contamination are good, but the releasability is low. In the examples, triglycerin behenate having a long fatty acid chain length and a relatively large molecular weight was a particularly good result with a good balance. Examples 1 and 2 having a blending amount of 1.0 part by mass or less were recognized as the best results.

  In Examples 1, 6, 7, 10 and Comparative Example 6, the addition amount and type of (D) polycarbodiimide were changed. In Example 7 with a large addition amount, fogging was reduced as compared with Example 1. However, the releasability decreased due to the decrease in crystallinity. Compared to Example 10 using polycarbodiimide in which all of the terminal isocyanates were blocked, the fogging of Example 1 was better. On the other hand, in Comparative Example 6 to which no polycarbodiimide was added, fogging and mold contamination were deteriorated.

  In Examples 1, 8, and 9, the blending ratio of (A) PBT and (B) PET is changed. It can be seen that as the blending amount of (B) increases, the heat resistance and the appearance after annealing tend to decrease.

[Examples 11 to 23, Comparative Examples 7 to 11]
Next, (E) Inorganic filler was examined. The blended components blended in the combinations shown in Table 2 were compounded with a co-directional twin-screw extruder set at a cylinder temperature of 260 ° C., and the resulting strand was cooled with water and pelletized. Each of the obtained pellets was dried at 130 ° C. for 4 hours and used for each of the above-described evaluation tests. The results are shown in Table 2.

  In Examples 11 to 20, various combinations of inorganic fillers are examined. Although Examples 11-14 use 1 type of inorganic filler, it can be said that it has the function excellent as a light reflector, such as surface smoothness, mold release property, and heat resistance. On the other hand, in Examples 15 to 20, two or more kinds of inorganic fillers are used in combination, heat resistance and releasability are particularly improved, and it has a highly balanced and excellent function as a light reflector. Recognize. When talc is used, heat resistance and releasability can be greatly improved by the crystal nucleating agent effect.

  In Examples 11, 12, 19 and Comparative Examples 7 to 9, the influence of the average particle diameter of the inorganic filler can be confirmed. It was recognized that the inorganic filler of the comparative example had a larger average particle size than that of the example and deteriorated the mirror appearance.

  In Examples 16 and 18, the amount of the inorganic filler was large, but the appearance was good. As in Comparative Examples 10 and 11, when the amount of the inorganic filler was further increased, the appearance deteriorated.

  In Example 15, 21-23, the influence by the compounding quantity of (A) PBT and (B) PET can be confirmed. (A) In Example 21 containing only PBT, the heat resistance was greatly improved, but (B) the appearance improvement effect by PET was not obtained, so the appearance was slightly deteriorated by the embossing of the filler. On the other hand, in Example 23 in which the blending amount of (B) PET was large, it was confirmed that the releasability and heat resistance were lowered. Although the appearance was remarkably improved, deterioration of the appearance was recognized after annealing due to the secondary shrinkage of (B) PET.

  By using the thermoplastic polyester resin composition of the present invention, when directly forming a metal vapor-deposited light reflector part by injection molding or the like, an optimal mold release agent and resin and additive decomposition component supplement gas are used. By suppressing the generation, it is possible to obtain a resin molded body having excellent mold releasability and heat resistance while reducing mold contamination and highly suppressing bleeding out to the surface of the molded product. Further, it is possible to obtain a high direct metal deposition property by having a filler particle size and content that do not affect the appearance of the mirror surface.

Claims (6)

(A) For 100 to 50 parts by mass of polybutylene terephthalate resin (B) For 100 parts by mass of polyester resin containing 0 to 50 parts by mass of polyethylene terephthalate resin (C) For all hydroxyl groups of polyglycerol, fatty acids There polyglycerol fatty acid ester 0.05 to 5 parts by mass formed by bonding, the (D) aliphatic or alicyclic polycarbodiimide compounds 0.05 to 5 parts by mass of (E) free machine filler 0 to 20 parts by weight When it contains and contains an inorganic filler, the thermoplastic polyester resin composition whose inorganic filler is only an inorganic filler with an average particle diameter of 3.0 micrometers or less . (C) The thermoplastic polyester resin composition according to claim 1, wherein the polyglycerol which is a constituent of the polyglycerol fatty acid ester is triglycerol and the fatty acid is behenic acid. (D) The thermoplastic polyester resin composition according to claim 1 or 2, wherein the aliphatic or alicyclic polycarbodiimide compound has an isocyanate group at the terminal. (E) The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein the inorganic filler contains two or more of talc, barium sulfate, calcium carbonate, and titanium dioxide. The component for light reflectors shape | molded using the thermoplastic polyester resin composition in any one of Claims 1-4. A light reflector in which a light-reflecting metal layer is directly formed on at least a part of the surface of the component for light reflector according to claim 5.