JP3020705B2 - 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 suitable for various electric and electronic parts, automobile parts, industrial parts and the like. It is.

[0002]

2. Description of the Related Art A rubber-reinforced resin (a so-called ABS resin) obtained by graft-polymerizing acrylonitrile and aromatic vinyl or acrylonitrile, aromatic vinyl and methacrylic acid ester onto a polymer mainly comprising a conjugated diolefin.
Is known as a resin having a large impact strength, and is used in a wide range of fields. However, high rigidity is one of the causes of application restrictions.

As a method of improving the rigidity of the ABS resin and imparting softness, there is a method of mixing the ABS resin with a soft resin. For example, a thermoplastic elastomer such as a polyester elastomer or an olefin elastomer is mixed. However, the mixture of the ABS resin and the thermoplastic elastomer has improved softness but insufficient toughness and heat resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a thermoplastic resin composition having excellent toughness and softness.

[0005]

The object of the present invention is to provide a rubber component containing 30 to 80% by weight of a conjugated diolefin as a main component,
10 to 70% by weight of a rubber-reinforced resin obtained by polymerizing acrylonitrile and aromatic vinyl, or 20 to 70% by weight of a resin component containing not more than the content of aromatic vinyl, and a relative viscosity of 1.8. 30 to 90% by weight of a thermoplastic copolyester resin having a weight of 3.2 to 3.2
And the thermoplastic copolymer polyester resin has terephthalic acid or an ester-forming derivative thereof and a hydrogenated dimer acid or an ester-forming derivative thereof as an acid component,
This is achieved by a thermoplastic resin composition characterized by being a polymer obtained by using 1,4-butanediol as a glycol component.

Hereinafter, the present invention will be described in detail. The rubber reinforced resin used in the present invention is a polymer obtained by graft polymerizing acrylonitrile and aromatic vinyl or further methacrylic acid ester to a polymer mainly composed of a conjugated diolefin, mainly butadiene as a rubber component. Usually, it is obtained by polymerizing a monomer in an emulsified state in the presence of a polybutadiene latex or a styrene / butadiene copolymer (SBR) latex and then coagulating and drying it. And the present invention is not limited to a specific manufacturing method. Further, a small amount of other monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, acrylic acid and esters thereof may be contained.

In the rubber reinforced resin used in the present invention, the copolymerization ratio of the rubber component mainly composed of a conjugated diolefin is 30.
It is important that the content is ８０80% by weight. If it is less than 30% by weight, the impact resistance is insufficient, while if it exceeds 80% by weight, the heat resistance becomes poor.

When the rubber-reinforced resin used in the present invention contains a methacrylic acid ester, it is important that the content of the methacrylic acid ester does not exceed the content of the aromatic vinyl. When the content of the methacrylate exceeds the content of the aromatic vinyl, the impact strength is reduced.

The compounding amount of the rubber reinforced resin used in the present invention is as follows:
It is important that the content be 10 to 70% by weight, and preferably 25 to 60% by weight. The compounding amount of rubber reinforced resin is 10
If the amount is less than the weight percentage, the elasticity is remarkably reduced, and the product cannot be commercialized. On the other hand, if it exceeds 70% by weight, the elasticity is not improved and the composition of the present invention cannot be obtained.

[0010] The acid component of the thermoplastic polyester resin used in the present invention comprises terephthalic acid and hydrogenated dimer acid. The hydrogenated dimer acid is obtained after separation of unsaturated fatty acids from a low polymer by a clay catalyst and removal of by-products such as trimer acid and monomer acid by hydrogenation, and has a preferable purity of 99% by weight or more.

As a preferred specific example, PRIPOL 1008 (36 carbon atoms, aromatic type /
Alicyclic type / linear aliphatic type = 9/54/37 (mol%) dimer acid), PRIPOL1009 (36/23 / mol (dim%) with 36 carbon atoms),
Further, as an ester-forming derivative, PR from Unichema
IPLAST3008 (dimethyl ester of PRIPOL1008).

The copolymerization composition ratio of the hydrogenated dimer acid, which is a component of the thermoplastic polyester resin used in the present invention, is preferably from 0.5 to 30 mol% based on the total acid components. Preferably it is 1 to 20 mol%. If it is less than 0.5 mol%, the toughness and softness are insufficient, while if it exceeds 30 mol%, the heat resistance decreases.

It is important that the glycol component of the thermoplastic copolymerized polyester resin contains 1,4-butanediol as a main component (for example, 70 mol% or more) in view of compatibility with the rubber reinforced resin.

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 or its ester-forming derivative, hydrogenated dimer acid or its ester-forming derivative, 1,4-butanediol may be directly or simultaneously esterified,
Alternatively, a method of performing polymerization after transesterification can be employed. These polymerization or esterification reactions,
In the transesterification reaction, various known catalysts, stabilizers, modifiers, additives and the like may be used.

It is important that the thermoplastic copolymer polyester resin of the present invention has a relative viscosity η _rel of 1.8 to 3.2. When η _rel is less than 1.8, the toughness of the composition is poor. On the other hand, when η _rel exceeds 3.2, the compatibility with the rubber-reinforced resin is poor and the toughness is poor.

The thermoplastic resin composition of the present invention may contain known nucleating agents, lubricants, antioxidants, ultraviolet absorbers, warpage inhibitors, coloring agents, and the like, if necessary.

It is preferable that all components of the thermoplastic resin composition of the present invention are sufficiently dispersed until a final molded article is obtained. As a method for this, for example, there is a method in which a pellet is formed by using a different direction rotating twin-screw kneading extruder, and the pellet is provided to a molding step.

[0018]

The thermoplastic resin composition of the present invention has excellent toughness and is suitable for various electric and electronic parts, automobile parts and industrial parts.

[0019]

The present invention will be specifically described below with reference to examples. In addition, physical property evaluation was performed according to the following method. Thermal deformation temperature: ASTM D648 (Load 4.6 kg /
cm ² ) Flexural modulus: ASTM D790 Tensile elongation at break: ASTM D638 (test speed 50 m
m / min) Izod impact strength (notched, 1/8 inch): A
STM D256 Relative viscosity η _rel : solvent Tetrachloroethane: phenol = 2: 3 (weight ratio), measurement temperature 20 ° C, concentration 1.00
0g / dl

Production Example of Rubber-Reinforced Resin A rubber obtained by graft-polymerizing 20% of acrylonitrile and 40% of styrene in an emulsified state in the presence of 40% of polybutadiene latex (solid content, hereinafter referred to as weight basis), and then coagulating and drying. To 100 parts by weight of the reinforced resin powder, 1.0 part by weight of 2,6-t-butyl-p-cresol and 1.0 part by weight of trisnonylphenylphosphite as a stabilizer were mixed and passed through a 25φ single screw extruder. Into a pellet. Similarly, an acrylonitrile / styrene ratio of 1
Rubber reinforced resins having different polybutadiene contents shown in Table 1 were produced at a constant ratio of / 2.

[0021]

[Table 1]

Production Example of Thermoplastic Copolyester Resin Dimethyl terephthalate, hydrogenated dimer acid (PRIPLAST 3008, manufactured by Unichema), 1,4-butanediol, transesterification and tetra-n-
Butyl titanate was added at the composition shown in Table 2,
Then, methanol produced by heating was distilled off to the outside of the system to carry out a transesterification reaction. 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 a degree of vacuum of 0.5 mmHg, followed by polycondensation. Table 2 also shows the sample names and the relative viscosities η _{rel of the} obtained thermoplastic copolymerized polyester resins.

[0023]

[Table 2]

Examples 1 to 8 and Comparative Examples 1 to 6 The rubber reinforced resin and the thermoplastic copolymerized polyester resin obtained by the above-mentioned methods were blended in the composition shown in Table 3 and preliminarily mixed. Pellets were obtained by melt mixing with a directional rotating twin screw extruder. 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 3.

[0025]

[Table 3]

Example 9 and Comparative Example 7 A rubber-reinforced resin copolymerized with methyl methacrylate was prepared according to the production example of the rubber-reinforced resin. The composition is shown in Table 4. Further, 40% by weight of this rubber-reinforced resin and 60% by weight of a thermoplastic copolymer polyester resin (sample name C) obtained by the above method were blended, and a mixed composition was produced according to Example 1, and the impact strength was measured. did. Table 4 also shows the results.
Shown in

[0027]

[Table 4]

Claims (3)

(57) [Claims] 1. A rubber reinforced resin obtained by polymerizing 30 to 80% by weight of a rubber component mainly containing a conjugated diolefin and 20 to 70% by weight of a resin component containing acrylonitrile and aromatic vinyl, and 10 to 70% by weight of a rubber component. 30 to 90% by weight of a thermoplastic copolymer polyester resin having a viscosity of 1.8 to 3.2
The thermoplastic copolymer polyester resin, terephthalic acid or an ester-forming derivative thereof and a hydrogenated dimer acid or an ester-forming derivative thereof as an acid component,
A thermoplastic resin composition, which is a polymer obtained by using 1,4-butanediol as a glycol component. 2. A resin component containing from 30 to 80% by weight of a rubber component mainly composed of a conjugated diolefin, acrylonitrile and aromatic vinyl, and containing a methacrylic acid ester within a range not exceeding the content of aromatic vinyl. 10% to 70% by weight of a rubber-reinforced resin obtained by polymerizing a rubber having a relative viscosity of 1.
Thermoplastic polyester resin 3 having 8-3.2
0 to 90% by weight, wherein the thermoplastic copolyester resin comprises terephthalic acid or an ester-forming derivative thereof and a hydrogenated dimer acid or an ester-forming derivative thereof as an acid component, and comprises 1,4-butanediol as a glycol. A thermoplastic resin composition, which is a polymer obtained as a component. 3. The thermoplastic copolymerized polyester resin has a hydrogenated dimer acid component in an amount of 0.5 to 3 with respect to the total acid component.
3. The composition according to claim 1, which accounts for 0 mol%.