JP6540258B2 - Polyester resin composition for automobile lamp members - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a polyester resin composition that can be used as an automotive lamp member of a black base attachment specification that effectively suppresses heat generation due to sunlight concentration and that has good design and heat resistance.

  Polybutylene terephthalate resin is widely used as an injection molded article in the fields of automobile parts, machine parts, electricity and communication parts, etc., taking advantage of its excellent injection moldability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc. It's being used. Furthermore, it is excellent in mold transferability, and is suitably used as a lamp member for an extension application of an automobile, etc. where a particularly good appearance is required. In addition, it is necessary to highly control the heat resistance of the resin and the suppression of gas generation (low gas property) at the time of molding or the like from the application.

  On the other hand, in recent years, headlamps for luxury cars and the like are equipped with LED lights, and the lamp design has also begun to be renewed. For example, in the reflector type (the light from the light source is reflected by the reflector and irradiated), it is necessary to deposit aluminum on the portion closest to the light source, but for the projector type (condensing the light from the light source on the front lens and irradiating it) There is also a design that changes the part closest to the light source to the black base specification. However, due to this change, when the sunlight is reflected by the projector lens, and the light is condensed on the surrounding black area, the sun light collection will be scratched due to the very high temperature of the condensed area. The light problem began to occur (this phenomenon has been known for a long time, but it has not been a problem in lamp design until now). In response to this problem, materials with non-storage, infrared light reflectivity, and infrared light transmission that do not become high temperature even if sunlight is collected, and heat resistance that does not get damaged even when high temperature There is a need for materials having the property.

  For example, Patent Document 1 discloses a polyethylene terephthalate resin composition that does not contain carbon black but contains a dye that is blackened by color adjustment as a technique for obtaining a black base-bonded polyester resin composition that suppresses the temperature rise due to sunlight. It is done. However, according to the composition of the present invention, the deterioration of the fogging due to the dye is often a problem, and it is practically difficult to use as a lamp member for an automobile. Furthermore, in the case of a crystalline resin having a relatively slow crystallization rate such as polyethylene terephthalate, the heat resistance due to crystallization is insufficient, so in a situation where high energy is concentrated such as sunlight concentration, the light collecting portion is It may melt and is not suitable for automotive lamp component applications.

  As a technique for transmitting infrared light, for example, in Patent Documents 2 to 4, a resin comprising polybutylene terephthalate or polybutylene terephthalate and a copolymer of polybutylene terephthalate, a polycarbonate resin, a styrene acrylonitrile resin, 1,4-cyclohexanedilide There is disclosed a resin composition obtained by blending an amorphous resin such as a polyester resin containing a methanol component. However, although these techniques are useful for increasing the infrared light transmission of polybutylene terephthalate resin, the addition of amorphous resin significantly reduces the heat distortion temperature, making it particularly practical for lamp member applications. It is difficult to use.

JP, 2014-125588, A JP, 2004-315805, A Patent No. 5034217 JP, 2008-106217, A

  The present invention has been made on the background of the problems of the prior art. That is, an object of the present invention is to provide a polyester resin composition for a lamp member of a black original attachment specification, which effectively suppresses heat generation due to sunlight concentration and has good design and heat resistance. is there.

  The above-mentioned subject is sufficient by suppressing the heat storage property by carbon black, ie, using non-heat storage pigments other than carbon black, using the pigment which has infrared light reflectivity, and using an organic dye if necessary. It has been found that it can be solved by producing a polyester resin composition having a blackish tint. Furthermore, the optimum polyester resin was selected as the composition, and the formulation satisfying the required fogging resistance (low gas resistance) was examined.

The present inventors diligently studied to complete the present invention.
That is, the present invention has the following constitution.
[1] Inorganic filler (B) having an average particle diameter of 3 μm or less 0.005 to 20 parts by mass, non-carbon black pigment (D1) 0.05 to 10 parts by mass, with respect to 100 parts by mass of polyester resin (A) And a polyester resin composition containing 0 to 10 parts by mass of an organic dye (D2), wherein the hue L ^* value of the CIE color difference system L ^* a ^* b ^* system of the polyester resin composition is 10 or less The polyester resin composition for lamp members for motor vehicles characterized by the above.
[2] The automobile according to [1], wherein the polyester resin (A) contains a polybutylene terephthalate resin (a) and a polyethylene terephthalate resin (b) in a mass ratio of 100: 0 to 50:50. Polyester resin composition for lamp members.
[3] The polyester resin composition for automotive lamp members according to [1] or [2], containing 0.05 to 3 parts by mass of the polycarbodiimide compound (C) with respect to 100 parts by mass of the polyester resin (A) .
[4] The inorganic filler (B) contains one or more selected from talc, barium sulfate, calcium carbonate and titanium dioxide, according to any one of [1] to [3]. Polyester resin composition for lamp members for automobiles.

  One of the features of the polyester resin composition for a lamp member of a motor vehicle of the present invention is that the blackness with high designability is realized while effectively suppressing the heat generation due to the sunlight concentration. Furthermore, the polyester resin composition for lamp members for motor vehicles excellent in fogging resistance, heat resistance, and mechanical characteristics can be obtained.

  Hereinafter, the present invention will be described in detail.

[Polyester resin (A)]
As polyester resin (A) which can be used by this invention, it is preferable that it is a polyester resin which makes a dicarboxylic acid component and a diol component a structural unit.
As the dicarboxylic acid component, one containing an aromatic dicarboxylic acid as a main component is preferable. The main component is usually 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more, based on all the dicarboxylic acid units. Apart from aromatic dicarboxylic acids, aliphatic dicarboxylic acids can be used.

As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, Aroma such as 7-naphthalene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, anthracene dicarboxylic acid Among these, terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid are preferable.
Specific examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid, which generally have 2 to 40 carbon atoms. A chain or alicyclic dicarboxylic acid may be mentioned.
The above dicarboxylic acid components can be used alone or in combination of two or more.
In addition to the dicarboxylic acid component and the diol component, a hydroxycarboxylic acid component or a lactone component may be copolymerized. The amount used is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, based on the total monomer components.

  As a diol component, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5 -Pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and the like. Among these, ethylene glycol, 1,3-propanediol and 1,4-butanediol are preferable.

Preferred polyester resins (A) include polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene naphthalate and polyethylene naphthalate.
The polyester resin (A) preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when the o-chlorophenol solution is measured at 25 ° C., and 0.52 to 1.25 dl. Is more preferably in the range of 0.5 to 1.12 dl / g, and most preferably in the range of 0.62 to 1.02 dl / g. It is. When the intrinsic viscosity of (a) is 0.36 to 1.60 dl / g, mechanical properties and moldability of the polyester resin composition for a lamp member of the present invention of the present invention become good.
In the present invention, it is preferable to contain the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in specific amounts. In the present invention, it is also preferable to use polytrimethylene terephthalate and polybutylene naphthalate as the polyester resin (A).

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

  The polybutylene terephthalate resin (a) which can be used in the present invention preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when the o-chlorophenol solution is measured at 25 ° C. And more preferably in the range of 0.52 to 1.25 dl / g, and still more preferably in the range of 0.58 to 1.12 dl / g, and more preferably 0.62 to 1.02 dl / g. Those in the range of g are most preferred. When the intrinsic viscosity of (a) is 0.36 to 1.60 dl / g, mechanical properties and moldability of the polyester resin composition for a lamp member of the present invention of the present invention become good.

  The polyethylene terephthalate resin (b) which can be used in the present invention is obtained by a usual polymerization method such as polycondensation reaction of terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative as main components. Polymer. It is preferable that the ethylene terephthalate repeating unit is a polymer having 80 mol% or more, the ethylene terephthalate repeating unit is more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%. Other copolymerization components may be included within a range that does not impair the properties, for example, about 20% by mass or less. Examples of the copolymer include polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polyethylene (terephthalate / decanedicarboxylate), polyethylene (terephthalate / naphthalate), poly (ethylene) / Cyclohexanedimethyl) / terephthalate, poly (butylene / ethylene) terephthalate, etc. may be used alone or in combination of two or more. By using the above-mentioned polyethylene terephthalate resin (b), moldability and surface appearance become better.

  The polyethylene terephthalate resin (b) which can be used in the present invention preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when the o-chlorophenol solution is measured at 25 ° C. In the range of 0.45 to 1.35 dl / g, more preferably in the range of 0.50 to 1.20 dl / g, and still more preferably 0.55 to 1.05 dl / g. The most preferable one is in the range of When the intrinsic viscosity of (b) is 0.36 to 1.60 dl / g, mechanical properties and moldability of the polyester resin composition for a lamp member of the present invention of the present invention become good.

In the present invention, the blending amount of the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) is 100: 0 to 50:50 in the mass ratio of (a) to (b) ((a) :( b)). Is preferred. More preferably (a): (b) = 100: 0 to 60: 40, still more preferably (a): (b) = 100: 0 to 70:30, particularly preferably (a): (b) = 100 0:80:20. Although it is possible to improve the surface appearance of the resin composition by blending the polyethylene terephthalate resin (b), if the blending amount exceeds 50 parts by mass, the releasability during injection molding of the resin composition may be deteriorated. The heat resistance of the resin may decrease.
In the present invention, the total amount of the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in the polyester resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more Is more preferable, and 100% by mass may be sufficient.

[Inorganic filler (B) having an average particle size of 3 μm or less]
The polyester resin composition for a lamp member of a motor vehicle of the present invention contains 0.005 to 20 parts by mass of the inorganic filler (B) with respect to 100 parts by mass of the polyester resin (A).
The inorganic filler (B) can further improve the heat resistance and the rigidity, and can control the shrinkage rate to be small. In particular, if the shrinkage ratio is large, mold release defects may occur due to adhesion to the mold during injection molding, or distortion may occur in the molded product if the molded product is large or the shape is complicated. Control of the contraction rate by (B) is important.
When content of an inorganic filler (B) is less than 0.005 mass part, the improvement effect of heat resistance and rigidity is small. If it exceeds 20 parts by mass, the relief of the filler impairs the surface smoothness necessary for use as a lamp member.
The content of the inorganic filler (B) is preferably 0.2 parts by mass or more from the viewpoints of improvement of heat resistance and rigidity, and surface smoothness, and the content of the inorganic filler (B) is 5 More preferably, it is at least 8 parts by mass.

  The inorganic filler (B) needs to have an average particle size (50% of weight (volume) cumulative particle size distribution) measured by a laser diffraction method of 3 μm or less. When the average particle size exceeds 3 μm, the surface smoothness is impaired, which is not preferable. The average particle size of the inorganic filler (B) is preferably 2.8 μm or less.

The inorganic filler (B) preferably contains one or more of talc, barium sulfate, calcium carbonate and titanium dioxide.
Among the above inorganic fillers, talc has a nucleating agent effect on the polyester resin, and the heat resistance of the polyester resin can be improved by adding a small amount thereof. However, since talc has a relatively large particle size, the surface smoothness is lowered due to the embossment on the resin surface when the addition amount is large.
On the other hand, barium sulfate, calcium carbonate and titanium dioxide do not have a nucleating agent effect on polyester resin, but because their particle size is smaller than talc, they can easily maintain surface smoothness even if their addition amount is large . In order to control the shrinkage rate, it is preferable that the addition amount of the inorganic filler is larger, and the use of barium sulfate, calcium carbonate and titanium dioxide is suitable.
From the viewpoint of heat resistance improvement and surface smoothness, it is preferable that talc contains 0.005 to 1 part by mass, and barium sulfate, calcium carbonate and titanium dioxide contain 2 to 20 parts by mass. More preferably, talc is 0.05 to 0.8 parts by mass, and barium sulfate, calcium carbonate and titanium dioxide are 3 to 19 parts by mass. More preferably, talc is 0.1 to 0.5 parts by mass, and barium sulfate, calcium carbonate and titanium dioxide are 5 to 18 parts by mass. With this content of barium sulfate, calcium carbonate and titanium dioxide, the shrinkage rate can also be controlled.

The inorganic filler (B) is a crystalline of talc while maintaining its surface smoothness by using a small amount of talc in combination with at least one member of the group consisting of barium sulfate, calcium carbonate and titanium dioxide. The nucleating agent effect and the reinforcing effect of the filler can be simultaneously obtained, and the heat resistance can be extremely improved.
When a small amount of talc and at least one member selected from the group consisting of barium sulfate, calcium carbonate and titanium dioxide are used in combination, when the total of the inorganic filler (B) is 100% by mass, Preferably, the total of at least one member in the group consisting of barium sulfate, calcium carbonate and titanium dioxide is 99.8-80% by mass with respect to 20% by mass.

The polyester resin composition for a lamp member of a motor vehicle of the present invention can exhibit good surface smoothness even if the inorganic filler (B) is not surface-treated, but in order to enhance compatibility and dispersibility, the inorganic filler (B) May be surface treated. In addition, when carrying out surface treatment, it is preferable to surface-treat to such an extent that other characteristics, such as fogging, are not affected by gas generation.
As surface treatment, treatment with a surface treatment agent, treatment with fatty acid, treatment with SiO ₂ -Al ₂ O _{3 and the} like can be mentioned. The surface treatment agent is not particularly limited, and for example, an aminosilane coupling agent, an epoxysilane coupling agent, a titanate coupling agent, an aluminate coupling agent and the like can be used.

[Polycarbodiimide Compound (C)]
It is preferable that the polyester resin composition for lamp members for motor vehicles of this invention contains 0.05-3 mass parts of polycarbodiimide compounds (C) with respect to 100 mass parts of polyester resin (A).
By setting the polycarbodiimide compound (C) in this range, gasifying components such as free carboxylic acid compounds and free hydroxyl group-containing compounds can be efficiently captured, and excellent low gas property can be realized.
When the amount of the polycarbodiimide compound (C) is more than 3 parts by mass, the reaction with the polyester resin (A) may cause gelation or the productivity may be significantly reduced. When the amount of the polycarbodiimide compound (C) is less than 0.05 parts by mass, the scavenging effect of the free acid and the compound containing a free hydroxyl group may be reduced, and the low gas property may be impaired. The compounding amount of the polycarbodiimide compound (C) is more preferably 0.1 to 2 parts by mass, still more preferably 0.15 to 1 parts by mass with respect to 100 parts by mass of the polyester resin (A). .

The polycarbodiimide compound (C) can have a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule.
A compound having a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule is a free acid or free hydroxyl group-containing compound derived from a raw material, a free acid or free hydroxyl group generated during heat treatment in a later heat treatment process or at high temperature. It is possible to immediately capture contained compounds and exert an effect of preventing volatilization.
Since the free acid and the compound containing a free hydroxyl group greatly affect the generation of gas, the capture thereof is effective for preventing volatilization. Since free carboxylic acids volatilize at relatively low temperatures and their volatiles crystallize in particular, they often cause fogging, so trapping of free carboxylic acids is extremely important.

As a functional group which reacts with carboxylic acid, a glycidyl group, an oxazoline group, an oxetane group, a carbodiimide group etc. are mentioned. However, general glycidyl group-containing compounds, oxazoline group-containing compounds and oxetane group-containing compounds are not quick in reaction, and there are cases where coexistence with a functional group that reacts with a hydroxyl group is difficult, and furthermore, volatilization of the compound itself is Because of its fierce, its use in applications requiring anti-fogging properties is often difficult. On the other hand, the reaction of the carbodiimide compound is quicker than that of the glycidyl group, the oxazoline group and the oxetane group, and the use for capturing free carboxylic acid is very preferable.
The functional group that reacts with a hydroxyl group is different from the functional group that reacts with a carboxylic acid, and includes, for example, an isocyanate group and an acid anhydride group, but an isocyanate group is particularly preferable from the viewpoint of reactivity. As a result of intensive studies, as a compound having a carboxylic acid group reactive group and a hydroxyl group reactive group in one molecule, a compound having a carbodiimide group and an isocyanate group in one molecule is most preferable.
The merit of containing a carboxylic acid group reactive group and a hydroxyl group reactive group in one molecule is that these functional groups can be easily reacted with any of the thermoplastic resin and the free acid or free hydroxyl group-containing compound, and the heat of large molecular weight By connecting the plastic resin and the decomposition product with the reactive compound, the volatilization of the decomposition product derived from the raw material can be significantly reduced. Therefore, in the case of a thermoplastic polyester resin containing a carboxylic acid as in the present invention, effects such as hydrolysis suppression can be imparted, and effects such as processability improvement as a resin composition can also be exhibited.

  Polycarbodiimide is a compound having two or more structures of -N = C = N- in one molecule, and known compounds produced by decarbon dioxide reaction of a diisocyanate compound can be used (US Pat. No. 2,941,956, JP-B-47-3279, J. Org. Chem., 28, 2069 to 2075 (1963), Chemical Review 1981, Vol. 81, No. 4, 619 to 621).

  Aliphatic or alicyclic isocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate and the like, and 4,4-diphenylmethane diisocyanate, as the diisocyanate compound. Diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, tetramethylxylylene Aromatic compounds such as di-isocyanate and 1,3,5-triisopropylphenylene-2,4-diisocyanate Isocyanate compounds may be mentioned, it can be used by copolymerizing them singly or in combination.

The polycarbodiimide compound (C) may have a branched structure, and functional groups other than the carbodiimide group and the isocyanate group may be introduced by copolymerization. Furthermore, the terminal isocyanate may be partially or completely blocked. Examples of end capping agents include monoisocyanate compounds such as phenyl isocyanate, tris isocyanate, dimethyl phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate, -OH group, -COOH group, -SH group, -NH-R (R is hydrogen Compounds having an atom or an alkyl group etc. can be used.
The advantage of blocking the terminal isocyanate partially or completely is that the reaction in the compound can be easily controlled, and the degree of polymerization and the melt viscosity can be controlled. When a certain amount or more of the polycarbodiimide compound not blocking the terminal isocyanate is added to the polyester resin (A), the melt viscosity may become extremely high due to the thickening, and the addition amount may be limited. If the addition amount of the polycarbodiimide compound is thereby limited, the expected effect may not be obtained. When such a problem arises, it is solvable by using the polycarbodiimide compound which blocked the terminal isocyanate.
Even if all the terminal isocyanates are blocked, the effect of capturing free carboxylic acids is high due to the high reactivity of the carbodiimide group, so a sufficiently low gas property can be obtained.

  Commercially available products include Stavacsol series manufactured by Line Chemie, Carbodilight series manufactured by Nisshinbo, Cosmonate LK manufactured by Mitsui Takeda Chemical Co., Cosmonate LL, and Luplanate MM-103 manufactured by BASF INOAC Polyurethane. Be Among them, it is preferable to use a polycarbodiimide compound having an aliphatic or alicyclic structure from the viewpoint of compatibility with fatty acid. When it is aromatic polycarbodiimide, compatibility with a fatty acid may be bad, a carbodiimide group and a fatty acid can not react efficiently, but an effect reduces. Among the commercially available products described above, Nisshinbo's Carbodilite series is preferably used because it has an aliphatic or alicyclic structure.

[Non-carbon black pigment (D1)]
The polyester resin composition for a lamp member of a motor vehicle of the present invention contains 0.05 to 10 parts by mass of the non-carbon black pigment (D1) with respect to 100 parts by mass of the polyester resin (A).
The non-carbon black pigment (D1) is preferably black in terms of design.
If the amount is less than 0.05 parts by mass of the non-carbon black pigment (D1), the blackness may be insufficient and the designability may be impaired. If the amount is more than 10 parts by mass, mechanical properties may deteriorate, bleed out and fogging may be a problem. The content of the non-carbon black pigment (D1) is more preferably 0.1 to 8 parts by mass, and still more preferably 1 to 7 parts by mass.

Known non-carbon black pigments (D1) can be used, and one or two or more pigments may be mixed and used. Non-carbon black pigments are often lower in blackness than carbon black, so when used as a lamp member for black base cars, the pigment concentration may be increased or blackness used when used in combination with a black dye. Is preferably high.
In the case of a black pigment having infrared light reflectivity, even if the pigment concentration is high, it is often difficult to reach a high temperature due to the condensation of sunlight, but if it exceeds 10 parts by mass (especially in the case of inorganic pigments) The amount of absorption of is increased, and may be damaged by the collection of sunlight. When the blackness is insufficient, it is preferable to add a black dye to adjust the blackness.
In the case of a black pigment having no infrared light reflectivity, if the pigment concentration is increased (particularly in the case of an inorganic pigment), the addition of about 5 parts by mass may result in high temperature due to the collection of sunlight. In this case, it is preferable to suppress the pigment concentration to 5 parts by mass or less and adjust the blackness in combination with the black dye.
The non-carbon black pigment (D1) may be added directly to the resin at the time of compounding, or may be added as a master batch.

Examples of non-carbon black pigments that can be added to polyester resin compositions include Cu-Cr-Mn, Co-Fe-Cr, Fe-Cr, Mn-Bi, Co-Cr-Fe-Mn, etc. And organic pigments such as azo pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, quinacridone pigments, and perylene pigments.
Among them, Fe-Cr, Mn-Bi, Co-Cr-Fe-Mn complex oxide pigments having infrared light reflectivity, organic pigments having low infrared light absorbability are preferably used. Be
These may be used alone, or two or more kinds of pigments may be mixed and used in color adjustment.
Inorganic pigments generally reflect or absorb infrared light because they do not have infrared light transparency. Therefore, among the complex oxide pigments, those having low infrared light reflectance, that is, they are more likely to absorb infrared light, and thus tend to increase in temperature due to sunlight concentration (however, temperatures are higher than carbon black). Hard to rise). A pigment having a low infrared light absorbability and a high infrared light reflectivity is preferable because it has a high temperature rise suppression effect due to sunlight concentration.

[Organic dye (D2)]
The polyester resin composition for a lamp member of a motor vehicle of the present invention contains 0 to 10 parts by mass of the organic dye (D2) with respect to 100 parts by mass of the polyester resin (A).
The organic dye (D2) is preferably black in terms of design.
When the blackness of the non-carbon black pigment (D1) is insufficient, the organic dye (D2) is preferably contained for the main purpose of compensating for it. When sufficient blackness can be obtained with the non-carbon black pigment (D1), the organic dye (D2) may not be contained.
If the amount of the organic dye (D2) exceeds 10 parts by mass, bleed out and fogging may be a problem. The content of the organic dye (D2) is more preferably 0 to 8 parts by mass, further preferably 0 to 5 parts by mass, particularly preferably 0 to 3 parts by mass, and most preferably 0 to 1 parts by mass.

A well-known thing can be used for an organic dye (D2), and 1 type, or 2 or more types of dye may be mixed and used. Those obtained by mixing two or more dyes and performing toning are preferred because black is easily expressed.
Examples of dyes that can be added to the polyester resin composition include dyes such as quinoline dyes, anthraquinone dyes, azo dyes, perinone dyes, perylene dyes, phthalocyanine dyes, carbonium dyes, and indigoid dyes.
The organic dye (D2) may be added directly to the resin at the time of compounding or may be added as a master batch. From the viewpoint of dispersibility and handling, it is preferable to add in a master batch. When the organic dye is commercially available as a masterbatch, the content of the dye is usually about 5 to 20% by mass in many cases, depending on the kind of base resin and dye used.

When the organic dye (D2) is added as a masterbatch, the hue (measured in pellet form) of the masterbatch pellet is the hue L ^* value (Color-L) according to the L ^* a ^* b ^* system of the CIE color difference system. ) Is preferably 22 or less, the hue a ^* value (Color-a) is -1.5 or more and 1.5 or less, and the hue b ^* value (Color-b) is preferably -1.5 or more and 1.5 or less ( All measured values by SCE method).
When the hue of the masterbatch of the organic dye (D2) is in the above range, sufficient blackness can be obtained without impairing the dispersibility and handling of the dye.
When the hue of the masterbatch exceeds the above range, the polyester resin composition may not obtain sufficient blackness, and the design may be impaired.
More preferably, the hue of the master batch pellet is 21 or less of the hue L ^* value (Color-L) according to L ^* a ^* b ^* system of CIE color difference system, and the hue a ^* value (Color-a) is -1 or more 1 or less, hue b ^* value (Color-b) is -1 or more and 1 or less (all are measured values by the SCE method).

In the polyester resin composition for a lamp member of a motor vehicle of the present invention, carbon black may be added for the purpose of adjusting the blackness in the range in which the infrared light reflectivity is not significantly reduced.
When most of the coloring agent is composed of a non-carbon black pigment and an organic dye, blackness can be obtained while retaining most of the infrared light reflectivity, if it is a very small amount of carbon black.
The content of carbon black is preferably 10% by mass or less, and 5% by mass or less, based on 100% by mass of the total amount of the non-carbon black pigment (D1) and the organic dye (D2). More preferable. If the content of carbon black is 10% by mass or more, the infrared reflectivity may be significantly reduced, and the temperature may be extremely high due to sunlight concentration.

It is preferable that the average value in wavelength 800-1100 nm of the spectral reflectance of the flat plate of 2 mm in thickness obtained from this polyester resin composition is 7% or more of the polyester resin composition for lamp members of the motor vehicle of this invention.
The details of the spectral reflectance measurement are as described in the section of Example, but a flat plate of 2 mm thickness obtained by injection molding a polyester resin composition for a lamp member of the automobile at a mold temperature of 60 ° C. Used and measured with a spectrophotometer. The average value is a value obtained by dividing the sum of reflectance at each wavelength by the number of measurements at 800 to 1100 nm. The number of measurements depends on the sampling pitch. For example, when the sampling pitch is 1 nm, reflectance data for each 1 nm can be obtained such as 800, 801, 802,..., 1098, 1099, and 1100 nm, and the number of measurements is 301. Therefore, in this case, the average value of the reflectances at the wavelengths of 800 to 1100 nm can be obtained by (sum of the reflectances at each wavelength / 301).
Even if sunlight condenses, it is hard to become high temperature because the average value of the reflectance of wavelength 800-1100 nm exists in this range.
The feature of the polyester resin composition for a lamp member of a motor vehicle according to the present invention is that the heat generation due to sunlight condensation is effectively suppressed while realizing high blackness with a designability, and further the heat resistance is improved by the inorganic filler. It is the point given. Therefore, even if sunlight condenses, it is difficult to become high temperature and it is hard to get scratched.
It becomes very high temperature by condensing of sunlight as the average value of the reflectance of wavelength 800-1100 nm is less than 7%. 15% or more is preferable and, as for the average value of the reflectance of wavelength 800-1100 nm, 20% or more is more preferable.

The polyester resin composition for a lamp member of a motor vehicle according to the present invention has the above-mentioned constitution, so that the hue L ^* value (Color-L) by the L ^* a ^* b ^* system of CIE color difference system is 10 or less (SCE method) It is a measured value).
When the L ^* value is 10 or less, the polyester resin composition for a lamp member of a car according to the present invention can have sufficient blackness, and sufficient blackness can be obtained even in a molded product obtained by melt molding or the like. Since it can be expressed, it is excellent in the designability. The hue L ^* value is preferably 8 or less, more preferably 7 or less. When the hue L ^* value is higher than 10, the blackness is insufficient and the designability is low.

It is preferable that the polyester resin composition for lamp members for motor vehicles of the present invention has a heat deformation temperature of 130 ° C. or higher at a load of 0.45 MPa. The heat distortion temperature is measured as described in the example section.
If the heat distortion temperature is less than 130 ° C., heat resistance may be insufficient, and in particular, it may not be used for applications requiring heat resistance. When the heat distortion temperature is 130 ° C. or more, it can be said that the polyester resin composition satisfies the heat resistance as a resin for a lamp member. The heat distortion temperature is more preferably 135 ° C. or higher. In that case, the heat resistance as the resin for a lamp member is highly satisfied, 140 ° C. or higher is more preferable, and in this case, it can be said highly satisfactory.

The polyester resin composition for a lamp member of a motor vehicle according to the present invention can have a haze value of 5% or less after the fogging test (160 ° C.) by containing a specific amount of the polycarbodiimide compound (C). . According to the present invention, the generation of gas can be effectively suppressed, and excellent fogging resistance can be provided.
If the amount of generated gas is large and the haze value of the glass plate after the fogging test (160 ° C.) exceeds 5%, there is a problem of fogging in practical use as various lamp parts. Furthermore, the mold may be easily contaminated during injection molding, which may adversely affect the quality and productivity.

The fogging test can be performed by the following method.
A small piece of about 40 mm × 40 mm in size is cut out of an injection-molded product (thickness 2 mm), and a total of 10 g is put in a glass cylinder (for example φ65 × 80 mm) with a bottom made of aluminum foil and put on a hot plate set. Furthermore, after covering with a slide glass (for example, 78 mm × 76 mm × 1 mm thickness) so that no gap is formed in the glass cylinder, heat treatment is performed at 160 ° C. for 24 hours (as a result of this heat treatment The deposit | attachment by the decomposition product etc. which sublimated from the resin composition precipitates. The haze value of the slide glass is measured using a haze meter or the like.

The polyester resin composition for a lamp member of a motor vehicle of the present invention may contain a release agent in the range not to impair the characteristics as the present invention in order to further improve the releasability.
The content of the release agent is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyester resin (A). If the amount of the releasing agent is less than 0.1 parts by mass, a sufficient releasing effect can not be obtained, and there may be a problem of releasing failure, releasing wrinkles and the like. The mold release agent itself contaminates the mold by becoming a gas and bleeding out, and adheres to the lens cover, mirror, etc. in a temperature environment in the range of 100 ° C. to 200 ° C. to cause fogging. There is a problem of causing (fogging). When the amount of the release agent exceeds 3 parts by mass, these problems become significant.

  The type of the releasing agent is not particularly limited as long as it can be used for polyester. For example, long-chain fatty acids or esters or metal salts thereof, amide compounds, polyethylene wax, silicone, polyethylene oxide and the like can be mentioned. The long chain fatty acid preferably has 12 or more carbon atoms in particular, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, etc. Partial or whole carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed. Examples of the amide compounds include ethylene bisterephthalamide, methylene bisstearylamide and the like. These release agents may be used alone or as a mixture.

In addition, various additives can be added to the polyester resin composition for a lamp member of a motor vehicle of the present invention, as needed, within a known range, as long as the characteristics of the present invention are not impaired. Examples of known additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, modifiers, antistatic agents, and flame retardants.
The polyester resin composition for a lamp member of a motor vehicle according to the present invention has a total of (A), (B), (C), (D1), and (D2) components ((C), (D2 component: 0 mass) %) And 85% by mass or more are preferable, 90% by mass or more is more preferable, and 95% by mass or more is more preferable.

  The polyester resin composition for a lamp member of a motor vehicle of the present invention can be manufactured by mixing the above-mentioned components and various stabilizers as required, 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, etc. can be used. Above all, it is preferable to use a twin-screw extruder. As general melt-kneading conditions, in a twin-screw extruder, the cylinder temperature is 230 to 270 ° C., and the kneading time is 2 to 15 minutes.

  It does not restrict | limit especially as a shaping | molding method of the polyester resin composition for lamp members of the motor vehicle of this invention, Well-known methods, such as injection molding, extrusion molding, blow molding, can be used. Among them, injection molding is preferably used from the viewpoint of versatility.

  The molded article of the polyester resin composition for a lamp member of a motor vehicle of the present invention can directly form (evaporate) a light reflecting metal layer on at least a part of the surface. The deposition method is not particularly limited, and known methods can be used.

  The molded article molded using the polyester resin composition for a lamp member of a car of the present invention can be used as a lamp member of a black original specification specification.

  Hereinafter, the present invention will be more specifically described by way of 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) Spectral reflectance of infrared light (wavelength 800 to 1100 nm) The pellets obtained in Examples and Comparative Examples were molded using an injection molding machine. Using an injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.), a flat molded article of 100 mm × 100 mm × 2 mm thickness having a mirror surface polished with a # 6000 file on one side was injection molded. Molding was performed at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C.
Using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation) (a barium sulfate white plate is used as a standard white plate), a spectral reflectance of a wavelength of 300 to 1500 nm as a sampling pitch of 1.0 nm and a slit width (20) Were measured, and the average value of the reflectance at a wavelength of 800 to 1100 nm (sum of reflectance at each wavelength / 301) was calculated.

(2) Hue The hue of the flat plate of the polyester resin composition for a lamp member of an automobile was measured by the following method.
Using an injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.), a flat molded article of 100 mm × 100 mm × 2 mm thickness having a mirror surface polished with a # 6000 file on one side was injection molded. Molding was performed at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C.
Measure the hue L ^* value (CIE color difference system) on the mirror side of the molded plate according to JIS Z 8722 and JIS Z 8781-4 using a precision spectrophotometric colorimeter TC-1500SX (manufactured by Tokyo Denshoku Co., Ltd.) did. It measured by D65 light source, 10 degrees of vision, 0 degree-d method, and SCE method.
The hue of the organic dye (D2) masterbatch pellet was measured by the following method.
Pellets are placed in the attached case according to JIS Z 8722 and JIS Z 8781-4, using a precision spectrophotometric colorimeter TC-1500SX (manufactured by Tokyo Denshoku Co., Ltd.), and set on a rotary table to obtain hue L ^* The a ^* b ^* values (CIE color difference system) were measured. It measured by D65 light source, 10 degrees of vision, 0 degree-d method, and SCE method.

(3) Haze value A small piece of about 40 mm × 40 mm in size is cut out from an injection-molded product with a thickness of 2 mm, and a total of 10 g is put into a glass tube (φ 65 × 80 mm) with a bottom made of aluminum foil and hot It was set on a plate (Neo-hot plate HT-1000, manufactured by As One Corporation). Further, the glass cylinder was covered with slide glass (78 mm × 76 mm × thickness 1 mm), and then heat treatment was performed at 160 ° C. for 24 hours. As a result of this heat treatment, deposits due to decomposition products and the like sublimed from the resin composition were deposited on the inner wall of the slide glass. The haze value of these slide glasses was measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(4) Appearance A 100 mm × 100 mm × 2 mm thick flat plate molded product having a mirror surface polished with a # 6000 file on one side was injection molded using an injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.). The molding was performed at a low injection speed where cylinder temperature is 260 ° C., mold temperature is 60 ° C., cycle time is 40 seconds, and filler float is likely to occur on the surface. The mirror surface of the molded article was visually evaluated for defects (whitening, surface roughness) due to the floatation of the filler.
◎: There is no whitening and no roughening of the surface.
○: Whitening and surface roughness are slightly recognized depending on the angle of visual observation, but there is no problem in practical use.
Δ: Whitening and rough surface are observed.
X: Whitening and surface roughness are extremely noticeable.

(5) Appearance after Annealing The flat molded product used in (4) Appearance evaluation described above is placed in a shelf-type isothermal dryer set at 130 ° C. for 4 hours and subjected to annealing treatment. It was visually evaluated whether there was any defect (whitening, rough surface) due to the floating of the glass.
◎: There is no whitening and no roughening of the surface.
○: Whitening and surface roughness are slightly recognized depending on the angle of visual observation, but there is no problem in practical use.
Δ: Whitening and rough surface are observed.
X: Whitening and surface roughness are extremely noticeable.

(6) Thermal deformation temperature (load: 0.45MPa)
Heat distortion temperature (HDT) was used as an index of heat resistance of the resin composition. A multi-purpose test piece of ISO-3167 was molded using an injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.), and the HDT was measured at a load of 0.45 MPa according to ISO-75.

(7) Thermal storage performance evaluation (measurement of reaching temperature)
Thermal storage temperature measurement was performed using a flat-plate-formed article injection-molded to a thickness of 2 mm.
A flat molded product is irradiated with an infrared lamp (250 W) at an irradiation distance of 400 mm in an environment of a measurement atmosphere of 23 ° C. and a humidity of 50%, and the surface reaching temperature of the central part of the flat molded product after 30 minutes is a noncontact thermometer It was measured by (Infrared thermography i5 manufactured by Optex Co., Ltd.).
By the high and low of the ultimate temperature, it is possible to compare the influence of the heat storage property on the difference of the resin composition and the pigment by the irradiation of sunlight. The lower the temperature reached, the better.
Note that this measurement value is the ultimate temperature when the sunlight is uniformly irradiated, and the trend of the ultimate temperature between levels does not differ from the trend under the actual environment, but under the actual environment, the sunlight The temperature reached by the concentration of light becomes higher (the temperature difference between the levels becomes larger in the case of the collection of sunlight).

  The blending components used in the examples and comparative examples are shown below.

Polyester resin (A);
Polybutylene terephthalate resin (a): IV = 0.83 dl / g, acid value = 30 eq / t
Polyethylene terephthalate resin (b): IV = 0.62 dl / g, acid value = 30 eq / t

Inorganic filler (B);
The following average particle diameter shows the value (50% diameter of weight (volume) cumulative particle size distribution) measured by the laser diffraction method.
(B-1) Talc (average particle size: 2.6 μm): Micro Ace SG-95 (manufactured by Nippon Talc Co., Ltd.)
(B-2) Talc (average particle size: 12.0 μm): Talcan PK-C (manufactured by Hayashi Kasei Co., Ltd.)
(B-3) Settable barium sulfate (average particle size: 0.7 μm): B-54 (manufactured by Sakai Chemical Industry Co., Ltd.)
(B-4) barium sulfate (average particle size: 11.6 μm): BMH-100 (manufactured by Sakai Chemical Industry Co., Ltd.)
(B-5) Calcium carbonate (average particle size: 1.8 μm): SCP E- # 2010 (manufactured by Hayashi Kasei Co., Ltd.)
(B-6) Calcium carbonate (average particle size: 20.0 μm): SCP E- # 45 (manufactured by Hayashi Kasei Co., Ltd.)
(B-7) Titanium dioxide (average particle size (secondary particle size): 0.6 μm): PF-739 (manufactured by Ishihara Sangyo Co., Ltd.)

Polycarbodiimide compound (C);
(C-1) Carbodilite HMV-15CA (manufactured by Nisshinbo Chemical Co., Ltd., a polycarbodiimide completely blocked at the terminal isocyanate)
(C-2) Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd., a polycarbodiimide having an isocyanate at the end)

Non-carbon black pigment (D1);
(D1-1) Infrared reflective inorganic pigment: IRR Black 6350 (Fe-Cr system; manufactured by Asahi Kasei Kogyo Co., Ltd.)
(D1-2) Infrared reflective inorganic pigment: Sicopal Black K 0095 (Co-Cr-Fe-Mn system; manufactured by BASF)
(D1-3) Organic pigment: Lumogen Black FK 4280 (perylene type; manufactured by BASF)
(D1-4) Organic pigment: CHROMOFINEBLACK A1103 (isoindolinone-azo system, manufactured by Dainichi Seika Kogyo Co., Ltd.)
(D1-5) Inorganic pigment: Black 3250 (Cu-Cr-Mn system; manufactured by Asahi Kasei Kogyo Co., Ltd.)

Organic dye (D2);
(D2-1) Organic dye masterbatch: PBF-TT2399B-PBT (PBT (polybutylene terephthalate) resin-based black dye masterbatch, toned product obtained by mixing a plurality of dyes, dye content 10% by mass; Resino Color Industries Co., Ltd. Product made), pellet hue: Color-L = 19.5, Color-a = -0.2, Color-b = -0.9

Carbon black pigments;
Carbon black (made by Mitsubishi Chemical Corporation)

Release agent;
Triglycerin Furbehenate: Poem TR-FB (manufactured by Riken Vitamin Co., Ltd.)
Stabilizers;
Antioxidant: Irganox 1010 (manufactured by BASF)

(Examples 1 to 20, Comparative Examples 1 to 7)
The compounding components blended in the combinations shown in Tables 1 to 3 were compounded by a co-axial twin-screw extruder set at a cylinder temperature of 260 ° C., and the obtained strand was water-cooled and pelletized. Each obtained pellet was dried at 130 ° C. for 4 hours and used for each of the evaluation tests described above. The results are shown in Tables 1 to 3. Examples 3 and 6 are described in both Table 1 and Table 2.

As shown in Table 1, molded articles obtained from the polyester resin composition for a lamp member of a car according to the present invention of Examples 1 to 13 show higher reflectance than Comparative Example 7 using only carbon black, and Color It can be seen that it has excellent visible light shielding properties and blackness with-L 10 10 and has excellent properties. In Examples 1 to 11, in particular, it was found that the haze value of the glass plate after the fogging test is low and the heat deformation temperature is high and the heat resistance is also excellent. Both of the appearance after molding and the appearance after annealing were good. Example 12 which did not contain a polycarbodiimide compound (C) had a somewhat inferior fogging property compared with Examples 3-5. In Example 13 in which the content ratio of the polyethylene terephthalate resin (b) was large, the heat distortion temperature was lower than in Examples 1 to 12, and the appearance and the annealed appearance were slightly inferior.
As shown in Table 2, molded articles obtained from the polyester resin composition for a lamp member of a car according to the present invention of Examples 3, 6, and 14 to 20 are all higher than Comparative Example 7 using only carbon black. The reflectance is shown, and it can be seen that the achieved temperature is low. In Examples 18 and 19 in which the amount of the organic dye added was small, the hue L ^* value was higher than in Example 3. In Example 20, the hue L ^* value was lowered by the addition of a small amount of carbon black.
The heat distortion temperature fell in Comparative Example 1 which did not contain the inorganic filler.
In Comparative Examples 2 to 4 using an inorganic filler having an average particle size of more than 3 μm, the appearance and the appearance after annealing were both deteriorated as compared with Examples 1 to 12. The reflectance was not measured because a good molded product was not obtained.
In Comparative Examples 5 and 6 in which the addition amount of the inorganic filler (B) is larger than the specified range, the appearance is deteriorated and the appearance after annealing is further deteriorated as compared with Examples 1 to 13. The reflectance was not measured because a good molded product was not obtained.
Comparative Example 7 using carbon black had a low infrared reflectance and a high ultimate temperature.

  The polyester resin composition for a lamp member of a car according to the present invention effectively suppresses heat generation due to sunlight concentration while realizing high blackness with high designability, and is excellent in heat resistance, low gas property, and designability Therefore, it is a polyester resin composition which can be used as a lamp member application of a car in which scratching due to sunlight concentration is particularly a problem, and has a great industrial utility value.

Claims (4)

Inorganic filler (B) having an average particle diameter of 3 μm or less, 0.005 to 20 parts by mass, non-carbon black pigment (D1) 0.05 to 10 parts by mass, and organic dye relative to 100 parts by mass of polyester resin (A) (D2) A polyester resin composition containing 0 to 10 parts by mass, wherein the non-carbon black pigment (D1) is Cu-Cr-Mn, Co-Fe-Cr, Fe-Cr, Mn -Or Bi-, Co-Cr-Fe-Mn complex oxide-based pigment, azo-based, anthraquinone-based, phthalocyanine-based, isoindolinone-based, quinacridone-based, perylene-based organic-based pigment selected alone or 2 it is of more species, automotive lamp member, wherein the hue L ^* value according to the L ^* a ^* b ^* system of CIE color difference system of the polyester resin composition is 10 or less Riesuteru resin composition.   The lamp member for an automobile according to claim 1, wherein the polyester resin (A) contains a polybutylene terephthalate resin (a) and a polyethylene terephthalate resin (b) in a mass ratio of 100: 0 to 50:50. Polyester resin composition.   The polyester resin composition for lamp members for motor vehicles according to claim 1 or 2, wherein 0.05 to 3 parts by mass of the polycarbodiimide compound (C) is contained with respect to 100 parts by mass of the polyester resin (A).   The lamp member for an automobile according to any one of claims 1 to 3, wherein the inorganic filler (B) contains one or more selected from talc, barium sulfate, calcium carbonate and titanium dioxide. Polyester resin composition.