JP2000281887A - Thermoplastic copolyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic copolyester resin composition which has excellent hydrolysis resistance, excellent oil resistance and excellent thermal aging resistance. SOLUTION: This thermoplastic copolyester resin composition comprises (A) 100 pts.wt. of a thermoplastic copolyester resin and 0. 01-10 pts.wt. of (B) a monocarbodiimide compound and/or (C) a polycarbodiimide compound. The thermoplastic copolyester resin A is produced from (a) a dicarboxylic acid component consisting mainly of (a-1) an aromatic dicarboxylic acid and (a-2) a hydrogenated dimer acid, wherein the amount of the hydrogenated dimer acid is 1 to 60 mol.% based on the total dicarboxylic acid component, and (b) a lower mol.wt. glycol consisting mainly of 1, 4-butanediol and having a mol.wt. of <=300.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent moldability, high mechanical strength, and rubber properties such as impact resistance, elastic recovery, and flexibility. The present invention relates to a thermoplastic copolymerized polyester resin composition which withstands long-term use and is also excellent in oil resistance and heat aging resistance.

[0002]

2. Description of the Related Art A copolymerized polyester resin obtained by copolymerizing a crystalline aromatic polyester such as polybutylene terephthalate with dimer acid has rubber properties such as impact resistance, elastic recovery, flexibility, and heat resistance. It is known as a polyester resin having excellent aging properties. For example,
JP-A-50-90697 discloses a copolymerized polyester resin composed of an acid component containing dimer acid in addition to terephthalic acid and a glycol component mainly composed of an aliphatic diol, and an aromatic amine-based stable resin during the polymerization. The use of agents is disclosed. Further, Japanese Patent Application Laid-Open No.
No. 4219 discloses a polyester obtained by copolymerizing hydrogenated dimer acid with polybutylene terephthalate, a hindered phenol-based antioxidant, a phosphorus-based antioxidant,
A resin composition containing a thioether-based antioxidant is disclosed.

However, Japanese Patent Application Laid-Open No. 50-9069 discloses
No. 7, the dimer acid copolymerized polyester resin is a polyester resin which is excellent to some extent in heat aging resistance, but does not have sufficient hydrolysis resistance and has a long term under hot or hot water or steam atmosphere. There was a problem that it could not withstand use. In addition, there is a problem that the oil resistance is not sufficient, and the strength and elongation are reduced in a relatively short period of time, making it unusable. Further, Japanese Patent Application Laid-Open No.
The resin composition disclosed in Japanese Patent No. 14219 is a polyester resin excellent in heat aging resistance to some extent, but still has the same problem that hydrolysis resistance and oil resistance are not sufficient.

[0004]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Accordingly, it is an object of the present invention to provide excellent moldability, high mechanical strength, rubber properties such as impact resistance, elastic recovery and flexibility, hydrolysis resistance, oil resistance and heat resistance. An object of the present invention is to provide a thermoplastic copolymer polyester resin composition having excellent aging properties.

[0006]

In order to achieve the above object, the thermoplastic polyester resin composition of the present invention comprises an aromatic dicarboxylic acid (a-1) and a hydrogenated dimer acid (a- 2) as a main component, and a hydrogenated dimer acid (a-2) is a dicarboxylic acid component (a) that is 1 to 60 mol% of all dicarboxylic acid components, and 1,4-butanediol as a main component. To 10 parts by weight of the monocarbodiimide compound (B) and / or the polycarbodiimide compound (C) based on 100 parts by weight of the copolymerized polyester resin (A) obtained from the low-molecular-weight glycol (b) having a molecular weight of 300 or less. And 100 parts by weight of the thermoplastic copolymerized polyester resin composition of (1), and further an aromatic amine-based antioxidant (D) and a hindered Phenol-based antioxidant (E), a sulfur-based antioxidant (F), a phosphorus antioxidant (G) is respectively 0.01 to 5 parts by weight, (D) alone,
(E) + (F) combination, (E) + (G) combination,
(E) + (F) + (G) combination, (D) + (E) +
(F) combination, (D) + (E) + (G) combination,
(D) + (E) + (F) + (G), and 100 parts by weight of the thermoplastic copolymerized polyester resin composition is further mixed with a polyamide resin ( H) 0.1 to 20 parts by weight.

In the thermoplastic copolyester resin composition of the present invention, the aromatic dicarboxylic acid (a
-1) is terephthalic acid or naphthalenedicarboxylic acid, the purity of the hydrogenated dimer acid (a-2) is 94% or more, and the purity of the hydrogenated dimer acid (a-2) is 98% % Or more, the monocarbodiimide compound (B) is bis (2,6-diisopropylphenyl) carbodiimide, and the polycarbodiimide compound (C) is a polymer of triisopropylphenylene-1,3-diisocyanate. Wherein the aromatic amine-based antioxidant (D) is a diphenylamine-based compound; the hindered phenol-based antioxidant (E) is a hindered phenol-based compound having a molecular weight of 500 or more; The antioxidant (F) is a thiodipropionate compound; The stopping agent (G) is a compound having a sulfur atom together with a phosphorus atom in the molecule, the phosphorus-based antioxidant (G) is a compound having two or more phosphorus atoms in the molecule, the polyamide resin The fact that (H) is a copolymerized polyamide resin is a preferable condition, and when these conditions are applied, it is possible to expect to obtain a more excellent effect.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The dicarboxylic acid component (a) of the thermoplastic copolyester resin (A) forming the copolyester resin composition of the present invention is an aromatic dicarboxylic acid (a-1).
And hydrogenated dimer acid (a-2) as main components. Specific examples of the aromatic dicarboxylic acid (a-1) include:
Terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, or an ester-forming derivative thereof are preferable. In addition, isophthalic acid, phthalic acid, diphenyl-4,4′-dicarboxylic acid, Phenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof can be used. As the hydrogenated dimer acid (a-2) used in the present invention, those obtained by hydrogenation of a purified dimer of a vegetable unsaturated fatty acid or ester-forming derivatives thereof can be used. . As the hydrogenated dimer acid (a-2), it is preferable to use a hydrogenated dimer acid obtained by removing a monomer or trimer by distillation purification. Since the polymerization reactivity and the physical properties of the copolymer are excellent, the hydrogenated dimer acid (a-2) preferably has a purity of 94% or more, particularly preferably 98% or more.

In the thermoplastic polyester resin (A) forming the thermoplastic polyester resin composition of the present invention, the hydrogenated dimer acid (a-2)
However, it is 1 to 60 mol%, preferably 5 to 55 mol%, more preferably 10 to 50 mol% of the total dicarboxylic acid component. 1 mol% of hydrogenated dimer acid (a-2)
If it is less than 30, the resulting thermoplastic copolymerized polyester resin composition has insufficient rubber-like elasticity such as impact resistance. Also 6
If it exceeds 0 mol%, the rigidity is greatly reduced, the melting point is low, the crystallization speed is low, and only a thermoplastic copolymer polyester resin composition having poor moldability can be obtained.

The low molecular weight glycol component (b) having a molecular weight of 300 or less of the thermoplastic copolymer polyester resin (A) forming the thermoplastic copolymer polyester resin composition of the present invention contains 1,4-butanediol as a main component. But
Other specific examples include aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol; 1,4-cyclohexanedimethanol; tricyclodecanedimethylol; Alicyclic diol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- ( 2-
Hydroxy) phenyl] sulfone, 1,1-bis [4-
(2-Hydroxyethoxy) phenyl] cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quarterphenyl. Further, two or more of these diol components can be used in combination.

In the thermoplastic copolymer polyester resin (A) forming the thermoplastic copolymer polyester resin composition of the present invention, if necessary, trifunctional or higher trifunctional acid such as trimellitic acid, trimesic acid or pyromellitic acid may be used. The functional carboxylic acid component, the polyfunctional oxy acid component and the polyfunctional hydroxy component are so small that they do not gel during polycondensation, for example, 0.05 to 3 mol% based on the total dicarboxylic acid component.
Degree can be used.

The preferred method for producing the thermoplastic polyester resin (A) for forming the thermoplastic polyester resin composition of the present invention includes, for example, a lower alcohol diester of an aromatic dicarboxylic acid and a hydrogenated dimer acid. A transesterification reaction and an esterification reaction of an excessive amount of low molecular weight glycol in the presence of a titanium compound and a hindered phenol compound, and a polycondensation of the obtained reaction product, or an aromatic dicarboxylic acid and hydrogen Esterifying the added dimer acid with an excess amount of glycol in the presence of a titanium compound, a tin compound, and a hindered phenol compound,
Examples include a method of polycondensing the obtained reaction product. Further, the hindered phenol compound may be added at the time of polycondensation, or a part thereof may be blended after completion of the polycondensation.

Specific examples of the monocarbodiimide compound (B) which is one of the components used in the thermoplastic polyester resin composition of the present invention include dimethylcarbodiimide, diisopropylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide,
Dodecylisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-o
-Tolylcarbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, di-β-naphthylcarbodiimide, benzylisopropylcarbodiimide, phenyl-o-tolylcarbodiimide and the like. Among these, the use of bis (2,6-diisopropylphenyl) carbodiimide is particularly preferred.

The polycarbodiimide compound (C), which is one of the components used in the thermoplastic polyester resin composition of the present invention, is a compound having at least two carbodiimide groups in the molecule and is usually derived from an isocyanate compound. Compound. Specific examples of these include phenylene diisocyanate, toluene diisocyanate, methylene bisphenyl diisocyanate, xylene diisocyanate, triisopropylphenylene-
Examples include carbodiimide compounds derived from aromatic diisocyanates such as 1,3-diisocyanate and tetramethylxylylene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. Further, urea-modified polycarbodiimide obtained by reacting an aliphatic diisocyanate with a primary or secondary organic aliphatic amine to introduce a urea bond into the aliphatic diisocyanate and then carbodiimidating the urea-modified polycarbodiimide is also included. Among these, use of a polymer of triisopropylphenylene-1,3-diisocyanate is particularly preferable.

These monocarbodiimide compounds (B)
And / or the compounding amount of the polycarbodiimide compound (C) is 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the thermoplastic copolymerized polyester resin (A).
5 parts by weight, more preferably 0.1 to 3 parts by weight.
If the compounding amount of the monocarbodiimide compound (B) and / or the polycarbodiimide compound (C) is less than 0.01 part by weight, the degree of obtaining the desired improvement effect is small,
On the other hand, if it exceeds 10 parts by weight, blooming occurs and the mechanical strength of the thermoplastic copolymerized polyester resin composition decreases, which is not preferable.

Specific examples of the aromatic amine antioxidant (D), which is one of the components used in the thermoplastic polyester resin composition of the present invention, include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,
Examples include 4′-bis (α, α-dimethylbenzyl) diphenylamine and 4-isopropoxydiphenylamine, and among these, the use of a diphenylamine compound is preferred.

Specific examples of the hindered phenolic antioxidant (E) which is one of the components used in the thermoplastic copolymerized polyester resin composition of the present invention include 2,4-dimethyl-6-t-butylphenol. , 2,6-di-t-
Butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-
Cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2′-methylene-bis-4-methyl-
6-t-butylphenol, 2,2′-methylene-bis (4-ethyl-6-t-butylphenol), 4,4 ′
-Methylene-bis (6-t-butyl-o-cresol), 4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6 -Cyclohexylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), bis (3-methyl- 4-hydroxy-
5-t-butylbenzyl) sulfide, 4,4'-thiobis (6-t-butyl-o-cresol), 2,2'-
Thiobis (4-methyl-6-t-butylphenol),
2,6-bis (2′-hydroxy-3′-tert-butyl-
5′-methylbenzyl) -4-methylphenol, 3,
Diethyl ester of 5-di-t-butyl-4-hydroxybenzenesulfonic acid, 2,2′-dihydroxy-3,
3′-di (α-methylcyclohexyl) -5,5′-dimethyl-diphenylmethane, α-octadecyl-3
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3 , 5-Triazine, hexamethylene glycol-bis [β- (3,5-di-t-butyl-4-hydroxyphenol) propionate], N, N′-hexamethylene-bis (3,5-di-t- Butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-
Bis-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t-butyl-
Dioctadecyl ester of 4-hydroxybenzenephosphonic acid, tetrakis [methylene-3 (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Isocyanurate, and tris [β- (3,5-di-
[tert-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like. Among them, it is particularly preferable to use those having a molecular weight of 500 or more, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

The sulfur-based antioxidant (F), which is one of the components used in the resin composition of the present invention, includes thioether-based, dithioate-based, mercaptobenzimidazole-based,
It is a compound containing sulfur such as thiocarbanilide type and thiodipropion ester type. Among these,
Particularly, use of a thiodipropion ester-based compound is preferred.

The phosphorus antioxidant (G), which is one of the components used in the resin composition of the present invention, includes phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkyl Compounds containing phosphorus such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite. Among these, it is preferable to use a compound having a sulfur atom together with a phosphorus atom in the molecule, or a compound having two or more phosphorus atoms in the molecule.

The combination of these antioxidants (D) to (G) is (D) alone, (E) + (F),
(E) + (G) combination, (E) + (F) + (G) combination, (D) + (E) + (F) combination, (D) +
(E) + (G) combination, (D) + (E) + (F) +
It is preferable to select from the combinations of (G).

The antioxidants (D) to (G)
Is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin (A). Parts by weight. Antioxidant (D) ~
If the amount of (G) is less than 0.01 part by weight, the degree of obtaining the desired improvement effect is small, and if it exceeds 5 parts by weight, blooming occurs or the mechanical strength of the thermoplastic copolyester resin composition. Is undesirably reduced.

The polyamide resin (H), which is one of the components used in the thermoplastic polyester resin composition of the present invention, is a polymer compound having an amide bond in the molecular chain, and is a polymer derived from lactam. And, adipic acid, sebacic acid, dodecanedioic acid, and ethylenediamine,
Examples thereof include a polymer of a salt obtained by a reaction with hexamethylenediamine, metaxylenediamine, or the like, and a polymer from ω-aminocarboxylic acid. These polyamide resins may be copolymers or different polymers.
You may use it in combination of types or more. Among these polyamide resins, when a binary or ternary or higher copolymerized polyamide resin is used, higher effects can be obtained.

The amount of the polyamide resin (H) is 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the thermoplastic copolymerized polyester resin (A).
More preferably, it is 0.5 to 5 parts by weight. If the blending amount of the polyamide resin (B) is less than 0.1 part by weight, the degree of obtaining the desired improvement effect is small, and if it exceeds 20 parts by weight, the flexibility and the inherent properties of the thermoplastic copolyester resin are reduced. It is not preferable because rubber-like properties are impaired.

The method for producing the thermoplastic polyester resin composition of the present invention is not particularly limited.
For example, a method in which a raw material obtained by blending a predetermined antioxidant with a thermoplastic copolyester resin is supplied to a screw-type extruder and melt-kneaded, or the screw-type extruder is first supplied with the copolyester resin and melted. Alternatively, a method in which an antioxidant is supplied from another supply port and kneaded, for example, may be employed as appropriate.

Various additives can be added to the thermoplastic copolymer polyester resin composition of the present invention as long as the object of the present invention is not impaired. For example, known molding auxiliaries such as nucleating agents and lubricants, light-fastening agents, coloring agents such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, and optional release agents Can be contained.

The thermoplastic copolyester resin composition of the present invention has excellent moldability, high mechanical strength, and rubber properties such as impact resistance, elastic recovery, and flexibility. Or it withstands long-term use in a steam atmosphere, and also has excellent oil resistance and heat aging resistance. For this reason,
It is useful for molded products, various sheets, various films, etc. for automobiles, electronic / electric equipment, precision equipment.

[0028]

EXAMPLES The effects of the present invention will be described below with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified. The physical properties shown in the examples were measured as follows. [Relative viscosity] 0.5 using o-chlorophenol as a solvent
% Polymer solution was measured at 25 ° C. [Melting Point] Differential Scanning Calorimeter (Du Pont DSC-
910) was measured at the top of the melting peak when heated at a rate of 10 ° C./min in a nitrogen gas atmosphere. [Hardness (Shore D scale)] Measured according to JIS K-7215. [Hydrolysis resistance] A JIS No. 2 dumbbell test piece produced by injection molding was put into a pressure-resistant cylinder together with a sufficient amount of ion-exchanged water, sealed, treated in a hot air oven at 100 ° C, and pulled. The time at which the elongation at break decreased to half of the initial value was evaluated. [Oil resistance] A JIS No. 2 dumbbell test piece made by injection molding was subjected to an ASTM No. 3 The sample was immersed in oil, and the time required for the tensile elongation at break to drop to half of the initial value was measured. [Heat resistant aging property] A JIS No. 2 dumbbell test piece produced by injection molding was aged in a hot air oven at 150 ° C, and the time required for the tensile elongation at break to fall to half of the initial value was measured. Reference Examples 1 to 3 145 parts of terephthalic acid, "Pripol" 1009, a hydrogenated dimer acid with a purity of 98% (manufactured by Unichema)
117 parts and 160 parts of 1,4-butanediol, together with 0.15 part of tetra-n-butyl titanate and 0.03 part of mono-n-butyl-monohydroxytin oxide, a reaction vessel equipped with a helical ribbon type stirring blade And an esterification reaction was carried out at 190 to 225 ° C. while distilling reaction water out of the system. 0.45 parts of tetra-n-butyl titanate was additionally added to the reaction mixture, and "Irganox" 1098 (an amide group-containing hindered phenol antioxidant manufactured by Ciba Geigy, molecular weight 637) was added.
After adding 15 parts, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 2 hours and 45 minutes. The obtained polymer is discharged into water in the form of a strand, cut, pelletized, and a copolymerized polyester resin (A) in which the hydrogenated dimer acid is 19 mol% of the total dicarboxylic acid component.
-1) was obtained. Similarly, copolymerized polyester resins (A-2) and (A-3) shown in Table 1 were obtained. Table 1 shows the physical properties of the obtained copolyester resin.

[0029]

[Table 1] [Monocarbodiimide compound] The monocarbodiimide compounds used in the following examples are as follows. B-1: Bis (2,6-diisopropylphenyl) carbodiimide [Polycarbodiimide compound] Monocarbodiimide compounds used in the following examples are as follows. C-1: Polymer of triisopropylphenylene-1,3-diisocyanate [Antioxidant] The antioxidants used in the following examples are as follows. D-1: Diphenylamine-based antioxidant manufactured by Uniroyal Corporation Nowgard "445 E-1: Hindered phenolic antioxidant" Irganox "1010 manufactured by Ciba Geigy (molecular weight: 1177.
7) F-1: Trilauryl trithiodipropionate G-1: Asahi Denka Kogyo Co., Ltd. phosphorus-based antioxidant "ADEKA STAB" PEP-4C (containing two phosphorus atoms in the molecule) [Production of polyamide resin A copolymer (polyamide resin (H-1)) having a composition ratio of polycaprolactam and polyhexamethylene adipamide of about 65/35, and polycaprolactam, polyhexamethylene adipamide and polyhexamethylene sebacamide Of about 45/35
/ 20 terpolymer (polyamide resin (H-
2)) was manufactured. Examples 1 to 8 Copolymerized polyester resin (A-1) obtained in Reference Example,
(A-2) and (A-3) were dry blended with a carbodiimide compound, an antioxidant, and a polyamide resin at a compounding ratio as shown in Table 2, and using a twin screw extruder having a 45 mmφ screw. After melt-kneading at 240 ° C., the mixture was pelletized. After drying the pellets at 80 ° C. for 5 hours, the molding temperature was 240 ° C., the mold temperature was 60 ° C., JIS
It was injection molded into a No. 2 dumbbell. Table 3 shows the results. Comparative Examples 1 to 8 Raw materials of the resin composition were dry-blended at the respective mixing ratios shown in Table 2, and pelletized as in Examples 1 to 8.
From these pellets and the polyester block copolymers (A-1) to (A-3) obtained in Reference Examples,
Dumbbells were prepared by injection molding in the same manner as in Examples 1 to 8, and evaluated similarly. The results are shown in Table 3.

[0030]

[Table 2]

[0031]

[Table 3] As is clear from the results in Table 3, the thermoplastic copolyester resin composition of the present invention is excellent in hydrolysis resistance, oil resistance, and heat aging resistance. On the other hand, the resin composition of the comparative example is inferior in hydrolysis resistance, oil resistance and heat aging resistance as compared with the composition of the present invention.

[0032]

As described above, a monocarbodiimide compound and / or
Alternatively, a thermoplastic copolymerized polyester resin composition containing a polycarbodiimide compound can provide a molded article having excellent hydrolysis resistance, oil resistance, and heat aging resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/36 C08K 5/36 5/49 5/49 // (C08L 67/02 79:00) (C08L 67/02 77:00 79:00) F-term (reference) 4J002 CF041 CM052 DA049 DH020 EJ028 EJ038 EN067 EN068 ER006 EV048 EV069 EV078 EV258 EW060 EW120 FD070 FD077 FD078 FD079 GM00 GN00 GQ00 4J029 AA01 CB01A01 CB01 CC06A CD04 CF15 CH02 DB02 HA01 HB01

Claims (14)

[Claims] 1. An aromatic dicarboxylic acid (a-1) and a hydrogenated dimer acid (a-2) as main components, and the hydrogenated dimer acid (a-2) is one of the total dicarboxylic acid components.
６０60 mol% of dicarboxylic acid component (a);
A monocarbodiimide compound (B) and / or a polycarbodiimide compound with respect to 100 parts by weight of a thermoplastic copolymerized polyester resin (A) obtained from a low molecular weight glycol (b) having a molecular weight of 300 or less and containing butanediol as a main component. (C) A thermoplastic copolymerized polyester resin composition containing 0.01 to 10 parts by weight. 2. An aromatic amine-based antioxidant (D), a hindered phenol-based antioxidant (E), and a sulfur-based oxidant are added to 100 parts by weight of the thermoplastic polyester resin composition according to claim 1. A thermoplastic copolymerized polyester resin composition comprising 0.01 to 5 parts by weight of each of an antioxidant (F) and a phosphorus-based antioxidant (G) in any of the following combinations. [(D) alone, (E) + (F) combination,
(E) + (G) combination, (E) + (F) + (G) combination, (D) + (E) + (F) combination, (D) +
(E) + (G) combination, (D) + (E) + (F) +
(G) combination] 3. A thermoplastic copolyester resin composition comprising 100 parts by weight of the thermoplastic copolyester resin composition according to claim 2 and 0.1 to 20 parts by weight of a polyamide resin (H). object. 4. The method according to claim 1, wherein said aromatic dicarboxylic acid (a-1) is terephthalic acid or naphthalenedicarboxylic acid.
4. The thermoplastic copolyester resin composition according to any one of items 1 to 3. 5. The thermoplastic copolymerized polyester resin composition according to claim 1, wherein the purity of the hydrogenated dimer acid (a-2) is 94% or more. 6. The thermoplastic polyester resin composition according to claim 1, wherein the purity of the hydrogenated dimer acid (a-2) is 98% or more. 7. The method according to claim 1, wherein the monocarbodiimide compound (B) is
The thermoplastic copolymer polyester resin composition according to any one of claims 1 to 6, which is bis (2,6-diisopropylphenyl) carbodiimide. 8. The polycarbodiimide compound (C),
The thermoplastic copolymerized polyester resin composition according to any one of claims 1 to 6, which is a polymer of triisopropylphenylene-1,3-diisocyanate. 9. The thermoplastic polyester resin composition according to claim 2, wherein the aromatic amine antioxidant (D) is a diphenylamine compound. 10. The thermoplastic polyester resin composition according to claim 2, wherein the hindered phenolic antioxidant (E) is a hindered phenolic compound having a molecular weight of 500 or more. 11. The thermoplastic copolyester resin composition according to claim 2, wherein the sulfur-based antioxidant (F) is a thiodipropionate compound. 12. The thermoplastic polyester resin composition according to claim 2, wherein the phosphorus-based antioxidant (G) is a compound having a sulfur atom as well as a phosphorus atom in the molecule. 13. The thermoplastic copolyester resin composition according to claim 2, wherein the phosphorus-based antioxidant (G) is a compound having two or more phosphorus atoms in a molecule. . 14. The thermoplastic copolyester resin composition according to claim 3, wherein said polyamide resin (H) is a copolyamide resin.