JP3067045B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent toughness and flame retardancy and suitable for various electric and electronic parts, automobile parts, industrial parts and the like. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Polyesters, especially polybutylene terephthalate, are excellent in heat resistance, mechanical properties and moldability, and are used in various fields. However, toughness is insufficient, and when a large amount of a flame retardant is added to impart flame retardancy, there is a problem that the toughness is significantly reduced.

As a method for improving the toughness of polybutylene terephthalate, a method of blending an α-olefin vinyl acetate copolymer with polybutylene terephthalate disclosed in Japanese Patent Publication No. Sho 45-26224 is disclosed in Japanese Patent Publication No. Sho 58-4.
No. 7419, a method of blending an α-olefin-glycidyl methacrylate copolymer with polybutylene terephthalate, and a thermoplastic polyester represented by polybutylene terephthalate described in JP-A-1-204968. And a method of blending a rubber copolymer with a graft copolymer obtained by grafting a (meth) acrylic acid alkyl ester to a copolymer mainly composed of an epoxy group-containing unsaturated compound unit.

[0004] However, if a flame retardant is added to the resin composition obtained by these methods in order to impart flame retardancy, the toughness is significantly reduced, and if the amount of the flame retardant is reduced, the flame retardancy cannot be imparted. .

[0005]

SUMMARY OF THE INVENTION The present inventors have made intensive studies to solve the problems of the prior art, and as a result,
An object of the present invention, which has been completed, is to provide a thermoplastic resin composition having excellent toughness and flame retardancy.

[0006]

The above objects are achieved by (a) 70-99.5 mol% of terephthalic acid or its ester-forming derivative, and (b) hydrogenated dimer acid or its ester-forming derivative of 0.5-30. Mole% as an acid component,
A thermoplastic resin composition characterized by comprising 15 to 100 parts by weight of a bromine-based flame retardant per 100 parts by weight of a thermoplastic polyester resin obtained by using butanediol as a glycol component. Is done.

Hereinafter, the present invention will be described in detail.

[0008] Terephthalic acid, which is one of the acid components of the thermoplastic copolyester resin in the present invention, improves the tensile strength of the thermoplastic copolyester resin, and its amount is 70 to 99.5 mol in the acid component. % Is important, and particularly preferably 80 to 99 mol%.

When the proportion of terephthalic acid is less than 70 mol%, that is, when the proportion of the hydrogenated dimer acid component exceeds 30 mol%, the tensile strength decreases. On the other hand, when the proportion exceeds 99.5 mol%, that is, when the hydrogenation When the proportion of the dimer acid component is less than 0.5 mol%, the effect of the soft segment is reduced, and the toughness is significantly reduced.

The hydrogenated dimer acid, which is another component of the thermoplastic copolymerized polyester resin in the present invention, separates unsaturated fatty acids from a low polymer of a clay catalyst by a clay catalyst, and hydrogenates the dimer acids to form a secondary acid such as trimer acid or monomer acid. Obtained after removal of the product, with a preferred purity of 99%
That is all.

Preferable examples are PRIPOL 1008 and PRIPOL 1009 manufactured by Unichema, and PRIM manufactured by Unichema as an ester-forming derivative.
PLAST3008.

Hydrogenated dimer acid improves the tensile elongation at break and impact strength of a thermoplastic copolymerized polyester resin,
It is important that the amount contributes to impart toughness, and the amount is 0.5 to 30 mol% in the acid component, and particularly preferably 1 to 20 mol%.

It is important that the glycol component of the thermoplastic polyester resin of the present invention is 1,4-butanediol.

The method for producing the thermoplastic polyester resin in the present invention is not particularly limited, and can be carried out according to a known method.

For example, terephthalic acid, hydrogenated dimer acid and 1,4-butanediol are directly or simultaneously esterified or transesterified, and then
A polymerization method can be adopted. In the polymerization or transesterification, various known catalysts, stabilizers, modifiers and additives may be used.

As the flame retardant used in the present invention, it is necessary to use a bromine-based flame retardant used for a thermoplastic resin.
It is important. Further, an inorganic flame retardant may be used in combination.

Examples of the brominated flame retardant include aliphatic type, aromatic type, phenol type, epoxy type, bisphenol type and biphenyl type.

Further, examples of the inorganic flame retardant include antimony trioxide, tin oxide, molybdenum oxide, zinc borate and the like.

In the present invention, the compounding amount of the flame retardant is 15 to 100 parts by weight of the thermoplastic polyester resin.
It is important that the amount is 100 parts by weight, especially 18 to 80 parts by weight.
Parts by weight are preferred. If it exceeds 100 parts by weight, the tensile elongation at break and the impact strength are significantly reduced, and the toughness becomes insufficient. On the other hand, when the amount is less than 15 parts by weight, UL-0 V-0
And flame retardancy becomes insufficient.

The composition of the present invention may optionally contain a nucleating agent, a lubricant, an antioxidant, an ultraviolet absorber, a warpage inhibitor, a coloring agent, and the like.

The composition of the present invention is obtained by sufficiently kneading a thermoplastic copolymer polyester resin and a flame retardant until a final molded article is obtained.
It is important that they are distributed. As a method for this, for example, a pellet-shaped resin may be prepared using a different-direction rotating twin-screw kneading extruder, and then subjected to a molding process.

[0022]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in toughness and flame retardancy, and is suitable for various electric and electronic parts, automobile parts, and industrial parts.

[0023]

The present invention will be specifically described below with reference to examples. In addition, physical property evaluation was performed according to the following method.

[0024]

[Table 1]

[0025]

[Production Example] The thermoplastic copolymer polyester resin used in the present invention was produced as follows. Dimethyl terephthalate, hydrogenated dimer acid (PRIPLAS manufactured by Unichema)
T3008), 1,4-butanediol, and tetra-n-butyl titanate as a transesterification and polymerization catalyst were added in the composition shown in Table 2, and methanol produced by heating to 210 ° C. was distilled out of the system. A transesterification reaction was performed. After the methanol distillation was almost completed, the reaction product was transferred to a polymerization vessel, and the temperature was raised to 250 ° C. and the degree of vacuum was set to 0.5 over 1 hour.
mmHg, and then polycondensation was performed for 2 hours.
Table 2 also shows sample names and melting points of the obtained thermoplastic copolyester resins.

[0026]

[Table 2]

[0027]

Examples 1 to 3 and Comparative Examples 1 and 2 A flame retardant (brominated epoxy oligomer / antimony trioxide = 2/1) was added to 100 parts by weight of the thermoplastic copolymer polyester resin C obtained in the above production example. (Weight ratio) The mixture, brominated epoxy oligomer: EBR107 manufactured by Manac Co., and antimony trioxide: ATOX-B manufactured by Nippon Seimitsu Co., Ltd. were blended in the composition shown in Table 3, and after pre-mixing, biaxial rotation of 30 mm diameter in different directions was performed. The mixture was melt-mixed with an extruder to obtain pellets.

The obtained pellets were dried under reduced pressure and then subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 3.

[0029]

[Table 3] * NB: Non Break

[0030]

Examples 4 to 8 and Comparative Examples 3 and 4 A brominated flame retardant and antimony trioxide (Nippon Seimitsu) shown in Table 4 were used with respect to 100 parts by weight of the thermoplastic polyester resin obtained in the above production example. (ATOX-B) (brominated flame retardant /
After mixing 50 parts by weight of antimony trioxide (2/1 weight ratio), and preliminarily mixing, the mixture was melt-mixed with a 30 mm-diameter bi-directional rotary extruder to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 4.

[0032]

[Table 4]

[0033]

Comparative Examples 5 to 9 100 parts by weight of polybutylene terephthalate (manufactured by Kanebo Co., Ltd., PBT724) were blended with an impact modifier and a flame retardant in the composition shown in Table 5, and after premixing,
The mixture was melt-mixed with a different-diameter biaxial rotary extruder having a diameter of mm to obtain pellets.

After the obtained pellets were dried under reduced pressure, they were subjected to injection molding to obtain test pieces, which were subjected to physical property tests. The results are shown in Table 5.

[0035]

[Table 5]

Claims (1)

(57) [Claims] 1) 70 to 99.5 mol% of (a) terephthalic acid or its ester-forming derivative, and (b) 0.5 to 30 of hydrogenated dimer acid or its ester-forming derivative.
It is characterized by comprising 15 to 100 parts by weight of a brominated flame retardant per 100 parts by weight of a thermoplastic copolymer polyester resin obtained by using mol% as an acid component and 1,4-butanediol as a glycol component. Thermoplastic resin composition.