JPS6361045A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact strength and moldability and suitable for automobile parts, etc., by compounding a polyester and a polycarbonate with a copolymer of ethylene and an unsaturated carboxylic acid ester a specific ethylenic copolymer. CONSTITUTION:(A) An aromatic polyester, preferably polytetramethylene terephthalate and/or polyethylene terephthalate and (B) an aromatic polycarbonate (the weight ratio of A:B is 95:5-55:45) are compounded with (C) a copolymer of ethylene and an unsaturated carboxylic acid ester, preferably an ethylene- ethyl acrylate copolymer having an ethyl acrylate content of 10-45wt% and (D) a copolymer of ethylene and an alpha,beta-unsaturated acid glycidyl ester, preferably an ethylene-glycidyl methacrylate (GMA) copolymer having a GMA content of 1-50% (the weight ratio of C:D is 95:5-5:95). The sum of C and D is 1-20% of the whole composition.

Description

Detailed Description of the Invention (Field of Industrial Application) This invention relates to a molding composition that is mainly composed of aromatic polyester and has excellent physical properties and processability, and is particularly suitable for large molded products such as automobile parts. .

(Prior Art) Conventionally, thermoplastic polyester (hereinafter abbreviated as "polyester") has been widely used as an engineering plastic, taking advantage of its characteristic characteristics and relatively low cost, especially polybutylene terephthalate. (hereinafter abbreviated as rPBT J) has a fast crystallization rate and is easy to process, so it is widely used as an NT resin for molding.However, polyester still has poor impact resistance and other properties compared to Ike's high-grade engineering plastics. It is lacking in physical properties, and various improvements have been proposed.

For example, Japanese Patent Publication No. 36-14035 proposes a composition in which polycarbonate and polyester are mixed to improve the processability and physical properties of both. Also, U.S. Patent No. 4
．． No. 044.073 discloses impact-modified compositions that combine certain PBT and certain polycarbonates. However, such a combination of polyester and polycarbonate alone does not yet provide sufficient physical properties and processability, and attempts have been made to improve this by adding a third and fourth component.

Japanese Patent Publication No. 39-20434 discloses polyolefins, Japanese Patent Application Publication No. 49-41442 discloses Bukugen-based graft copolymers, and Japanese Patent Publication Publication No. 51-39749 discloses ethylene-vinyl acetate copolymers. , Japanese Patent Publication No. 58-933
Publication No. 57 describes butyl rubber and acrylic polymer,
JP-A-59-66448 discloses various polyolefins or copolymers thereof.
The publication proposes attempts to improve impact resistance and processability by using various impact modifiers and linear low density polyethylene.

For example, Japanese Patent Publication No. 58-13588 proposes a thermoplastic resin composition characterized by containing an ethylene-ethyl acrylate copolymer in addition to an aromatic polyester or an aromatic polycarbonate. However, as can be seen in the notched Izot test at room temperature in the example, the impact resistance is too insufficient for large parts such as automobile parts. .

Furthermore, in JP-A-56-30460, it is disclosed that thermoplastic polyester contains 1 to 20% by weight of an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid, and glass fiber. A polyester composition for molding has been proposed. However, systems containing a small amount of olefin copolymer are severely lacking in impact resistance, and systems containing a large amount are extremely stiff even if the impact resistance is satisfied! In other words, the materials disclosed in these documents do not require improvement in processability. However, it is not suitable for large-sized molded products, and has the problem that impact resistance and rigidity cannot be improved in a well-balanced manner.

(Means for Solving the Problems) As a result of intensive research in order to solve the above problems in polyester compositions, the present inventors found that for polyester and polycarbonate compositions mainly composed of polyesters,
By blending a specific amount of a combination of a copolymer of ethylene and an unsaturated carboxylic acid ester and an olefinic copolymer consisting of a glycidyl ester of ethylene and an α,β-unsaturated acid, the elastic modulus can be reduced too much. They discovered that the impact resistance was significantly improved without any problems, and arrived at the present invention.

That is, the present invention relates to aromatic polyester (A), aromatic polycarbonate (B), copolymer of ethylene and unsaturated carboxylic acid ester (b), and ethylene copolymer consisting of ethylene and glycidyl ester of α,β-unsaturated acid. Polymer (
D) and the weight ratio of A to day is 95:5 to 55:45
and the sum of C and D is 1 to 1 for the entire composition.
The thermoplastic resin composition is 20% by weight and has a weight ratio of C to C in the range of 95:5 to 5:95.

The aromatic polyester (to 1) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is mainly composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction as a component. Examples of aromatic dicarboxylic acid components include dicarboxylic acids having a pencene nucleus such as terephthalic acid and isophthalic acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid; These include dicarboxylic acids having a naphthalene nucleus or ester-forming derivatives thereof.

Further, as the acid component, 20 mol % or less of dicarboxylic acids other than aromatic dicarboxylic acids (eg, adipic acid, sepacic acid) or ester-forming derivatives thereof may be substituted. Examples of the diol component include ethylene glycol, tetramethylene glycol, hexamethylene glycol, and diethylene glycol/lz.

Aliphatic glycols such as cyclohexanediol, 1.
These include diols having an aromatic ring such as 4-bisoxyethoxybenzene and bisphenol A, or their ester-formable derivatives.

The aromatic polyester used in the present invention may be not only one type of aromatic polyester but also a mixture of two or more types of aromatic polyester. Preferably polytetramethylene terephthalate, polytrimethylene terephthalate, polyethylene breclate, polytetramethylene/-), 5-naphthalate, polyhexamethylene-2,6-naphthalate and mixtures thereof, more preferably Polytetramethylene terephthalate, polytrimethylene terephthalate, polytetramethylene-2,6
- naphthalates and mixtures thereof.

The aromatic polycarbonate (B) used in the present invention is f
Although many types of aromatic polycarbonates can be employed, 4,4'-dihydroxydiphenylalkane polycarbonates are particularly preferred. Specifically, 2.2' −
(4,4'-dihydroxydiphenyl)-propane (hereinafter abbreviated as bisphenol A) is preferably used as a polycarbonate as the hydroxyl component and obtained by a transesterification method or a phosgene method. Furthermore, part or all of bisphenol may be substituted with other 4.4'-dihydroxydiphenylalkane, 4.4'-dihydroxydiphenyl sulfone, 4.4'-dihydroxydiphenyl ether, etc., or two or more types of aromatic Group polycarbonates may be mixed and used.

The copolymer of ethylene-unsaturated carboxylic acid ester used in the present invention is ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer (hereinafter referred to as rEE).
(abbreviated as AJ), ethylene-butyl acrylate copolymer, etc. Among these, EEA is particularly preferred. These ethylene copolymers are obtained by polymerizing ethylene and unsaturated carboxylic acid esters at high temperature and pressure in the presence of a Rancal initiator, and the molecular weight is not particularly limited, but the melt index (Ml) as 0.1~300g
/10 minutes is suitable. The content of unsaturated carboxylic acid ester in the copolymer is 10 to 45% by weight.
A range of is preferred.

Furthermore, in the ethylene copolymer composed of ethylene and glycidyl ester of an α,β-unsaturated acid used in the present invention, the glycidyl ester of an α,β-unsaturated acid has the general formula %formula%(2 (in the formula R is a hydrogen atom or a lower alkyl group), specifically glycidyl acrylate, glycidyl methacrylate (hereinafter abbreviated as "Gλjo"),
Glycidyl ethacrylate, etc., and GMA is particularly preferably used. The amount of the α,β-unsaturated glycidyl ester copolymer is suitably in the range of 1 to 50% by weight.

The composition of the present invention comprises the above-mentioned aromatic polyester (A), aromatic polycarbonate (B), copolymer of ethylene and unsaturated carboxylic acid ester (C,), and ethylene and α, β
- An ethylene copolymer (D) consisting of a glycidyl ester of an unsaturated acid is an essential component, and the weight ratio of A to day is 95:5 to 55:45, preferably 90:10 to
65:35, and the sum of C and D is 1 to 20% by weight based on the total composition, and the weight ratio of C to C is 95:5 to 5.
It is a thermoplastic resin composition in the range of 5:95. If the ratio of B to A is less than 95:5, a composition with excellent impact resistance and dimensional accuracy cannot be obtained. B against A
The impact resistance improves as the ratio of
If the ratio exceeds 5:45, the same impact resistance as above is not remarkable, and conversely, the flexural modulus at temperatures above 140° C. decreases markedly, making it impossible to paint the exterior panels of automobiles at the same time as steel plates, making it unsuitable.

If the sum of C and D is less than 1% by weight based on the total composition, the effects of first impact properties, moldability, and thermal stability will be insufficient;
If the amount exceeds 1% by weight, the heat deformation temperature and flexural modulus of the resulting composition will drop significantly, which is undesirable.

If the ratio of D to C is less than 95:5, the impact resistance will not be sufficiently improved, and if the ratio of D to C is more than 5:95, the rigidity, especially the rigidity at high temperatures, will not be sufficient.

Further, to the thermoplastic resin composition of the present invention, a fibrous reinforcing material and/or an inorganic optical fiber material may be added as required for the purpose of improving physical properties such as rigidity and impact resistance.

Filling materials suitable for use in the present invention include, but are not limited to, talc, milled glass fiber, flake glass, glass balloons, mica,
Carbon black, etc.

When these fillers are treated with a silane coupling agent such as aminosilane or a titanium coupling agent, a layer effect may appear.

- The blending amount of the filler is 0% to 1% based on the total composition, and the blending amount of the fibrous reinforcing material is 0% to the total composition.
~30% by weight. The total amount of both is 5 to 5 for the entire composition.
20% is preferable. If the filler is mixed in an amount exceeding the above range, not only will it have no effect on stiffness, but the DuPont impact properties will be significantly lowered.

Other thermoplastic resins, such as polyethylene, may be used in the compositions of the invention, as long as they do not impair the purpose of the invention.

Polypropylene, polyamide, polystyrene, etc. may also be blended. In addition, antioxidants or heat stabilizers (hindered phenol type, phosphite type, hydroquinone type,
(thioether type, etc.), ultraviolet absorbers (benzotriazole type, resorcinol type, salicylate type, etc.), dyes or pigments, flame retardants, antistatic agents, nucleating agents (crystallization accelerators), lubricants or mold release agents, etc. You can also. The above additives may be used in combination.

The method for producing the composition of the present invention is not particularly limited.

One example is the method of using an au reroll, which involves heating multiple rolls! The raw materials are added and kneaded. Ike's method: Melt and knead in a Banbury mixer or pressure kneader. However, these methods generally involve patch operation and have poor productivity, so a method using an extruder is preferred. As the extrusion limit, the extrusion limit of a full-flight screw may be used (5), but since this may result in insufficient kneading, it is preferable to use an extruder having a kneading zone or a multi-screw extruder.

Further, when kneading the composition of the present invention, it is possible to knead three types of resins simultaneously, or to knead two types in advance and then add the remaining one type and knead them.

In addition, when kneading, the moisture in the raw materials is preferably reduced to 300p.
It is recommended that it be dried to a temperature below pm. It is also preferable to dry the composition when producing molded articles. This means that it contains more than a certain amount of water (
This is because it may cause deterioration of durability and damage physical properties.

As described above, the temperature when kneading or molding the composition of the present invention is 220 to 280°C, preferably 230°C.
It is better to knead at a temperature of ~270°C; kneading at too high a temperature may result in deterioration of physical properties.

(Effects of the Invention) The present invention: As has been explained above, and as is clear from the examples described below, the present invention is applied as a modifier for aromatic polyesters and aromatic polycarbonates. By blending a copolymer of ethylene and unsaturated carboxylic acid ester in a specific ratio, impact resistance and strength are increased without significantly reducing rigidity compared to when this is not blended or when a pond modifier is used. In particular, it has a major feature in that it significantly improves strength at low temperatures.

It is also characterized by excellent fluidity during molding and low mold shrinkage, and has a wide range of uses as a molding composition. Examples of applications include rough parts of vehicles such as automobiles (bumpers,
(exterior panels, interior panel spoilers, radiator grills, console boxes, meter housings, etc.)
Examples include electrical product parts (various housings, cabinets, interior and exterior panels, etc.), various pirate tool parts, packaging materials, household goods, etc.

1. Fruit) cans (row) The invention will be illustrated by the following examples and comparative examples.

Example 1-4 As the aromatic polyester (A), polybutylene lentilephthalate (r1401-XO6J, trade name, manufactured by Toshi 0@) was used, and as the aromatic polycarbonate (B), Panlite L-1225J (trade name) was used as the aromatic polycarbonate (B). , Music University Kasei (11)
copolymer (C) of ethylene and unsaturated carboxylic acid ester, ester ethyl acrylate copolymer (εEA-A4250 J, trade name, manufactured by Nippon Petrochemical Co., Ltd.), ethylene and α, β unsaturated carboxylic acid Ethylene-based copolymer (D) consisting of glycidyl ester of ethylene and chrycidyl methacrylate copolymer containing 15.1% by weight of glycidyl methacrylate (manufactured by Nippon Petrochemical Co., Ltd.) is shown in Table 1. Two-sleeve kneading iso (with composition ratio)
Manufactured by Ikegai Iron Works Co., Ltd., PC:,! -30) using 2
A kneaded extrusion bed was produced at 50°C. This was molded using an injection molding machine (15-150 manufactured by Toshiba Kiori) to prepare test pieces N01 and X02, and their physical properties were measured by the method of Rudder T1.1.

(The results are also listed in Table 1.

The flexural modulus was measured at room temperature (23°C) using AST, ID-79,0, and the impact strength was AST
Izot impact strength was measured at -30°C in accordance with I0-256.

The heat sag test was 1 on a 100mm piece.
The sag width was measured after 1 hour at 60°C.

In addition, 4 types or 5 types of resins, fillers, etc. were pelletized in the same manner as in Example 1 with the composition ratios shown in Table 1.
Test pieces No. 3, No. 4 were prepared in the same manner as above, and their physical properties were measured. The results are also listed in Table 1.

Comparative Examples 5 to 10 Resin etc. were pelletized in the same manner as in Example 1 using the composition ratios shown in Table 2.
Test pieces of No. 5 to No. 1O were prepared, and the physical property values listed in Table 2 were obtained.

Claims (1)

[Claims] 1. Aromatic polyester (A), aromatic polycarbonate (B), copolymer of ethylene and unsaturated carboxylic acid ester (C), and glycidyl ester of ethylene and α,β-unsaturated acid The weight ratio of A to B is in the range of 95:5 to 55:45, and the sum of the weights of C and D is 1 to 20% by weight based on the total composition.
A thermoplastic resin composition characterized in that the weight ratio of C to D is in the range of 95:5 to 5:95. 2. The thermoplastic resin composition according to claim 1, wherein the aromatic polyester (A) is polytetramethylene terephthalate and/or polyethylene terephthalate. 3. Copolymer of ethylene and unsaturated carboxylic acid ester (
The heat composition resin composition according to claim 1 or 2, wherein C) is ethylene-ethyl acrylate. 4. The thermoplastic resin composition according to claim 3, wherein the ethyl acrylate content in the ethylene-ethyl acrylate copolymer is 10 to 45% by weight. 5. Any one of claims 1 to 4, wherein the ethylene copolymer (D) consisting of ethylene and glycidyl ester of an α,β-unsaturated acid is an ethylene-glycidyl methacrylate copolymer. Thermoplastic resin composition according to item 1. 6. The thermoplastic resin composition according to claim 5, wherein the content of glycidyl methacrylate in the ethylene-glycidyl methacrylate copolymer is 1 to 50% by weight.