JPWO2016194757A1 - Infrared light transmitting polyester resin composition - Google Patents

Abstract

The present invention relates to a polyester resin composition suitable for use as a design member (particularly a lamp member) having a black original specification, having excellent infrared light transmittance, good heat resistance, and low gas properties. It contains 0.005 to 20 parts by mass of an inorganic filler having an average particle diameter of 3 μm or less and 0.5 to 3 parts by mass of an infrared light transmissive black dye with respect to 100 parts by mass of the resin, and the following requirements (1) and ( It is a polyester resin composition satisfying 2). (1) The average value of transmittance at a wavelength of 800 to 1100 nm of a 2 mm thick flat plate obtained from the polyester resin composition is 5% or more and less than 20%. (2) Color-L ≦ 7

Description

  The present invention relates to a polyester resin composition suitable for use as a design member (particularly a lamp member) of black original specification having infrared light transparency and excellent heat resistance and low gas properties.

  Polybutylene terephthalate resin is widely used as an injection-molded product in the fields of automobile parts, mechanical parts, electrical / communication parts, etc. by utilizing 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 can be suitably used for lamp members for automotive extension applications that require particularly good appearance. In addition, it is necessary to highly control the heat resistance of the resin and the suppression of gas generation (low gasity) during molding.

  On the other hand, in recent years, LED lights are mounted on headlamps of luxury cars and the like, and lamp designs have begun to be completely renewed. For example, in the reflector type (light reflected from the light source is reflected by the reflector), it is necessary to deposit aluminum on the part immediately adjacent to the light source, but this is the projector type (light source light is condensed and irradiated on the front lens). There are also designs that have been changed to have a black original specification for the part closest to the light source. However, due to this change, when the sunlight is reflected by the projector lens and the light is collected on the surrounding black part, the sunlight collection is such that the condensing part becomes very hot and scratches are caused. The light problem started to occur (although this phenomenon has been known for a long time, it has never been a problem in lamp design). In response to this problem, there is a demand for a material that transmits infrared light that does not become high temperature even when sunlight is condensed, and a material that has heat resistance and does not get scratched even at high temperatures.

  As a technique for transmitting infrared light, for example, Patent Documents 1 to 3 disclose that polybutylene terephthalate or a resin composed of polybutylene terephthalate and a polybutylene terephthalate copolymer, polycarbonate resin, styrene acrylonitrile resin, 1,4-cyclohexanediene. A resin composition comprising an amorphous resin such as a polyester resin containing a methanol component is disclosed. However, these technologies are useful for increasing the infrared light transmittance of polybutylene terephthalate resin, but the thermal deformation temperature is remarkably lowered by the addition of amorphous resin. It is difficult to use.

  Moreover, as a technique for obtaining a black original polyester resin composition that suppresses temperature rise caused by solar sunshine, for example, Patent Document 4 discloses a polyethylene terephthalate resin composition containing a pigment that does not contain carbon black but is blackened by color matching. It is disclosed. According to the present invention, the use of a non-carbon black pigment can reduce the temperature corresponding to the amount of heat stored due to the infrared light absorption of carbon black, but its temperature rise inhibiting effect is small and greatly improved. There is room.

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

  The present invention has been made against the background of such prior art problems. That is, an object of the present invention is a polyester resin composition that has infrared light permeability, is suitable for use as a design member (particularly a lamp member) with black original specifications, and is excellent in heat resistance and low gas properties. To provide things.

An effective technique for solving the above problem is to produce an infrared light transmissive resin using a black dye having infrared light transmittance as a resin colorant. As a result, even if light in the infrared region of sunlight is transmitted and condensed, the temperature rise can be extremely effectively suppressed.
However, it is often difficult for a crystalline resin to exhibit a dark color due to the high whiteness derived from the crystalline phase. On the other hand, when an excessive amount of dye is added to darken the color, since the dye is generally difficult to dissolve in the crystalline resin, deterioration of bleeding and fogging often becomes a problem.

The present inventors diligently studied and completed the present invention.
That is, the present invention has the following configuration.
[1] For 100 parts by mass of the polyester resin (A), 0.005 to 20 parts by mass of an inorganic filler (B) having an average particle diameter of 3 μm or less, and 0.5 to 3 of an infrared light transmitting black dye (D). A polyester resin composition comprising a mass part, wherein the polyester resin composition satisfies the following requirements (1) and (2).
(1) The average value of transmittance at a wavelength of 800 to 1100 nm of a 2 mm thick flat plate obtained from the polyester resin composition is 5% or more and less than 20%. (2) Color-L ≦ 7
[In the above formula, Color-L represents the hue L ^* value by the L ^* a ^* b ^* system of the CIE color difference system of the polyester resin composition. ]
[2] The polyester resin according to [1], wherein the polyester resin (A) contains the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in a mass ratio of 100: 0 to 50:50. Composition.
[3] The polyester resin composition according to [1] or [2], which contains 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 of talc, barium sulfate, calcium carbonate, and titanium dioxide, according to any one of [1] to [3] Polyester resin composition.
[5] A lamp part comprising the polyester resin composition according to any one of [1] to [4].

  One of the characteristics of the polyester resin composition of the present invention is that it achieves blackness with high designability while having infrared light transmittance. Furthermore, a polyester resin composition excellent in fogging resistance, heat resistance and mechanical properties can be obtained.

  The present invention is described in detail below.

[Polyester resin (A)]
The polyester resin (A) that can be used in the present invention is preferably a polyester resin having a dicarboxylic acid component and a diol component as constituent units.
As the dicarboxylic acid component, those having an aromatic dicarboxylic acid as a main component are preferable. The main component is usually 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more with respect to all dicarboxylic acid units. In addition to aromatic dicarboxylic acids, aliphatic dicarboxylic acids can be used.

Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, Fragrances such as 7-naphthalenedicarboxylic 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-naphthalenedicarboxylic acid are preferable.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. Examples include chain or alicyclic dicarboxylic acids.
The above dicarboxylic acid components can be used alone or in admixture 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 all monomer components.

  Examples of the diol component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 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, Examples include 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.

Preferable 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 an o-chlorophenol solution is measured at 25 ° C., and is 0.52 to 1.25 dl. / G is more suitable, more preferred is 0.58 to 1.12 dl / g, and most preferred is 0.62 to 1.02 dl / g. It is. When the intrinsic viscosity of (A) is 0.36 to 1.60 dl / g, the mechanical properties and moldability of the polyester resin composition of the present invention are improved.
In this invention, it is preferable to contain polybutylene terephthalate resin (a) and polyethylene terephthalate resin (b) with a specific compounding quantity.
Moreover, in this invention, it is also preferable to use polytrimethylene terephthalate resin (c) and polybutylene naphthalate resin (d) as a polyester resin (A). In that case, the polytrimethylene terephthalate resin (c) can be used as an alternative to the polyethylene terephthalate resin (b), and the polybutylene naphthalate resin (d) can be used as an alternative to the polybutylene terephthalate resin (a). is there.

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

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

  The polybutylene naphthalate resin (d) that can be used in the present invention is the same as the polybutylene terephthalate resin (a).

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

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

  The polytrimethylene terephthalate resin (c) that can be used in the present invention is the same as the polyethylene terephthalate resin (b).

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 mass ratio ((a) :( b)) of (a) and (b). It is preferable that More preferably (a) :( b) = 100: 0 to 60:40, further preferably (a) :( b) = 100: 0 to 70:30, particularly preferably (a) :( b) = 100 : 0 to 80:20. It is possible to improve the surface appearance of the resin composition by blending the polyethylene terephthalate resin (b). However, if the blending amount exceeds 50 parts by mass, the resin composition may be deteriorated during injection molding or the resin may be deteriorated. As the heat resistance of the polyester resin composition decreases or the crystallization speed of the polyester resin composition slows down, crystallization gradually proceeds under a temperature environment in the range of 100 ° C. to 200 ° C., and the infrared light transmittance gradually increases. 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 may be 100% by mass.

  In the description of the above blending amounts, “polybutylene terephthalate resin (a)” means “at least one of polybutylene terephthalate resin (a) and polybutylene naphthalate resin (d)”, “polyethylene terephthalate resin (b)” , “At least one of polyethylene terephthalate resin (b) and polytrimethylene terephthalate resin (c)”.

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

  The inorganic filler (B) needs to have an average particle diameter (50% diameter of volume cumulative particle size distribution) measured by a laser diffraction method of 3 μm or less. When the average particle diameter exceeds 3 μm, the infrared light transmittance of the polyester resin composition may be lowered, and the surface smoothness is further impaired. The average particle diameter of the inorganic filler (B) is preferably 2.8 μm or less. The lower limit of the average particle size of the inorganic filler (B) is preferably 0.05 μm from the viewpoints of suppressing aggregation (defective dispersion) and handling properties (ease of feeding, etc.).

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 crystal nucleating agent effect on the polyester resin, and can improve the heat resistance of the polyester resin with a small amount of addition. However, since the particle diameter of talc is relatively large, if the addition amount is large, the surface smoothness is lowered due to the embossment on the resin surface.
On the other hand, barium sulfate, calcium carbonate, and titanium dioxide do not have a crystal nucleating agent effect on the polyester resin. However, since the particle diameter is smaller than that of talc, it is easy to maintain the surface smoothness even if the addition amount is large. . In order to control the shrinkage rate, it is preferable that the amount of the inorganic filler added is large, and use of barium sulfate, calcium carbonate, or titanium dioxide is suitable.
From the viewpoint of improving heat resistance and surface smoothness, talc preferably contains 0.005 to 1 part by mass, and barium sulfate, calcium carbonate and titanium dioxide preferably 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. By using this content of barium sulfate, calcium carbonate, and titanium dioxide, the shrinkage rate can also be controlled.

The inorganic filler (B) is a combination of a small amount of talc and at least one member selected from the group consisting of barium sulfate, calcium carbonate, and titanium dioxide. A nucleating agent effect and a filler reinforcing effect can be obtained simultaneously, and the heat resistance can be greatly improved.
When a small amount of talc is used in combination with at least one member selected from the group consisting of barium sulfate, calcium carbonate, and titanium dioxide, when the total amount of the inorganic filler (B) is 100% by mass, talc 0.2 to The total of at least one selected from the group consisting of barium sulfate, calcium carbonate, and titanium dioxide is preferably 99.8 to 80% by mass with respect to 20% by mass.

The polyester resin composition of the present invention can exhibit good surface smoothness even if the inorganic filler (B) is not surface-treated, but the inorganic filler (B) is surface-treated in order to improve compatibility and dispersibility. May be. In the case of surface treatment, it is preferable to perform the surface treatment to such an extent that gas generation does not affect other characteristics such as fogging.
Examples of the surface treatment include treatment with a surface treatment agent, treatment with a fatty acid, treatment with SiO ₂ —Al ₂ O ₃ , and the like. 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, or the like can be used.

The polyester resin composition of the present invention has an effect of improving heat resistance and rigidity and controlling shrinkage ratio by containing an inorganic filler (B), and transmitting infrared light as compared with the case of not containing an inorganic filler (B). Although there is a tendency to decrease, other important effects can be obtained.
However, since the polyester resin composition of the present invention has a transmittance of 5% or more and less than 20% (average value of transmittance at a wavelength of 800 to 1100 nm of a flat plate having a thickness of 2 mm), compared to a transmittance of 0%. In addition, the temperature rise suppression effect is much greater.

[Polycarbodiimide compound (C)]
It is preferable that the polyester resin composition of this invention contains 0.05-3 mass parts of polycarbodiimide compounds (C) with respect to 100 mass parts of polyester resins (A).
By setting the polycarbodiimide compound (C) within this range, gasification components such as a free carboxylic acid compound and a free hydroxyl group-containing compound can be efficiently captured, and excellent low gas properties can be realized.
If the polycarbodiimide compound (C) is more than 3 parts by mass, gelation may be caused by reaction with the polyester resin (A), or infrared light transmittance may be reduced due to compatibility problems. On the other hand, when the polycarbodiimide compound (C) is less than 0.05 parts by mass, the scavenging effect of the free acid or free hydroxyl group-containing compound is reduced, and the low gas property may be impaired. The blending amount of the polycarbodiimide compound (C) is preferably 0.07 parts by mass, more preferably 0.08 parts by mass with respect to 100 parts by mass of the polyester resin (A). It is more preferably 1 part by mass, particularly preferably 0.15 part by mass, and the upper limit is preferably 2 parts by mass, more preferably 1 part by mass, and 0.5 parts by mass. More preferably.

The polycarbodiimide compound (C) can have a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule.
Such a compound having a carboxylic acid reactive group and a hydroxyl reactive group in one molecule includes a free acid derived from a raw material or a free hydroxyl group-containing compound, a free acid or a free hydroxyl group generated during a subsequent heat treatment process or use at a high temperature. Capturing the contained compounds immediately and exerting the effect of preventing volatilization.
Since free acids and free hydroxyl group-containing compounds greatly affect the generation of gas, their capture is effective in preventing volatilization. In particular, free carboxylic acid volatilizes at a relatively low temperature, and the volatiles crystallize, which often causes fogging. Therefore, capturing the free carboxylic acid is extremely important.

Examples of the functional group that reacts with the carboxylic acid include a glycidyl group, an oxazoline group, an oxetane group, and a carbodiimide group. However, general glycidyl group-containing compounds, oxazoline group-containing compounds, and oxetane group-containing compounds do not react quickly, and it may be difficult to coexist with a functional group that reacts with a hydroxyl group. Since it is intense, it is often difficult to use it in applications requiring fogging resistance. On the other hand, carbodiimide compounds have a faster reaction than glycidyl groups, oxazoline groups, and oxetane groups, and are very preferably used for capturing free carboxylic acids.
The functional group that reacts with a hydroxyl group is different from the functional group that reacts with a carboxylic acid, and examples thereof include an isocyanate group and an acid anhydride group, and an isocyanate group is particularly preferred from the viewpoint of reactivity. As a result of extensive studies, the compound having a carboxylic acid group-reactive group and a hydroxyl group-reactive group in one molecule is most preferably a compound having a carbodiimide group and an isocyanate group in one molecule.
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 easily react with either a thermoplastic resin or a free acid or a free hydroxyl group-containing compound, and have a large molecular weight. By connecting the plastic resin and the decomposition product with a reactive compound, volatilization of the decomposition product derived from the raw material can be greatly reduced. Therefore, in the case of the thermoplastic polyester resin containing a carboxylic acid as in the present invention, effects such as hydrolysis inhibition can be imparted, and effects such as improved processability as a resin composition can be exhibited.

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

  Examples of the diisocyanate compound include aliphatic or alicyclic isocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, and methylcyclohexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4. '-Diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, tetra Methyl xylylene diisocyanate, 1,3,5-triisopropylphenylene-2,4-diisocyanate, etc. Aromatic isocyanate compounds may be mentioned, it can be used by copolymerizing them singly or in combination.

Further, the polycarbodiimide compound (C) may have a branched structure, and a functional group other than a carbodiimide group or an isocyanate group may be introduced by copolymerization. Further, a part or all of the terminal isocyanate may be blocked. As end-capping agents, monoisocyanate compounds such as phenyl isocyanate, tris isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, -OH group, -COOH group, -SH group, -NH-R (R is hydrogen) A compound having an atom or an alkyl group) or the like can be used.
The merit of blocking part or all of the terminal isocyanate is that the reaction in the compound can be easily controlled, and the degree of polymerization and melt viscosity can be controlled. When a certain amount or more of a polycarbodiimide compound in which the terminal isocyanate is not blocked is added to the polyester resin (A), the melt viscosity may be remarkably increased due to thickening, and the addition amount may be limited. Thus, if the amount of polycarbodiimide compound added is limited, the expected effect may not be obtained. When such a problem arises, it can be solved by using a polycarbodiimide compound in which a terminal isocyanate is blocked.
Even if all of the terminal isocyanates are blocked, the effect of capturing the free carboxylic acid due to the high reactivity of the carbodiimide group is high, so that a sufficiently high low gas property can be obtained.

  Examples of commercially available products include Rhein Chemie's Starbucksol series, Nisshinbo's Carbodilite series, Mitsui Takeda Chemical Cosmonate LK, Cosmonate LL, BASF INOAC Polyurethane Lupranate MM-103, and the like. It is done. Especially, it is preferable to use the polycarbodiimide compound which consists of an aliphatic or alicyclic structure from a compatible viewpoint with a fatty acid. If it is an aromatic polycarbodiimide, the compatibility with the fatty acid may be poor, and the carbodiimide group and the fatty acid cannot react efficiently, reducing the effect. In the above-mentioned commercial products, the Nisshinbo Carbodilite series has an aliphatic or alicyclic structure and is preferably used.

[Infrared light transmissive black dye (D)]
The polyester resin composition of the present invention contains 0.5 to 3 parts by mass of an infrared light transmissive black dye (D) with respect to 100 parts by mass of the polyester resin (A).
If the infrared light transmissive black dye (D) is less than 0.5 part by mass, the blackness may be insufficient and the design may be impaired. If it exceeds 3 parts by mass, bleeding out and fogging may become a problem. The content of the infrared light transmissive black dye (D) is more preferably 0.5 to 2 parts by mass, and still more preferably 0.5 to 1.5 parts by mass.

As the infrared light transmitting black dye (D), a known one can be used, and one or two or more dyes may be mixed and used. Since the polyester resin composition of the present invention is a crystalline resin and it is often difficult to exhibit a dark color due to the high whiteness derived from the crystalline phase, two or more dyes are mixed. The toned color is preferable because it easily develops black color.
Examples of the dye that can be added to the polyester resin composition include dyes such as quinoline compounds, anthraquinone compounds, and perinone compounds. These have good heat resistance and are hardly thermally decomposed during compounding or injection molding of the polyester resin composition.
From the viewpoint of heat resistance and fogging properties, the molecular weight per molecule of the infrared light transmitting black dye is preferably 350 or more, more preferably 380 or more, and further preferably 400 or more. The melting point is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. It is sufficient that either the molecular weight or the melting point satisfy this range, and it is particularly preferable that both the molecular weight and the melting point satisfy this range. When two or more infrared light transmissive dyes are used in combination, the molecular weight and melting point of each dye alone preferably satisfy the above ranges.
However, even if the molecular weight and the melting point satisfy the above ranges, there are cases in which the dye is also volatilized due to the vaporization of the gasification component due to the high interaction with the gasification component contained in the resin. is there. In the present invention, anthraquinone compounds and perinone compounds can be preferably used from the viewpoint of fogging properties, and dyes obtained by mixing anthraquinone compounds and perinone compounds can be more preferably used. The infrared light transmitting black dye (D) is particularly preferably a dye in which an anthraquinone compound having a molecular weight of 350 or more and a melting point of 150 ° C. or more and a perinone compound having a molecular weight of 350 or more and a melting point of 150 ° C. or more are mixed. As a masterbatch containing such a dye, “infrared light transmissive dye masterbatch: PBF-TT2399B-PBT (manufactured by Resino Color Industry Co., Ltd.)” can be used.

The dye 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 properties, it is preferable to add them in a master batch.
When the infrared light transmitting black dye is commercially available as a masterbatch, the dye content is usually about 5 to 20% by mass, although it depends on the type of base resin and dye used. .

When the infrared light transmitting black dye is added as a master batch, the hue of the master batch pellet (measured value in the form of pellet) is the hue L ^* value by the L ^* a ^* b ^* system of the CIE color difference system (Color -L) is 22 or less, hue a ^* value (Color-a) is from -1.5 to 1.5, and hue b ^* value (Color-b) is from -1.5 to 1.5. Preferred (both measured values by SCE method).
When the hue of the master batch of the infrared light transmitting black dye is within the above range, the polyester resin composition of the present invention can obtain sufficient blackness without impairing the dispersibility and handling of the dye. .
If the hue of the masterbatch exceeds the above range, the polyester resin composition may not obtain sufficient blackness, and the designability may be impaired.
The hue of the master batch pellet is more preferably a hue L ^* value (Color-L) of 21 or less and a hue a ^* value (Color-a) of −1 or more according to the CIE color difference L ^* a ^* b ^* system. 1 or less, hue b ^* value (Color-b) is −1 or more and 1 or less (both measured values by SCE method).

Since the polyester resin composition of the present invention has the above-described configuration, the average value of the transmittance at a wavelength of 800 to 1100 nm of a 2 mm thick flat plate obtained from the polyester resin composition is 5% or more and less than 20%. is there. Details of the transmittance measurement are as described in the Examples section, but using a 2 mm thick flat plate obtained by injection molding the polyester resin composition at a mold temperature of 60 ° C., a spectrophotometer was used. Measured. The average value is a value obtained by dividing the sum of transmittance at each wavelength by the number of measurements in the range of 800 to 1100 nm. The number of measurements depends on the sampling pitch. For example, when the sampling pitch is 1 nm, transmittance data is obtained every 1 nm, such as 800, 801, 802,..., 1098, 1099, 1100 nm, and the number of measurements is 301. Therefore, in this case, the average value of transmittance at wavelengths of 800 to 1100 nm is obtained by (sum of transmittance at each wavelength / 301).
Since the average value of the transmittances at wavelengths of 800 to 1100 nm is in this range, even if sunlight is collected, it is difficult to reach a high temperature.
The polyester resin composition of the present invention is characterized in that infrared light transmittance is enhanced while achieving excellent design blackness, and excellent heat resistance is imparted by an inorganic filler. Therefore, even if sunlight condenses, it is hard to become high temperature and is hard to be damaged.
By reducing the content of the inorganic filler and remarkably reducing the crystallinity of the resin composition, it is possible to set the average value of transmittance at a wavelength of 800 to 1100 nm to 20% or more, but rigidity and heat resistance are improved. It is not preferable because it is damaged. If the average value of the transmittance at a wavelength of 800 to 1100 nm is less than 5%, the temperature may become very high due to sunlight collection. 10% or more is preferable and the average value of the transmittance | permeability of wavelength 800-1100nm is preferable 18% or less.

Since the polyester resin composition of the present invention has the above-described configuration, the hue L ^* value (Color-L) by the L ^* a ^* b ^* system of the CIE color difference system is 7 or less (measured value by the SCE method). .
When the L ^* value is 7 or less, the polyester resin composition of the present invention can have sufficient blackness, and can exhibit sufficient blackness even in a molded product obtained by melt molding or the like. Therefore, it is excellent in design property. The hue L ^* value is preferably 6 or less, more preferably 5 or less. When the hue L ^* value is higher than 7, the blackness is insufficient and the design property is low.

The polyester resin composition of the present invention preferably has a heat distortion temperature of 130 ° C. or higher at a load of 0.45 MPa. The heat distortion temperature is measured as described in the Examples section.
When the heat distortion temperature is less than 130 ° C., the heat resistance is insufficient, and in particular, it may not be used for applications requiring heat resistance. When the heat distortion temperature is 130 ° C. or higher, it can be said that the polyester resin composition satisfies the heat resistance as a lamp member resin. The heat distortion temperature is more preferably 135 ° C. or higher, in which case the heat resistance as a lamp member resin is more highly satisfied, and 140 ° C. or higher is more preferable, and in that case, it can be said that the heat deformation temperature is more highly satisfied.
When the average value of the transmittance at a wavelength of 800 to 1100 nm is set to 20% or more by reducing the content of the inorganic filler and significantly reducing the crystallinity of the resin composition, the heat distortion temperature is less than 130 ° C. Since there are many, it is not preferable.

The polyester resin composition of this invention can make the haze value of the glass plate after a fogging test (160 degreeC) into 5% or less by containing specific amount of a polycarbodiimide compound (C). According to the present invention, gas generation can be effectively suppressed and excellent fogging resistance can be achieved.
When the amount of gas generated is large and the haze value of the glass plate after the fogging test (160 ° C.) exceeds 5%, there is a practical problem of fogging as various lamp parts. In addition, the mold is likely to be contaminated during injection molding, which may adversely affect quality and productivity.

The fogging test can be performed by the following method.
Cut out a small piece of about 40 mm x 40 mm from an injection molded product (thickness 2 mm), put a total of 10 g in a glass tube (for example, φ65 x 80 mm) with an aluminum foil covered, and place it on a hot plate. set. Further, the glass tube is covered with a slide glass (for example, 78 mm × 76 mm × thickness 1 mm) so that there is no gap between the glass tube, and then heat treated at 160 ° C. for 24 hours. Deposits due to decomposition products sublimated from the resin composition are deposited). The haze value of the slide glass is measured using a haze meter or the like.

In the polyester resin composition of the present invention, it is preferable that the transmittance at a wavelength of 300 to 700 nm of a 2 mm-thick flat plate obtained from the polyester resin composition is substantially 0%. The transmittance measurement at this wavelength is the same as described above.
“Substantially” means that noise during measurement is not taken into consideration. Usually, when it is 0 ± 0.05%, it can be regarded as substantially 0%. In the present invention, the fact that the transmittance at a wavelength of 300 to 700 nm is in the range of 0 ± 0.05% is substantially 0%.
It is preferable that the transmittance at a wavelength of 300 to 700 nm is substantially 0% because the visible light hiding property is high and the design property is high. When the transmittance at a wavelength of 300 to 700 nm exceeds 0% (substantially 0%), the visible light concealing property is not sufficient, and the design property is low.

In order to further improve the releasability, the polyester resin composition of the present invention may contain a release agent as long as the characteristics of the present invention are not impaired.
As for content of a mold release agent, 0.1-3 mass parts is preferable with respect to 100 mass parts of polyester resins (A). If the release agent is less than 0.1 parts by mass, a sufficient release effect cannot be obtained, and there may be problems such as defective release and release wrinkles. The mold release agent itself becomes a gas and bleeds out to contaminate the mold, and adheres to the lens cover, mirror, etc. in a temperature environment in the range of 100 ° C to 200 ° C. There is a problem of generating (fogging). When the release agent exceeds 3 parts by mass, these problems become significant.

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

In addition, the polyester resin composition of the present invention can contain various additives in a known range as long as the characteristics of the present invention are not impaired, if necessary. Examples of known additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, modifiers, antistatic agents, flame retardants and the like.
The polyester resin composition of the present invention is a total of the components (A), (B), (C), and (D) (the component (C) may be 0% by mass) and occupies 85% by mass or more. Preferably, it occupies 90% by mass or more, and more preferably 95% by mass or more.

  As a method for producing the polyester resin composition of the present invention, it can be produced by mixing the above-described components and various stabilizers as required, and melt-kneading. Any method known to those skilled in the art can be used as the melt-kneading method, and a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury mixer, or the like can be used. Among these, it is preferable to use a twin screw extruder. As general melt-kneading conditions, in a twin-screw extruder, the cylinder temperature is 230 to 270 ° C., and the kneading time is 2 to 15 minutes.

  The method for molding the polyester resin composition of the present invention is not particularly limited, and known methods such as injection molding, extrusion molding, and blow molding can be used. Among these, an injection molding method is preferably used from the viewpoint of versatility.

  In the molded article of the polyester resin composition of the present invention, a light reflecting metal layer can be directly formed (deposited) on at least a part of the surface. The vapor deposition method is not particularly limited, and a known method can be used.

  A molded product molded using the polyester resin composition of the present invention can be suitably used as a design member (particularly a lamp member). For example, it can be used as a member for automobile lamps (head lamps, etc.), light reflectors (extensions, reflectors, housings, etc.), lighting equipment, electrical / electronic parts, household goods, etc.

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

(1) Infrared light (wavelength 800 to 1100 nm) / visible light (wavelength 300 to 700 nm) transmittance 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 plate molded product having a thickness of 100 mm × 100 mm × 2 mm 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 Corp.) (a barium sulfate-based white plate is used as a standard white plate), a transmittance of a wavelength of 300-1500 nm is obtained with a sampling pitch of 1.0 nm and a slit width (12). Measurements were made, and the average value of transmittances at wavelengths of 800 to 1100 nm (sum of transmittances at each wavelength / 301) was calculated.
Separately, the transmittance at a wavelength of 300 to 700 nm was measured by the same method.

(2) Hue The hue of the flat plate of the polyester resin composition was measured by the following method.
An injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.) was used, and a 100 mm × 100 mm × 2 mm thick flat plate molded product was injection molded using a mold having a mirror surface polished on the # 6000 file on one side. Molding was performed at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C.
Using a precision spectrophotometric colorimeter TC-1500SX (manufactured by Tokyo Denshoku Co., Ltd.), the hue L ^* value (CIE color difference system) on the mirror surface side of the molded plate is measured according to JIS Z 8722 and JIS Z 8781-4. did. Measurement was performed by a D65 light source, a 10 ° field of view, a 0 ° -d method, and an SCE method.
The hue of the infrared light transmissive black dye masterbatch pellet was measured by the following method.
Using a precision spectrophotometric colorimeter TC-1500SX (manufactured by Tokyo Denshoku Co., Ltd.), in accordance with JIS Z 8722 and JIS Z 8781-4, the pellets are placed in the attached case, set on a turntable, and hue L ^* The a ^* b ^* value (CIE color difference system) was measured. Measurement was performed by a D65 light source, a 10 ° field of view, a 0 ° -d method, and an SCE method.

(3) Haze value A small piece having a size of about 40 mm × 40 mm was cut out from an injection molded product having a thickness of 2 mm, and a total of 10 g was put into a glass tube (φ65 × 80 mm) whose aluminum foil was covered to make a bottom, and hot The plate was set on a plate (Neo Hot Plate HT-1000, manufactured by AS ONE). Furthermore, after the glass tube was covered with a slide glass (78 mm × 76 mm × thickness 1 mm), heat treatment was performed at 160 ° C. for 24 hours. As a result of this heat treatment, deposits due to decomposition products sublimated from the resin composition were deposited on the inner wall of the slide glass. The haze values of these slide glasses were measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

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

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

(6) Thermal deformation temperature (load: 0.45 MPa)
The 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 HDT was measured at a load of 0.45 MPa according to ISO-75.

  The compounding components used in 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
Polytrimethylene terephthalate resin (c): IV = 0.93 dl / g, Cortera (manufactured by Shell)

Inorganic filler (B);
The following average particle diameter is a value (50% diameter of volume cumulative particle size distribution) measured by a laser diffraction method.
(B-1) Talc (average particle size: 2.6 μm): Microace 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) Precipitated 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: 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., polycarbodiimide with all terminal isocyanates blocked)
(C-2) Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd., polycarbodiimide having an isocyanate at the terminal)

Infrared light transmitting black dye (D);
(D-1) Infrared light transmissive dye masterbatch: PBF-TT2399B-PBT (PBT (polybutylene terephthalate) resin-based black dye masterbatch, toning product in which anthraquinone compound and perinone compound are mixed, dye-containing 10% by mass in total; manufactured by Resino Color Industry Co., Ltd.), pellet hue: Color-L = 19.5, Color-a = −0.2, Color-b = −0.9
Dyes other than black;
Purple dye: DCC-V01301 (Ningbo DCC Chemicals)
Black pigment;
Carbon black (Mitsubishi Chemical Corporation)

Release agent;
Triglycerin flubehenate: Poem TR-FB (manufactured by Riken Vitamin)
Stabilizers;
Antioxidant: Irganox 1010 (BASF)

(Examples 1-13, Comparative Examples 1-9)
The compounding components blended in the combinations shown in Tables 1 and 2 were compounded with a same-direction twin-screw extruder set at a cylinder temperature of 260 ° C., and the resulting strand was cooled with water and pelletized. Each of the obtained pellets was dried at 130 ° C. for 4 hours and used for each of the above-described evaluation tests. The results are shown in Tables 1 and 2.

As shown in Table 1, the molded articles obtained from the polyester resin compositions of Examples 1 to 11 and 13 of the present invention have an infrared light transmittance of 5% or more and less than 20%, and a visible light transmittance of 0. %, Color-L ≦ 7, which has excellent visible light hiding properties and blackness, and the haze value of the glass plate after the fogging test is as good as 5% or less, indicating that it has excellent characteristics. Moreover, it turned out that all have a heat distortion temperature of 130 degreeC or more, and also has the outstanding heat resistance. Both the appearance after molding and the appearance after annealing were good. In Example 12, which did not contain the polycarbodiimide compound (C), the fogging property was poor as compared with Examples 3-5.
In Comparative Example 1 containing no inorganic filler, the infrared light transmittance was high, but the heat distortion temperature was lowered.
In Comparative Examples 2 to 4 using an inorganic filler having an average particle diameter of more than 3 μm, both the appearance and the appearance after annealing were deteriorated as compared with the Examples. The transmittance was not measured because a good molded product could not be obtained.
In Comparative Examples 5 and 6 in which the amount of the inorganic filler (B) added was larger than the specified range, the appearance deteriorated compared to the examples, and the appearance after annealing was further deteriorated. The transmittance was not measured because a good molded product could not be obtained.
In Comparative Example 7 in which the infrared light-transmitting black dye (D) is less than 0.5 parts by mass and Comparative Example 8 in which a purple dye is used, the hue L ^* value is 7 or more, and sufficient blackness cannot be obtained. It was. In Comparative Example 9 in which the black pigment was added, the infrared light transmittance was 0%.

The polyester resin composition of the present invention has a design property (especially a flaw due to sunlight collection) because it has a black color with a high design property and has infrared light transmittance and is excellent in heat resistance and low gas properties. It is a polyester resin composition suitable for use as a lamp member application in which sticking is a problem, and has great industrial utility value.

Claims (5)

0.00100 to 20 parts by mass of an inorganic filler (B) having an average particle diameter of 3 μm or less and 0.5 to 3 parts by mass of an infrared light transmitting black dye (D) with respect to 100 parts by mass of the polyester resin (A). A polyester resin composition containing the polyester resin composition, wherein the polyester resin composition satisfies the following requirements (1) and (2).
(1) The average value of transmittance at a wavelength of 800 to 1100 nm of a 2 mm thick flat plate obtained from the polyester resin composition is 5% or more and less than 20%. (2) Color-L ≦ 7
[In the above formula, Color-L represents the hue L ^* value by the L ^* a ^* b ^* system of the CIE color difference system of the polyester resin composition. ]   The polyester resin composition according to claim 1, wherein the polyester resin (A) contains the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in a mass ratio of 100: 0 to 50:50.   The polyester resin composition of Claim 1 or 2 which contains 0.05-3 mass parts of polycarbodiimide compounds (C) with respect to 100 mass parts of polyester resins (A).   The polyester resin composition 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. The component for lamps which consists of a polyester resin composition in any one of Claims 1-4.