JP2003041104A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester-based thermoplastic resin composition excellent in repulsive elasticity. SOLUTION: This thermoplastic resin composition is obtained by blending 10-90 wt.% polybutylene terephthalate-based copolyester resin consisting of terephthalic acid or its ester-forming derivative and its dimmer acid or its ester-forming derivative as acid components, and 1,4-butane diol as a glycol component, with 90-10 wt.% thermoplastic polyurethane elastomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic molding material composed of a polybutylene terephthalate copolymer polyester resin and a thermoplastic polyurethane elastomer,
The present invention relates to a polyester-based thermoplastic resin composition suitable for miscellaneous goods parts and industrial parts typified by sports parts that require high impact resilience.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin (PB
Thermoplastic polyester resins such as T) and polyethylene terephthalate resin (PET) are used for various purposes by various molding methods. In particular, PBT
Due to its excellent electrical properties, mechanical properties, flame retardancy, and injection moldability, it has expanded its applications centering on automobile parts and electric / electronic parts, and has steadily expanded the market.

However, due to the brittleness that is a characteristic of crystalline resins, there has been a limit to the expansion of applications. In order to improve this brittleness, for example, an alloy with a rubber component or a part of a diol component is changed to polytetramethyleneoxyglycol (P
A copolymer product (polyester elastomer) substituted with TMG) has been developed and put on the market. However, in the case of alloying with a rubber component, brittleness is certainly improved, but in order to approach the properties of rubber having high impact resilience, increasing the compounding amount of the rubber component deteriorates the compatibility with PBT and is practically used. The upper one becomes unusable. PTM for polyester elastomer
When the copolymerization composition ratio of G is increased, the high impact resilience, which is a property of rubber, is increased, but the melt fluidity is lowered and it is not suitable for injection molding.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems of the prior art and to provide a polyester thermoplastic resin composition having high impact resilience.

[0005]

The above object is a polybutylene terephthalate system comprising terephthalic acid or an ester-forming derivative thereof and dimer acid or an ester-forming derivative thereof as an acid component and 1,4-butanediol as a glycol component. This is achieved by a thermoplastic resin composition comprising 90 to 10% by weight of a thermoplastic polyurethane elastomer with respect to 10 to 90% by weight of a copolyester resin.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polybutylene terephthalate-based copolyester resin used in the present invention mainly comprises terephthalic acid and dimer acid as an acid component and 1,4-butanediol as a glycol component.

The raw material for dimer acid, which is one of the acid components, is
It is an unsaturated fatty acid having 18 carbon atoms or a lower alkyl ester thereof, such as oleic acid, linoleic acid, linolenic acid, and elaidic acid. These are polymerized with a viscosity catalyst such as montmorillonite to obtain a mixture of a dimer acid having 36 carbon atoms, a trimer acid having 54 carbon atoms and a monomer acid having 18 carbon atoms. The dimer acid used in the present invention can be obtained by subjecting this mixture to vacuum distillation, molecular distillation and hydrogenation reaction.

The dimer acid obtained is a chain-like, aromatic ring,
It is a mixture having each structure of an alicyclic monocycle and an alicyclic polycycle. When the content of linoleic acid, which is a raw material of dimer acid, is large, the chain structure decreases and the cyclic structure increases. Dimer acid has the general formula

[Chemical 1] (In the formula, R represents an alkyl group, and R _m , R _n , R _p and R _q
It is preferable that the chain dimer acid represented by the formula (3) has a chain dimer acid content of 10% by weight or more from the viewpoint of high impact resilience. Further, the dimer acid is preferably hydrogenated in terms of thermal stability. Further, the dimer acid is preferably copolymerized in the polybutylene terephthalate-based copolyester resin in an amount of 1 mol% to 20 mol%. This is because the impact resilience is not improved when the content is less than 1 mol%. On the other hand, when it exceeds 20 mol%, the heat resistance becomes insufficient.

A preferred specific example of dimer acid, which is one of the acid components of the polybutylene terephthalate-based copolyester resin used in the present invention, is P manufactured by Unichema.
RIPOL 1008, PRIPOL 1009, and PRIKLAST 3008, PRI manufactured by Unichema as an ester-forming derivative of PRIPOL 1008.
PRI as an ester-forming derivative of POL 1009
PLAST 1899 is an example.

Other acid components of the polybutylene terephthalate copolymer polyester resin used in the present invention include:
Examples thereof include isophthalic acid and 2,6-naphthalenedicarboxylic acid.

Further, it is important that the glycol component of the polybutylene terephthalate copolymer polyester resin used in the present invention is mainly 1,4-butanediol. Other components may be used together in small amounts. In particular,
Examples thereof include ethylene glycol, 1,3-propanediol, diethylene glycol, propylene glycol and polytetramethyleneoxy glycol.

The method for producing the polybutylene terephthalate-based copolyester resin in the present invention is not particularly limited and can be carried out according to a known method.

For example, terephthalic acid, dimer acid, 1,
A method in which 4-butanediol is simultaneously or stepwise directly esterified or subjected to an ester exchange reaction and then polymerized can be adopted. In the polymerization or transesterification reaction, various known catalysts, stabilizers, modifiers or additives may be used.

The thermoplastic polyurethane elastomer used in the present invention is a block polymer having a crystalline urethane of short chain glycol and diisocyanate as a hard segment phase and a rubbery urethane of long chain polyol and diisocyanate as a soft segment phase. here,
The long-chain polyol is a polyether having a molecular weight of 500 to 3000, polyester, polycaprolactone, polycarbonate or the like. The short-chain glycol is 1,4-butanediol or the like, and the diisocyanate is MDI, for example. The manufacturing method mainly includes a one-shot method and a prepolymer method. The former is obtained by mixing and stirring (polymerizing) the above three components, heating and aging, and then granulating.
The latter is obtained by previously forming a prepolymer from a long-chain polyol and a diisocyanate, mixing and stirring (polymerization) with a short-chain glycol, heating and aging, and then granulating.

The thermoplastic urethane elastomer is classified into polyether type, polyester type, polycaprolactone type, polycarbonate type, etc. according to the kind of the soft segment. The thermoplastic urethane elastomer used in the present invention is a polybutylene terephthalate type copolyester resin. In terms of compatibility with, a polyester type is particularly preferable.

In the present invention, it is important that the blending composition of the polybutylene terephthalate copolymer polyester resin and the thermoplastic urethane elastomer is 10 to 90% by weight.

When the content of the thermoplastic urethane elastomer is less than 10% by weight, the impact resilience is poor. On the other hand, when it exceeds 90% by weight, the heat resistance decreases.

The resin composition of the present invention may contain a compatibilizing agent of a polybutylene terephthalate type copolyester resin and a thermoplastic urethane elastomer.
Specific examples include polymers having a glycidyl group in the side chain.

Various additives can be added to the resin composition of the present invention within a range not departing from the object of the present invention. Specifically, for example, antioxidants and heat stabilizers (including, for example, hindered phenols, hydroquinones, thioethers, phosphites and substitution products thereof and combinations thereof), ultraviolet absorbers (eg resorcinol, salicylate, benzotriazole, etc.) Benzophenone etc.), crystal nucleating agent (eg kaolin, talc etc.), lubricant and mold release agent (eg montanic acid and its salt, stearic acid and its salt, stearyl alcohol, stearyl amide, silicone resin etc.), reinforcing material (glass fiber) , Carbon fiber, whiskers, etc.), dyes, pigments, antistatic agents, sliding agents (graphite, fluorine compounds, molybdenum compounds, etc.), and other coloring agents.

The resin composition of the present invention preferably has the respective components sufficiently dispersed. For that purpose, for example, a biaxial different-direction rotary extruder is used as the kneading extruder, but the kneading extruder is not limited to this.

[0021]

INDUSTRIAL APPLICABILITY The present invention relates to a polyester-based thermoplastic resin composition having high impact resilience, and is useful as a sundries component or an industrial component typified by sports components that require high impact resilience.

[0022]

The present invention will be described in more detail with reference to the following examples. The physical properties were evaluated according to the following methods.

Impact resilience: JIS K6301 Vicat softening point: JIS K7206

The polybutylene terephthalate copolymer polyester resin used in the present invention was produced as follows. 24.3 kg of 1,4-butanediol, 5 g of tetra-n-butyl titanate as a transesterification catalyst and dimethyl terephthalate having the composition shown in Table 1 were charged into a 100 L reaction kettle at a heating rate of 40 ° C. per hour. 210
The mixture was heated to ° C, the produced methanol was distilled out of the system, and transesterification was performed. After the distillation of methanol was almost completed, 5 g of tetra-n-butyl titanate as an esterification catalyst and dimer acid (PRIPO manufactured by Unichema Co., Ltd.) were used.
L1009) was added with the composition shown in Table 1 and heated to a temperature rising rate of 20 ° C. per hour to 230 ° C. to perform an esterification reaction. Next, the reaction product was transferred to a polymerization machine, tetra-n-butoxy titanate was added as a polymerization catalyst in the composition shown in Table 2, and the temperature was 250 ° C. and the degree of vacuum was 67 over 1 hour.
After bringing to Pa, polycondensation was carried out for 3 hours. Table 1 shows the sample names of the obtained thermoplastic copolyester resins.

[0025]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 and 2 Table 2 shows the polybutylene terephthalate copolymer polyester resin and polyester thermoplastic urethane elastomer (C60A10WH, manufactured by BASF Polyurethane Elastomers Co.) obtained by the above method. Compounded in the composition shown in Fig. 1 and rotating in the same direction twin-screw extruder (TEX30 manufactured by Nippon Steel Co., Ltd.
After kneading with (α), pelletizing, and drying, predetermined test pieces were obtained by injection molding (PROMAT SG75, manufactured by Sumitomo Heavy Industries, Ltd.) and subjected to physical property evaluation. The results obtained are also shown in Table 2.

[0027]

[Table 2]

A glycidyl group-containing polymer (Modiper A4200 manufactured by NOF CORPORATION) was selected as a compatibilizer, and the composition shown in Table 2 was blended in the same manner as in Example 1 and evaluated.
The results are shown in Table 2.

As described above, the thermoplastic resin composition of the present invention is excellent in impact resilience, and is useful for general goods parts such as sports parts and industrial parts which require high impact resilience.

Claims (4)

[Claims] 1. A polybutylene terephthalate-based copolyester resin 10 to 90 comprising terephthalic acid or an ester-forming derivative thereof and dimer acid or an ester-forming derivative thereof as an acid component and 1,4-butanediol as a glycol component. A thermoplastic resin composition comprising 90 to 10 wt% of a thermoplastic polyurethane elastomer with respect to wt%. 2. The thermoplastic resin composition according to claim 1, wherein the dimer acid is a hydrogenated dimer. 3. The thermoplastic resin composition according to claim 1, wherein dimer acid is copolymerized in the polybutylene terephthalate-based copolyester resin in an amount of 1 to 20 mol%. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polyurethane elastomer is a polyester type.