JP2021121685A - Polyester-based resin composition and component for vehicle lighting body - Google Patents

Abstract

To provide a polyester-based resin composition and a component for a vehicle lighting body which are excellent in surface quality and appearance, and appearance in vapor deposition while maintaining high mechanical strength, and prevents gas generation in molding while exhibiting high thermal conductivity.SOLUTION: A polyester-based resin composition contains, with respect to 100 pts.mass of a thermoplastic polyester resin (A), 0.01-10 pts.mass of one or more inorganic fillers (B) selected from calcium carbonate, talc and kaolin having an average particle diameter of 2 μm or less, 0.01-10 pts.mass of alumina (C) having an average particle diameter of 8 μm or less and an aspect ratio of 1.5 or less, and 1-20 pts.mass of an acrylonitrile-styrenic copolymer (D).SELECTED DRAWING: None

Description

The present invention relates to a polyester-based resin composition and vehicle lamp body parts, and more particularly to a polyester-based resin composition and vehicle lamp body parts having high appearance, high thermal conductivity, and no gas generation.

Interior and exterior parts for vehicles such as automobiles are required to have high strength and excellent appearance, and are being reduced in weight by thinning and downsizing for the purpose of cost reduction and resource saving. Thermoplastic polyester resins such as polybutylene terephthalate resin are excellent in mechanical properties, electrical properties, etc., as well as chemical resistance, heat resistance, etc., so they can be used for various parts for automobiles and other vehicles. Is also widely used.

Among vehicle parts, parts that require mechanical characteristics and appearance are, for example, lamp-related parts such as automobile headlamps, and lamp extensions that have a light-collecting and reflecting function along with reflectors. There is a member called. In the lamp extension, metal is vapor-deposited on a thin-walled molded product having a complicated reflection structure for condensing and reflecting light, usually about 2 mm. At present, the mainstream of lamp extensions is to perform aluminum vapor deposition on the surface of a molded body of a reinforced resin in which an inorganic filler is mixed with a polybutylene terephthalate resin.

In recent years, when the headlamp is actually used outdoors for a long period of time, there is a problem that sunlight is reflected by the projector lens of the headlamp and the light is condensed on the extension part and the resin is melted. It has occurred.
In order to solve this problem, a material containing a black pigment that transmits infrared rays has been proposed so that the temperature does not rise even when sunlight is condensed (see Patent Document 1). However, such a material has a problem that it generates a lot of gas, and the maintenance frequency at the time of molding is high, so that it is not yet sufficiently satisfactory.

On the other hand, in order to suppress the temperature rise, a material with high thermal conductivity may solve the above problem, but a material with high thermal conductivity contains a large amount of inorganic filler with a large particle size. This is a material that is not suitable for extension applications that require a high-gloss appearance because the smoothness is greatly impaired.

International Publication No. 2016/194757

Under such circumstances, a polyester-based resin material that has a high appearance, exhibits high thermal conductivity, and does not generate gas is strongly desired. An object (problem) of the present invention is to provide a polyester-based resin composition having a high appearance, high thermal conductivity, and no gas generation.

As a result of diligent studies to solve the above problems, the present inventor has a polyester resin composition containing a specific amount of an inorganic filler having a specific average particle size and an alumina particle having a specific average particle size and an aspect ratio. We have found that the material is a polyester resin material that does not generate gas while maintaining high mechanical strength, excellent surface texture, appearance, and appearance when vapor-deposited, and exhibiting high thermal conductivity. ..
The present invention relates to the following polyester-based resin compositions and vehicle lamp body parts.

[1] 0.01 to 10 parts by mass of one or more inorganic fillers (B) selected from calcium carbonate, talc, and kaolin having an average particle diameter of 2 μm or less with respect to 100 parts by mass of the thermoplastic polyester resin (A). A polyester resin composition containing 0.01 to 10 parts by mass of alumina (C) having an average particle size of 8 μm or less and an aspect ratio of 1.5 or less.
[2] The polyester-based resin composition according to the above [1], wherein the alumina (C) is spherical alumina.
[3] The polyester-based product according to the above [1] or [2], which further contains 1 to 20 parts by mass of the acrylonitrile-styrene-based copolymer (D) with respect to 100 parts by mass of the thermoplastic polyester resin (A). Resin composition.
[4] The polyester system according to any one of the above [1] to [3], further containing 0.01 to 5 parts by mass of carbon black (E) with respect to 100 parts by mass of the thermoplastic polyester resin (A). Resin composition.
[5] The polyester resin according to any one of the above [1] to [4], wherein the polyester resin powder having an average particle size of 1000 μm or less accounts for 1 to 50% by mass in 100% by mass of the thermoplastic polyester resin (A). Composition.
[6] A component for a vehicle lamp body made of the polyester resin composition according to any one of the above [1] to [5].

The polyester-based resin composition of the present invention is excellent in surface texture, appearance, and appearance when vapor-deposited while maintaining high mechanical strength, exhibits high thermal conductivity, and does not generate gas during molding. It is a material, and the product obtained by thin-filming aluminum on its surface has an extremely good appearance, has excellent heat-resistant vapor deposition, and exhibits high thermal conductivity. In particular, it can be suitably used as a lamp extension or the like.

In the polyester resin composition of the present invention, one or more inorganic fillers (B) selected from calcium carbonate, talc, and kaolin having an average particle diameter of 2 μm or less are 0 to 100 parts by mass of the thermoplastic polyester resin (A). It is characterized by containing 0.01 to 10 parts by mass of alumina (C) having an average particle size of 8 μm or less and an aspect ratio of 1.5 or less by 0.01 to 10 parts by mass.

Hereinafter, embodiments of the present invention will be described in detail. Although the description described below may be based on embodiments and specific examples, the present invention is not construed as being limited to such embodiments and specific examples.
In addition, in this specification, "~" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.

[Thermoplastic polyester (A)]
The polyester-based resin composition of the present invention contains a thermoplastic polyester resin (A).
The thermoplastic polyester resin is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, polycondensation of these compounds, or the like, and may be either a homopolyester or a copolyester. ..

As the dicarboxylic acid compound constituting the thermoplastic polyester resin, an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably used.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, Biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulphon-4,4'-dicarboxylic acid , Diphenylisopropyridene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p -Terphenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid and the like can be mentioned, and terephthalic acid can be preferably used.

Two or more of these aromatic dicarboxylic acids may be mixed and used. As is well known, dimethyl ester or the like can be used as an ester-forming derivative in the polycondensation reaction in addition to the free acid.
In addition, if it is a small amount, along with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecandioic acid and sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 , 4-Cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids can be mixed and used.

Examples of the dihydroxy compound constituting the thermoplastic polyester resin include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, and triethylene glycol. , Cyclohexane-1,4-dimethanol and other alicyclic diols, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.
Aromatic diols such as hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.

In addition to the bifunctional monomers as described above, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure, and fatty acids for adjusting the molecular weight, etc. A small amount of the monofunctional compound can also be used in combination.

As the thermoplastic polyester resin (A), a resin mainly composed of a polycondensation of a dicarboxylic acid and a diol, that is, a resin in which 50% by mass, preferably 70% by mass or more of the total resin is composed of this polycondensate is used. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.

Of these, polyalkylene terephthalate in which 95 mol% or more of the acid component is terephthalic acid and 95% by mass or more of the alcohol component is an aliphatic diol is preferable. Typical examples are polybutylene terephthalate and polyethylene terephthalate. It is preferable that these are close to homopolyester, that is, 95% by mass or more of the total resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.

The intrinsic viscosity (Iv) of the thermoplastic polyester resin (A) is preferably 0.3 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.5 to 1.5 dl / g are more preferable. If the intrinsic viscosity is lower than 0.3 dl / g, the obtained resin composition tends to have low mechanical strength, and if it is higher than 2 dl / g, the fluidity of the resin composition becomes poor and the moldability becomes poor. It may deteriorate, or the surface properties of the molded product obtained thereby may not be sufficient as parts for vehicle lamps.
In the present invention, the intrinsic viscosity of the thermoplastic polyester resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The amount of the terminal carboxyl group of the thermoplastic polyester resin (A) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and 30 eq / ton or less. Is even more preferable. If it exceeds 50 eq / ton, gas is likely to be generated during melt molding of the resin composition. The lower limit of the amount of terminal carboxyl groups is not particularly specified, but is usually 10 eq / ton.
The amount of the terminal carboxyl group of the polyester resin is a value obtained by dissolving 0.5 g of the polyester resin in 25 ml of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. say.
As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent can be used. Just do it.

In the present invention, the amount of terminal carboxyl groups of the thermoplastic polyester resin is measured by dissolving 0.5 g of the polyester resin in 25 ml of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. The value.

Among them, the thermoplastic polyester resin (A) preferably contains a polybutylene terephthalate resin and / or a polyethylene terephthalate resin, and 50% by mass or more of the thermoplastic polyester resin (A) is a polybutylene terephthalate resin. More preferred.

Polybutylene terephthalate resin is produced by melt-polymerizing a dicarboxylic acid component containing terephthalic acid as a main component or an ester derivative thereof and a diol component containing 1,4-butanediol as a main component by a batch method or a continuous method. can do. Further, the degree of polymerization (or molecular weight) can be increased to a desired value by producing a low molecular weight polybutylene telecturate resin by melt polymerization and then performing solid phase polymerization under a nitrogen stream or under reduced pressure.

The polybutylene terephthalate resin preferably has a production method in which a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component are continuously melt-polycondensed.

The catalyst used in carrying out the esterification reaction may be a conventionally known catalyst, and examples thereof include titanium compounds, tin compounds, magnesium compounds, and calcium compounds. Of these, particularly suitable ones are titanium compounds. Specific examples of the titanium compound as an esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If an intrinsic viscosity of less than 0.5 dl / g is used, the obtained resin composition tends to have low mechanical strength. Further, if the value is higher than 2 dl / g, the fluidity of the resin composition is deteriorated and the moldability is likely to be deteriorated, and the surface characteristics of the molded product obtained thereby may not be sufficient as parts for vehicle lamps. ..

The amount of the terminal carboxyl group of the polybutylene terephthalate resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. .. If it exceeds 50 eq / ton, gas is likely to be generated during melt molding of the resin composition. The lower limit of the amount of the terminal carboxyl group is not particularly determined, but is usually 10 eq / ton in consideration of the productivity of producing the polybutylene terephthalate resin.
As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent can be used. Just do it.

Further, the polyethylene terephthalate resin is a resin having an oxyethylene oxyterephthaloyl unit composed of terephthalic acid and ethylene glycol as a main constituent unit with respect to all the constituent repeating units, and includes a constituent repeating unit other than the oxyethylene oxyterephthaloyl unit. You may be. The polyethylene terephthalate resin is produced by using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as a main raw material, but other acid components and / or other glycol components may be used together as a raw material.

Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-. Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

Examples of the diol component other than ethylene glycol include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, and cyclohexane. Examples thereof include alicyclic glycols such as dimethanol, aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S, and the like.

Polyethylene terephthalate resins are branched components, such as trifunctional acids such as tricarbaryl acid, trimellitic acid, trimellitic acid, etc., or acids or glycerin, trimethylolpropane, pentaerythrit having tetrafunctional ester form performance such as pyromellitic acid. An alcohol having a trifunctional or tetrafunctional ester-forming ability such as, etc. is copolymerized with 1.0 mol% or less, preferably 0.5 mol% or less, and more preferably 0.3 mol% or less. May be good.

The ultimate viscosity of the polyethylene terephthalate resin is preferably 0.3 to 1.5 dl / g, more preferably 0.3 to 1.2 dl / g, and particularly preferably 0.4 to 0.8 dl / g.

The concentration of the terminal carboxyl group of the polyethylene terephthalate resin is preferably 3 to 50 eq / ton, particularly preferably 5 to 40 eq / ton, more preferably 10 to 30 eq / ton. By setting the terminal carboxyl group concentration to 50 eq / ton or less, gas is less likely to be generated during melt molding of the resin composition, and the mechanical properties tend to be improved. Conversely, the terminal carboxyl group concentration is set to 3 eq / ton or more. This tends to improve heat resistance, retention heat stability, and hue, which is preferable.
As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent can be used. Just do it.

The thermoplastic polyester resin (A) also preferably contains a polybutylene terephthalate resin and a polyethylene terephthalate resin together. In particular, by containing a specific amount of the polyethylene terephthalate resin in the polybutylene terephthalate resin, the shrinkage rate can be lowered and the surface appearance characteristics such as glossiness can be further improved, which is preferable.
When the polybutylene terephthalate resin and the polyethylene terephthalate resin are contained, the content of the polybutylene terephthalate resin and the polyethylene terephthalate resin is preferably 10 to 50% by mass based on 100% by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin. It is more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass. If the content of the polyethylene terephthalate resin exceeds 50% by mass, the moldability may be significantly lowered, which is not preferable.

Further, in the present invention, it is preferable to use a part of the thermoplastic polyester resin (A) in the form of powder instead of pellets. By blending a thermoplastic polyester resin powder, while maintaining high mechanical strength, it has a low shrinkage rate and excellent mold releasability, and has excellent surface texture, appearance, and appearance when vapor-deposited, and it becomes cloudy even when used at high temperatures. It is preferable because a polyester resin material whose generation is suppressed can be obtained.

The polyester resin used for the thermoplastic polyester resin powder is not particularly limited as long as it is a thermoplastic polyester resin, but preferably either a polybutylene terephthalate resin or a polyethylene terephthalate resin is used, and it is also preferable to use both powders in combination. The polybutylene terephthalate resin and the polyethylene terephthalate resin are as described above.

The polyester resin powder is a powder of the polyester resin, and the polyester resin may be polymerized into a powder by an interfacial polymerization method or a solution polymerization method, or may be produced by crushing polyester resin pellets. However, from the viewpoint that the particle size can be easily controlled, it is preferable to adopt a method of crushing the polyester resin pellets.
As a means for pulverizing the pellets, there are a multi-stage pulverization method in which the pellets are roughly pulverized and then finely pulverized, a method in which miniaturization is performed in one stage, and the like, but the method is not limited. Specific examples of the crushing means include a crushing means using a hammer mill, a turbo mill, a jet mill, a pin mill, a centrifugal mill, a rotoplex, a parberizer, a wet crushing, a chopper mill, an ultra rotor, etc., and a normal temperature or freezing crushing method is used. be able to. When adopting these crushing methods, a method devised to prevent temperature rise is useful, specifically, a palberizer (manufactured by Herbold, Germany), an ultra rotor (manufactured by Altenburg Machinen Jachering, Germany), etc. The means used are useful.

The polyester resin powder preferably has an average particle size of 1000 μm or less, and preferably 50 to 1000 μm. If it is less than 50 μm, it tends to induce manufacturing troubles such as blocking in the resin composition manufacturing process. On the other hand, if the average particle size is larger than 1000 μm, the appearance tends to be poor, and the effect of the present invention may not be obtained. The average particle size of the polyester resin powder is more preferably 100 μm or more, further preferably 150 μm or more, and particularly preferably 200 μm or more, preferably 900 μm or less.
Here, the average particle size of the polyester resin powder refers to the median size (D50) obtained from the particle size distribution map using a laser diffraction / scattering type particle size distribution measuring device.

Preferably the bulk density of the polyester resin powder is 0.2 to 0.8 g / cm ^3, more preferably ^{0.3~0.7g / cm 3, 0.4~0.6g / cm} 3 Is more preferable. By using such a bulky polyester resin powder, it is easy to suppress scattering and classification of the inorganic filler (B) and the like during the production of the resin composition, and the appearance is poor due to the secondary aggregation of the inorganic filler (B). It is less likely to occur and is preferable.
The bulk density refers to a value measured by the method described in JIS K7365.

The content of the polyester resin powder is preferably 1 to 50% by mass, more preferably 3% by mass or more, further 5% by mass or more, and particularly 7% by mass or more in the thermoplastic polyester resin (A). It is preferable, more preferably 45% by mass or less, further 40% by mass or less, particularly preferably 30% by mass or less, and most preferably 20% by mass or less.
With such a powder content, the mixture is better due to the coexistence of the polyester resin powder than the mixing with the inorganic filler (B) in the presence of only the resin pellets, and the secondary aggregation of the inorganic filler (B) is improved. Is suppressed, uniform dispersion is achieved, and it becomes easy to obtain a molded product having excellent surface properties and appearance while maintaining high mechanical strength, and further, a resin composition having excellent water absorption and hydrolyzability. It is preferable because it tends to be.

[Inorganic filler (B)]
The polyester-based resin composition of the present invention contains one or more inorganic fillers (B) selected from calcium carbonate, talc, and kaolin having an average particle size of 2 μm or less.
There are various types of inorganic fillers, but in the present invention, calcium carbonate, talc or kaolin is used, and the average particle size thereof is 2 μm or less.
As the inorganic filler (B), calcium carbonate, talc or kaolin may be used alone, or two or more of them may be used in combination at any ratio.

The average particle size of the inorganic filler (B) is 2 μm or less, but if it exceeds 2 μm, the surface smoothness of the molded product is lowered, and the appearance is deteriorated when a metal such as aluminum is directly vapor-deposited on the surface. The average particle size is more preferably 1 μm or less, further preferably 0.5 μm or less, and particularly preferably 0.4 μm or less. The lower limit is usually 0.01 μm, preferably 0.05 μm, more preferably 0.08 μm, and particularly preferably 0.1 μm.
The average particle size of the inorganic filler (B) in the present invention refers to the median size (D50) obtained from the particle size distribution map measured by the laser diffraction type particle size distribution measuring device.

The specific gravity of the inorganic filler (B) ^{is preferably 4 g / cm 3} or less, more preferably 3.5 g / cm ³ or less, and even more preferably 3 g / cm ³ or less. When the inorganic filler (B) having such a specific gravity is contained, the effect of improving the appearance of the molded product by using the polyester resin powder becomes more remarkable. The specific gravity of the inorganic filler (B) refers to a value measured by a true hydrometer based on the helium gas substitution method.

It is also preferable that the inorganic filler (B) is surface-treated in order to improve the affinity with the resin. Examples of the surface treatment agent include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, higher fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate and magnesium stearate, and polyethylene wax. Selected from hydrocarbon lubricants such as liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin and derivatives thereof, silane coupling agents, titanate coupling agents, and aluminum coupling agents. At least one type is mentioned.

Kaolin is an aluminum silicate salt, and usually, dehydrated water of crystallization by firing is preferably used. The chemical composition of kaolin contains about 40 to 50% by mass of _{Al 2} O _{3 and about 50 to 60% by mass of SiO 2} , and further, as a small amount component, Na ₂ O, TiO ₂ , CaO, Fe ₂ O ₃ , MgO. also often contain or K _{2 O} or the like. Among the kaolins, calcined kaolin is preferable from the viewpoint of the appearance of the molded product obtained by using the resin composition.

It is a white, powdery crystalline mineral. The chemical composition of talc contains _{60 to 70% by mass of SiO 2 and} 30 to 40% by mass of MgO, and _{often contains Al 2} O ₃ , Fe ₂ O ₃ , CaO and the like as impurities.

Talc is a plate-like particles having a layered structure, the chemical compositional a hydrous magnesium silicate, the normal SiO ₂ 58 to 66 wt%, the MgO 28 to 35 wt%, about the _{H 2} O 5 It contains about mass%, and Fe ₂ O ₃ is 0.03 to 1.2 mass%, Al ₂ O ₃ is 0.05 to 1.5 mass%, and Ca O is 0.05 to 1.2 as other small amount components. In many cases, it contains% by mass, K ₂ O in an amount of 0.2% by mass or less, and Na ₂ O in an amount of 0.2% by mass or less.

The inorganic filler (B) is particularly preferably calcium carbonate, and examples thereof include synthetic calcium carbonate, natural calcium carbonate, and surface-treated calcium carbonate obtained by surface-treating them with silicic acid or the like or an organic acid or the like.
Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide gas. Calcium hydroxide can be produced, for example, by reacting calcium oxide with water. Calcium oxide can be produced, for example, by calcining rough limestone with coke or the like. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.
Natural calcium carbonate is obtained by pulverizing naturally produced rough calcium carbonate such as limestone by a known method. Examples of the method for crushing rough calcium carbonate include a method of crushing with a roller mill, a high-speed rotary mill (impact shearing mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, a jet mill and the like.

The average particle size of calcium carbonate is preferably 0.01 to 2 μm, more preferably 0.05 to 1 μm, still more preferably 0.08 to 0.5 μm, and 0.1 to 0. It is particularly preferably .4 μm. It is preferable to use calcium carbonate having such an average particle size because calcium carbonate is less likely to aggregate and the diffuse reflectance after aluminum vapor deposition tends to be excellent.

The silicic acids used for the surface treatment of calcium carbonate are not particularly limited as long as they can adhere silica to the surface of calcium carbonate. Examples of silicic acids include alkali metal silicates such as sodium silicate and potassium silicate.
For silicic acids, for example, alkali silicate can be used as silica hydrosol, which can be used for surface treatment. The silica hydrosol can be produced by a known method. For example, a silica hydrosol can be produced from sodium silicate by an acid decomposition method. As an acid decomposition method, for example, an amorphous silica hydrosol is obtained by adding an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid or acrylic acid, or an acidic substance such as aluminum sulfate or carbon dioxide to an aqueous sodium silicate solution. There is a method of generating. Furthermore, it can also be produced by a dialysis method in which sodium silicate is passed through a semipermeable membrane to produce a silica hydrosol. Further, a silica hydrosol can be produced by an ion exchange method using an ion exchange resin.

Examples of organic acids used for surface treatment of calcium carbonate include fatty acids, resin acids, lignins and derivatives thereof. Two or more kinds of organic acids may be mixed and used.
Examples of fatty acids include saturated or unsaturated fatty acids having 6 to 24 carbon atoms. The number of carbon atoms of the fatty acid is preferably 10 to 20. Specific examples of saturated or unsaturated fatty acids having 6 to 24 carbon atoms include stearic acid, palmitic acid, lauric acid, behenic acid, oleic acid, erucic acid, linoleic acid and the like. In particular, stearic acid, palmitic acid, lauric acid, and oleic acid are preferable.

Examples of fatty acid derivatives include fatty acid salts and fatty acid esters. Examples of the fatty acid salt include alkali metal salts such as sodium salt and potassium salt of saturated or unsaturated fatty acids having 6 to 24 carbon atoms. The number of carbon atoms of the fatty acid salt is preferably 10 to 20.

Examples of the fatty acid ester include an ester of the saturated or unsaturated fatty acid having 6 to 24 carbon atoms and a saturated fatty alcohol having 6 to 18 carbon atoms. The number of carbon atoms in the fatty acid ester is preferably 10 to 20. The saturated aliphatic alcohol preferably has 10 to 18 carbon atoms.

The content of the inorganic filler (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the content is less than 0.1 parts by mass, the heat resistance is insufficient and the effect of reducing the shrinkage rate cannot be sufficiently obtained. On the contrary, if it exceeds 10 parts by mass, agglomerates derived from the inorganic filler increase, so that it is difficult to obtain a good appearance. The content of the inorganic filler (B) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 2.5 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). Yes, preferably 7 parts by mass or less, more preferably 5 parts by mass or less.

[Alumina (C)]
The polyester-based resin composition of the present invention contains alumina (C) having an average particle size of 8 μm or less and an aspect ratio of 1.5 or less.
The particle shape of alumina may be spherical or crushed, including an ellipse, but the alumina (C) is not limited as long as the aspect ratio (major axis / minor axis ratio) is 1.5 or less. , Spherical ones including those having an elliptical cross section are preferable. The aspect ratio (major axis / minor axis ratio) is preferably 1.4 or less, more preferably 1.4 or less, particularly 1.3 or less, particularly 1.2 or less, and particularly 1.1 or less. Is preferable.

The average particle size of alumina (C) is 8 μm or less, preferably 0.3 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, particularly 1.5 μm or more, and preferably 7. It is preferably 5.5 μm or less, more preferably 7 μm or less, further 6.5 μm or less, and particularly preferably 6 μm or less.
Here, the average particle size of alumina (C) refers to the median size (D50) obtained from the particle size distribution map using a laser diffraction / scattering type particle size distribution measuring device.

As the alumina (C), spherical alumina is particularly preferable from the viewpoint of high thermal conductivity, mechanical strength, fluidity, and appearance of the resin composition. Spherical alumina is an alumina powder having a spherical or near-spherical particle shape, and has an aspect ratio (major axis / minor axis) of 1 to 1.3, preferably 1 to 1.2, particularly 1 to 1. Spherical alumina of 1.1 is preferred.

Spherical alumina is usually spheroidized alumina particles produced by supplying and spraying an aluminum hydroxide powder, an alumina powder, or an alcohol slurry of aluminum powder into a flame. The particle size and aspect ratio of the spherical alumina powder can be adjusted by adjusting the particle size of the raw material alumina powder and the alcohol slurry concentration of the alumina powder.

The content of alumina (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the content is less than 0.1 parts by mass, the thermal conductivity is insufficient and the heat dissipation effect cannot be sufficiently obtained. On the contrary, if it exceeds 10 parts by mass, it is difficult to obtain excellent surface smoothness. The content of alumina (C) is preferably 0.2 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 7 parts by mass or less, more preferably 6 parts by mass or less.

The total content of the inorganic filler (B) and alumina (C) is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further, with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 4 parts by mass or more, preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and further 15 parts by mass or less.

Further, in the present invention, the ratio of the contents of the thermoplastic polyester resin powder, the inorganic filler (B) and the alumina (C) is 30 in terms of the mass ratio of the thermoplastic polyester resin powder: (B) and (C). : 70 to 95: 5, more preferably 40:60 to 93: 7, and even more preferably 50:50 to 90:10. With such a content ratio, the dispersed state of the inorganic filler (B) and alumina (C) is good, excellent surface smoothness can be obtained, and it is stable in the production of a resin composition such as melt kneading. It tends to be possible to feed the product, which is preferable.

[Acrylonitrile-styrene copolymer (D)]
The polyester-based resin composition of the present invention preferably further contains an acrylonitrile-styrene-based copolymer (D).
The acrylonitrile-styrene-based copolymer (D) is a copolymer of acrylonitrile and a styrene-based monomer, and may be a copolymer with another copolymerizable monomer.

Examples of the styrene-based monomer constituting the acrylonitrile-styrene-based copolymer (D) include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, and vinyl. Examples thereof include naphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, tribromstyrene, etc., with styrene and α-methylstyrene being more preferable, and styrene being particularly preferable.

Examples of copolymerizable monomers other than styrene-based monomers and acrylonitrile include (meth) acrylic acid ester-based monomers and maleimide-based single amounts such as maleimide, N-methylmaleimide, and N-phenylmaleimide. Examples thereof include α, β-unsaturated carboxylic acids such as body, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and their anhydrides.
Among these, (meth) acrylic acid ester-based monomers are preferably mentioned, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and the like. Amil (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, Benzyl (meth) acrylate and the like can be mentioned, and methyl methacrylate and the like can be mentioned in particular.
The notation of (meth) acrylate indicates that it contains both methacrylate and acrylate, and the notation of (meth) acrylic acid ester indicates that it includes both methacrylic acid ester and acrylic acid ester.

The method for producing the acrylonitrile-styrene copolymer (D) is not limited, and known methods can be adopted. For example, bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization and the like are used.

The acrylonitrile monomer in the acrylonitrile-styrene copolymer (D) is preferably 5 to 95% by mass, more preferably 8 to 45% by mass. The content of the unit derived from the styrene-based monomer is preferably 50 to 95% by mass, more preferably 55 to 92% by mass.

Further, acrylonitrile - as a melt volume rate of the styrene copolymer (D) (MVR), preferably in the range 220 ° C., under a load 10kg of 5 to 100 cm ^3/10 min, 10~80cm ^3/10 min Is more preferable.
The mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer (D) is preferably in the range of 60,000 to 220,000, and more preferably 80,000 to 200,000.
In the present invention, the mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer (D) is measured by the GPC (gel permeation chromatography) method.

Examples of the acrylonitrile-styrene copolymer include an acrylonitrile-styrene copolymer (AS resin) and an acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and an acrylonitrile-styrene copolymer (AS resin) is particularly preferable. ..

The content of the acrylonitrile-styrene copolymer (D) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the content is less than 1 part by mass, the effect of improving the surface appearance tends to be poor, and if it exceeds 20 parts by mass, the heat resistance and impact resistance tend to decrease. The content of the acrylonitrile-styrene copolymer (D) is more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, still more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less. In particular, it is preferably 8 parts by mass or less.

[Carbon black (E)]
The polyester-based resin composition of the present invention preferably contains carbon black (E). By containing carbon black, the weather resistance and appearance of the polyester resin composition and the molded product, the reflection characteristics on the metal vapor deposition surface, and the like are improved.

The type, raw material type, and manufacturing method of carbon black (E) are not limited, and any of furnace black, channel black, acetylene black, ketjen black, and the like can be used. The number average particle size is not particularly limited, but is preferably 5 to 60 nm. By using carbon black having a number average particle size in a predetermined range as described above, it is possible to obtain a composition in which blister is unlikely to occur at a high temperature.
For the number average particle size, an aggregate magnified image is obtained according to the procedure described in the ASTM D3849 standard (standard test method for carbon black-morphological characterization by electron microscopy), and the aggregate image is used as a unit constituent particle. The particle size of 3,000 particles can be measured and calculated by arithmetic mean.

Nitrogen adsorption specific surface area of the carbon black (E) ^{(unit: m} 2 / g) is preferably usually less than 1000 m ² / g, is preferably Among them 50 to 400 m ² / g. It is preferable that the nitrogen adsorption specific surface area is ^{less than 1000 m 2} / g because the fluidity of the polyester resin composition and the appearance of the molded product tend to be improved.
The nitrogen adsorption specific surface area can be measured according to JIS K6217.

Further, DBP (dibutyl phthalate) absorption amount of carbon black (E) ^is preferably less than 300 cm 3/100 g, is preferably Among them 30~200cm ³ / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, preferably tends to increase the appearance of fluidity and a molded article of the polyester resin composition of the present invention.
Incidentally, DBP absorption ^(unit: cm 3 / 100g) can be measured according to JIS K6217. The pH of the carbon black used is not particularly limited, but is usually 2 to 10, preferably 3 to 9, and even more preferably 4 to 8.

Carbon black (E) can be used alone or in combination of two or more. Further, carbon black can be granulated using a binder, and can be used in a masterbatch in which carbon black is melt-kneaded at a high concentration in another resin. By using the melt-kneaded masterbatch, it is possible to improve the handleability at the time of extrusion and the dispersibility in the resin composition. Examples of the resin include polystyrene-based resins, polyester-based resins, and acrylic-based resins.
The content of carbon black in the masterbatch is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 60% by mass.

The content of carbon black (E) is preferably 0.01 to 5 parts by mass, more preferably 0.1 parts by mass or more, and further preferably 0. parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is 3 parts by mass or more, particularly 0.5 parts by mass or more, more preferably 2 parts by mass or less, further preferably 1.5 parts by mass or less, and particularly preferably 1.0 part by mass or less. If the content is less than 0.01 parts by mass, the weather resistance may be insufficient, and if it exceeds 5 parts by mass, mechanical properties such as moldability and impact resistance tend to deteriorate.

[Other ingredients]
The polyester-based resin composition of the present invention can contain a thermoplastic resin other than those described above as long as the effects of the present invention are not impaired. Specific examples of other thermoplastic resins include polycarbonate resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyetherimide resin, and polyether ketone resin. , Polyethylene resin and the like.
However, when the resin other than the thermoplastic polyester resin (A) and the acrylonitrile-styrene copolymer (B) is contained, the content is 20 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

Further, the polyester-based resin composition of the present invention may contain various additives other than those described above, and such additives include stabilizers, mold release agents, flame retardants, and flame retardant aids. , Anti-drip agent, UV absorber, antistatic agent, anti-fog agent, anti-blocking agent, plasticizer, dispersant, antibacterial agent, colorant and the like.

[Stabilizer]
It is preferable that the polyester resin composition of the present invention contains a stabilizer because it has an effect of improving thermal stability and preventing deterioration of mechanical strength and hue. As the stabilizer, a phosphorus-based stabilizer, a sulfur-based stabilizer and a phenol-based stabilizer are preferable, and a phenol-based stabilizer is particularly preferable.

Examples of the phosphorus-based stabilizer include phosphoric acid, phosphoric acid, phosphoric acid ester, phosphoric acid ester and the like, and among them, an organic phosphate compound, an organic phosphite compound or an organic phosphonite compound is preferable.

The organic phosphate compound is preferably given the following general formula:
(R ¹ O) _3-n P (= O) OH _n
(In the formula, R ¹ is an alkyl group or an aryl group, which may be the same or different. N represents an integer of 0 to 2.)
It is a compound represented by. More preferably, a long-chain alkyl acid phosphate compound in which ^{R 1 has 8 to 30 carbon atoms can be mentioned.} Specific examples of the alkyl group having 8 to 30 carbon atoms include an octyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a dodecyl group, a tridecyl group, an isotridecyl group and a tetradecyl group. Examples thereof include a hexadecyl group, an octadecyl group, an eikosyl group, and a triacontyl group.

Examples of long-chain alkyl acid phosphates include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, and cyclohexyl. Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid Examples thereof include phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate and the like. Among these, octadecyl acid phosphate is preferable, and this product is commercially available under the trade name "ADEKA STAB AX-71" of ADEKA Corporation.

The organic phosphite compound is preferably preferably the following general formula:
R ² OP (OR ³ ) (OR ⁴ )
^(Wherein, R 2, ^{R 3} and ^{R 4} are each a hydrogen atom, an alkyl group or an aryl group having 6 to 30 carbon atoms having 1 to 30 carbon ^atoms, of R 2, ^{R 3} and ^{R 4} At least one of them is an aryl group having 6 to 30 carbon atoms.)
Examples thereof include compounds represented by.

Examples of the organic phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, dilaurylhydrogenphosphite, triethylphosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phenylphosphite, tristearyl phosphite, diphenylmonodecylphosphite, monophenyldidecylphosphite, diphenylmono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite , Hydrogenated bisphenol A phenol phosphite polymer, diphenylhydrogenphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4 '-Isopropyridene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4- tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritoldi Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis ( 2,4-Dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable.

The organic phosphonite compound is preferably given the following general formula:
R ^5- P (OR ⁶ ) (OR ⁷ )
^(Wherein, R 5, ^{R 6} and ^{R 7} are each a hydrogen atom, an alkyl group or an aryl group having 6 to 30 carbon atoms having 1 to 30 carbon ^atoms, of R 5, ^{R 6} and ^{R 7} At least one of them is an aryl group having 6 to 30 carbon atoms.)
Examples thereof include compounds represented by.

Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Nite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrax (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite 2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite and the like. ..

As the sulfur-based stabilizer, any conventionally known sulfur atom-containing compound can be used, and among them, thioethers are preferable. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine). ), 2-Mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickeldibutyldithiocarbamate, nickelisopropylxanthate, trilauryltrithiophosphite. Of these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferred.

Examples of the phenolic stabilizer include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4). -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate is preferred.

Above all, it is preferable to use a hindered phenol-based stabilizer having a melting point of 150 ° C. or higher. When the melting point is 150 ° C. or higher, the thermal stability of the stabilizer itself becomes high, so that the stabilizer itself loses its stabilizing effect due to deterioration, or during the production of a resin composition such as melt kneading or in a high temperature environment such as injection molding. However, it becomes difficult to generate gas. Further, even if the vehicle lamp body component provided with the metal thin film on the obtained molded product is exposed to a high temperature atmosphere, the surface of the metal thin film is violated and the vehicle lamp body component is prevented from becoming cloudy. The melting point is more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit of the melting point is usually 350 ° C. or lower, preferably 300 ° C. or lower, and more preferably 280 ° C. or lower.

As the stabilizer, one type may be contained, or two or more types may be contained in any combination and ratio.

The content of the stabilizer is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect improvement in thermal stability and compatibility of the resin composition, and a decrease in molecular weight and deterioration of hue during molding are likely to occur, and 1 part by mass is used. If it exceeds the amount, the amount becomes excessive, and there is a tendency that silver streak occurs and hue deterioration is more likely to occur. The content of the stabilizer is more preferably 0.005 to 0.7 parts by mass, still more preferably 0.01 to 0.5 parts by mass.

[Release agent]
The polyester-based resin composition of the present invention preferably contains a mold release agent.
Examples of the release agent include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound, and a polysiloxane-based silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, bechenic acid, lignoceric acid, cerotic acid, melissic acid, tetraliacontanic acid, montanic acid, and adipine. Examples include acid and azelaic acid.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic term also contains an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acid and alcohol include montanic acid ester wax, beeswax (mixture containing myricyl palmitate as the main component), stearic acid stearate, behenyl behenate, stearyl behenate, and glycerin monopalmi. Examples thereof include tate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like. ..

Examples of the aliphatic hydrocarbon compound include polyolefin waxes such as liquid paraffin, paraffin wax, microcrystalline wax and polyethylene wax, fisher-tropus wax, and α-olefin oligomers having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 200 to 30,000, more preferably 1000 to 15,000, further preferably 1500 to 10000, and particularly preferably 2000 to 5000. The aliphatic hydrocarbon compound may be a single substance, or a mixture of various constituents and molecular weights can be used as long as the main component is within the above range. Of these, polyolefin wax is preferable.

As the polyolefin wax, any conventionally known polyolefin wax can be used, for example, preferably a type of olefin having 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 10 carbon atoms, or any proportion of the polyolefin wax. Examples thereof include (co) polymers containing more than one species (meaning polymerization or copolymerization; the same shall apply hereinafter).

Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, α-olefin having 4 to 30 carbon atoms (preferably 4 to 12, more preferably 4 to 10), and 4 to 30 carbon atoms (preferably 4). -18, more preferably 4-8) diene. Examples of α-olefins include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene. Examples of the diene include butadiene, isoprene, cyclopentadiene, 11-dodecadiene and the like.

As the polyolefin wax, polyethylene wax is preferable from the viewpoint of mold releasability and heat resistance.
The method for producing polyethylene wax is arbitrary, and for example, it can be produced by polymerization of ethylene or thermal decomposition of polyethylene.

As the release agent, one having an acid value of 10 to 40 mgKOH / g is preferable because it has a small release resistance, a remarkable effect of improving the release property, and a small amount of volatile matter. The acid value is more preferably 11 to 35 mgKOH / g, still more preferably 12 to 32 mgKOH / g. If the acid value is in the range of 10 to 40 mgKOH / g, one having an acid value of less than 10 mgKOH / g and one having an acid value of more than 40 mgKOH / g may be used in combination, and the acid value of the plurality of types of release agents as a whole may be determined. It may be 10 to 40 mgKOH / g.

Examples of the mold release agent having an acid value of 10 to 40 mgKOH / g include the above-mentioned ester of an aliphatic carboxylic acid and an alcohol having an acid value of 10 to 40 mgKOH / g, and the above-mentioned aliphatic hydrocarbon compound, preferably. Is a polyolefin wax containing a carboxyl group (carboxylic acid (anhydrous) group, that is, a carboxylic acid group and / or a carboxylic acid anhydride group; the same applies hereinafter), a haloformyl group, an ester group, a metal carboxylate base, a hydroxyl group, and an alcoholic acid. A modified polyolefin wax having a functional group compatible with the polyester resin, such as a group, an epoxy group, an amino group, and an amide group, is preferable.

Carboxyl groups used for modification of polyolefin wax include low molecular weight compounds containing carboxylic acid groups such as maleic acid, maleic anhydride, acrylic acid, and methacrylic acid, low molecular weight compounds containing sulfo groups such as sulfonic acid, and phosphones. Examples thereof include low molecular weight compounds containing a phospho group such as an acid. Among these, low molecular weight compounds containing a carboxylic acid group are preferable, and maleic acid, maleic anhydride, acrylic acid, methacrylic acid and the like are particularly preferable. These carboxylic acids may be used alone or in combination of two or more at any ratio.
The amount of acid added to the modified polyolefin wax is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the modified polyolefin wax.

Specific examples of the haloformyl group include a chloroformyl group and a bromoformyl group. The means for imparting these functional groups to the polyolefin wax may be any conventionally known method, and specifically, for example, copolymerization with a compound having a functional group, post-processing such as oxidation, or the like. Method may be used.

As the type of the functional group, a carboxyl group is preferable because it has an appropriate affinity with the polyester resin. The concentration of the carboxyl group in the modified polyolefin wax may be appropriately selected and determined, but if it is too low, the affinity with the polyester resin is small, the effect of suppressing volatile matter is small, and the release effect is reduced. There is. On the contrary, if the concentration is too high, for example, the polymer main chain constituting the polyolefin wax is excessively cut during the modification, and the molecular weight of the modified polyolefin wax is excessively lowered, so that volatile components are generated more and the polyester resin. Fogging may occur on the surface of the molded product.
As the modified polyolefin wax, polyethylene oxide wax is preferable.

In addition, 1 type may be contained in the mold release agent, and 2 or more types may be contained in arbitrary combinations and ratios.
The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 2 parts by mass, based on 100 parts by mass of the thermoplastic polyester resin (A). It is 1 part by mass or less. If the content of the release agent is less than the lower limit of the above range, the effect of the release property may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, the hydrolysis resistance There is a possibility that the mold will be reduced and the mold will be contaminated during injection molding.

[Manufacturing of polyester resin composition]
The polyester-based resin composition of the present invention can be produced according to a conventional method for preparing a resin composition. That is, the thermoplastic polyester resin (A), the inorganic filler (B) and the alumina (C), other resin components added as desired and various additives are mixed well together and then in a single-screw or twin-screw extruder. Melt and knead. Further, it is also possible to prepare a resin composition without mixing each component in advance or by mixing only a part thereof in advance and supplying it to an extruder using a feeder to melt-knead it. For example, a method of producing a polyester-based resin composition by melt-kneading a pre-blended product in which an inorganic filler (B) is previously blended with a polyester resin powder and polyester resin pellets can also be adopted. In this case, the preliminary blend and the polyester resin pellets can also be fed to the extruder from separate feeders. Further, a masterbatch of a part thereof may be blended and melt-kneaded. Further, it is also possible to produce various molded products by directly supplying a mixture in which each component is mixed to a molding machine such as an injection molding machine without melt-kneading.

The heating temperature for melt-kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause a poor appearance. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation and the like. It is desirable to use an antioxidant or a heat stabilizer in order to suppress decomposition during kneading and molding in the subsequent process.

[Molding]
The method for producing a molded product using the polyester-based resin composition of the present invention is not particularly limited, and a molding method generally used for the polyester-based resin composition can be arbitrarily adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, Blow molding method and the like can be mentioned. Among them, the injection molding method is preferable because the effects of the present invention are remarkable, such as good productivity and surface properties of the obtained molded product.

The molded product is excellent in surface texture, appearance, and appearance when vapor-deposited while maintaining high mechanical strength, and the occurrence of fogging is suppressed even under high temperature use, so these characteristics are strictly required. It is particularly preferably used as a base for vehicle lamp body parts, particularly reflectors and lamp extensions.

The lamp extension is provided around the lamp in the lamp chamber formed by the body of the lamp and the cover (or outer lens), and has high brightness, smoothness, and uniformity due to the directionality and reflectance of the lamp light source. High reflectance and heat resistance that can withstand heat generation from a light source are required. At least one surface of the lamp extension is mirror-treated with a metal thin film layer by vapor deposition of a metal such as aluminum. The lamp extensions for automobile lamps are often used for headlights and taillights, but are not limited to these, as well as headlights (headlamps), taillights (tail lamps), and brake lights (stop lamps). , Direction indicator lights (so-called blinkers), side lights, backward lights, etc.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not construed as being limited to the following examples.
The components used in the following examples and comparative examples are as shown in Table 1 below.

(Examples 1 to 6, Comparative Examples 1 to 5)
After uniformly mixing each component shown in Table 1 above with a tumbler mixer at the ratio shown in Table 2 below (all parts by mass), a twin-screw extruder (“TEX30α” manufactured by Japan Steel Works, Ltd. (L / D =) Using 42), the resin composition melt-kneaded under the conditions of a cylinder set temperature of 260 ° C. and a screw rotation speed of 200 rpm was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of a polyester-based resin composition. The resin temperature at the outlet of the extruder was 285 ° C.

[Liquidity (MVR)]
Takara using Kogyo Co. melt indexer, 265 ° C. The pellets obtained above, the melt flow volume MVR per unit measured time under a load of 2.16 kgf ^(Unit: cm 3 / 10min) measured bottom.

[Tensile breaking strength, tensile breaking elongation]
After the pellets obtained above are dried at 120 ° C. for 5 hours, ISO multipurpose is used under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (mold clamping force 85T) manufactured by Japan Steel Works. The test piece (4 mm thick) was injection molded.
In accordance with ISO527, the tensile strength at break (unit: MPa) and the elongation at break (unit:%) were measured using the above-mentioned ISO multipurpose test piece (thickness of 4 mm).

[Maximum bending strength, flexural modulus]
In accordance with ISO178, the maximum bending strength (unit: MPa) and flexural modulus (unit: MPa) were measured at a temperature of 23 ° C. using the above-mentioned ISO multipurpose test piece (thickness of 4 mm).

[Charpy impact strength with notch]
^{In accordance with ISO179, the notched Charpy impact strength (unit: kJ / m 2} ) of the notched test piece obtained by notching the ISO multipurpose test piece (4 mm thick) was measured at a temperature of 23 ° C.

[Thermal conductivity]
The pellets obtained above are dried at 120 ° C. for 5 hours before injection molding, and molded by an injection molding machine (“NEX80” manufactured by Nissei Resin Industry Co., Ltd.) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Obtained a plate-shaped molded product having a size of 100 mm × 100 mm × 3 mm.
Using this as a sample, the thermal conductivity in the plane direction under normal temperature conditions was measured using a hot disk method thermophysical property measuring device "TPS-2500S" manufactured by Kyoto Electronics Industry Co., Ltd.

[Appearance evaluation]
The pellets obtained above are dried at 120 ° C. for 5 hours before injection molding, and maintained by an injection molding machine (“NEX80” manufactured by Nissei Resin Industry Co., Ltd.) at a cylinder temperature of 260 ° C., an injection speed of 60 mm / sec, and an injection time of 30 sec. A substrate for a light reflector having a molded body shape of 60 mm × 60 mm × 3 mm using a mirror-finished mold with a surface finish of # 14000 abrasive under the conditions of a pressure of 60 MPa, a cooling time of 15 sec, and a mold temperature of 60 ° C. Got
The surface of the obtained light reflector substrate was vapor-deposited with aluminum so that the aluminum film thickness was 150 nm without any primer treatment to obtain a light reflector.

(I) Presence or absence of foreign matter The surface roughness of the substrate for the light reflector was measured by using a laser microscope "VK-X100" manufactured by KEYENCE Co., Ltd. under the condition of a magnification of 200 times, and the surface roughness was adjusted to 5 arbitrarily selected regions. The measurement was performed, and the maximum height (Rz) was measured according to JIS B0601.

(Ii) Heat resistant vapor deposition characteristics (heat resistance of aluminum vapor deposition surface)
Next, the above-mentioned aluminum-deposited light reflector was heat-treated with a hot air dryer (Blower constant temperature incubator DN-43 manufactured by Yamato Scientific Co., Ltd.) at 160 ° C. for 24 hours, and a spectrocolorimeter (CM of Konica Minolta Co., Ltd.) was used. -3600d ”) was used to measure the diffusion reflectance of the aluminum-deposited surface at a wavelength of 550 nm by the normal reflected light removal method, which was used as an index of the heat-resistant vapor deposition characteristics. When the amount of change in diffuse reflectance before and after the heat treatment was less than 1%, it was judged as "○" (pass), and when it was 1% or more, it was judged as "x" (fail).

(Iii) Comprehensive judgment of appearance The above (i) maximum height Rz is 5 μm or less, and the above (ii) heat-resistant vapor deposition characteristics are “○” (pass), and those that are not are “×” ( Fail).
The above results are shown in Table 2 below.

The polyester-based resin composition of the present invention is excellent in surface texture, appearance, and appearance when vapor-deposited while maintaining high mechanical strength, exhibits high thermal conductivity, and does not generate gas during molding. Since it is a material and the product obtained by vapor-depositing aluminum on the surface thereof has an extremely good appearance and exhibits high thermal conductivity, it can be suitably used as a component for a vehicle lamp body of an automobile or the like.

Claims (4)

0.01 to 10 parts by mass of one or more inorganic fillers (B) selected from calcium carbonate, talc, and kaolin having an average particle diameter of 2 μm or less, with an average particle diameter of 100 parts by mass, based on 100 parts by mass of the thermoplastic polyester resin (A). A polyester type containing 0.01 to 10 parts by mass of alumina (C) having an aspect ratio of 8 μm or less and an aspect ratio of 1.5 or less, and 1 to 20 parts by mass of an acrylonitrile-styrene copolymer (D). Resin composition. The polyester-based resin composition according to claim 1, wherein the alumina (C) is spherical alumina. The polyester resin composition according to claim 1 or 2 , further containing 0.01 to 5 parts by mass of carbon black (E) with respect to 100 parts by mass of the thermoplastic polyester resin (A). The polyesulte-based resin composition according to any one of claims 1 to 3 , wherein the polyester resin powder having an average particle size of 1000 μm or less occupies 1 to 50% by mass in 100% by mass of the thermoplastic polyester resin (A).