JPH09194699A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having excellent mechanical properties, low warpage and excellent flame retardancy. SOLUTION: This composition comprises 100 pts.wt. mixture comprising a thermoplastic polyester resin (A) based on a polybutylene terephthalate, an ABS resin (B) and a graft copolymer (C) comprising an ethylene/glycidyl methacrylate copolymer and an acrylonitrile/styrene copolymer, 10-150 pts.wt. mixture of glass fibers (D) with glass flakes (E) and 10-150 pts.wt. mixture of a bromoacrylate oligomer (F) with at least one material selected from among antimony trioxide, antimony pentoxide and zinc borate. The mixing ratio is such that 0.1<=B/(A+B+C)<=0.4, 0.02<=C/(A+B+C)<=0.1, D/E=4/1 to 1/4, and F/G=1/1 to 5/1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition having mechanical properties, low warpage and flame retardancy, and the resin composition is suitable for automobile parts, industrial parts and the like.

[0002]

2. Description of the Related Art Polyesters, especially polybutylene terephthalate, are excellent in moldability, electrical characteristics, heat resistance and mechanical characteristics, and the addition of a reinforcing material such as glass fiber greatly improves strength and rigidity. Widely used in electric / electronic parts, automobile parts, industrial parts, etc.

However, in a polybutylene terephthalate-based resin molded product reinforced with glass fibers or the like, the arrangement direction (flow direction) of the fibrous reinforcing material during molding such as injection molding.
In many cases, there is a difference in shrinkage between the and the direction orthogonal thereto, and as a result, there is a drawback that the molded product is warped and the dimensional accuracy is reduced.

For this reason, many methods for suppressing warpage of polybutylene terephthalate resin molded products have been proposed. For example, a method has been proposed in which a spherical warpage suppressing material such as glass beads and a flaky warpage suppressing material such as mica powder are blended (JP-A-54-69159, etc.).

However, when glass beads are mixed, the warp suppressing effect is insufficient in a combined use system with a fibrous reinforcing material such as glass fiber, and the strength of a polybutylene terephthalate resin molded product is not sufficient when only glass beads are used. Insufficient rigidity. On the other hand, when mica powder is blended, the strength of the welded part of the molded product is significantly reduced.

Further, since polybutylene terephthalate is flammable, when it is used for electric / electronic parts, a flame retardant mainly of a halogen type epoxy oligomer or carbonate oligomer and an inorganic flame retardant auxiliary agent are added, Flame retardation is being implemented.

However, a polybutylene terephthalate resin molded product containing such a flame retardant and a warpage suppressing material has low impact resistance and toughness, and in an electric component using this, for example, a connector or a controller cover, molding is performed. However, problems such as breakage may occur during the assembly or use process, and improvements in impact resistance and toughness are required.

In JP-A-1-185348, a thermoplastic resin having a multi-phase structure and an ABS resin are blended to improve impact resistance, but such a method does not heal the dimensional stability.

[0009]

SUMMARY OF THE INVENTION The present inventors have made intensive studies to solve the problems of the prior art, and as a result,
The object of the present invention, which has been completed, is to provide a polyester resin composition having low warpage, flame retardancy, and good mechanical properties.

[0010]

That is, the object of the present invention is to
Thermoplastic polyester resin (A) mainly composed of polybutylene terephthalate, ABS resin (B) and ethylene-
10 to 150 parts by weight of a mixture of glass fiber (D) and glass flakes (E) based on 100 parts by weight of a mixture of a glycidyl methacrylate copolymer and a graft copolymer (C) of an acrylonitrile-styrene copolymer, and Mixture 10-1 of the brominated acrylate oligomer (F) represented by the chemical formula 1 and any one kind or two or more kinds (G) of antimony trioxide, antimony pentoxide and zinc borate.
50 parts by weight are blended, and the blending ratio of each is 0.1 ≦ (B)
/((A)+(B)+(C))≦0.4, 0.02 ≦
(C) / ((A) + (B) + (C)) ≦ 0.1, (D)
/ (E) = 4/1 to 1/4, (F) / (G) = 1/1 to
It is achieved by a thermoplastic resin composition characterized by being 5/1.

[0011]

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[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The polybutylene terephthalate resin used in the present invention is a known polycondensation reaction of a dicarboxylic acid containing terephthalic acid as a main component or an ester-forming derivative thereof with a glycol component containing 1,4-butanediol as a main component. It is a polymer obtained by.

Specifically, terephthalic acid or its ester-forming derivative (such as dimethyl terephthalate) is used as a main component, and isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,
Dicarboxylic acid component composed of 4'-diphenoxyethanedicarboxylic acid, p-oxybenzoic acid, sebacic acid, adipic acid, dimer acid and the like, and 1,4-butanediol as the main component, ethylene glycol or ethylene It is formed by polycondensation with a glycol component which is appropriately used in combination with glycols such as oxide, trimethylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol.

The thermoplastic polyester resin mainly composed of polybutylene terephthalate used in the present invention may be a mixture of the above polybutylene terephthalate and another thermoplastic polyester resin. Here, the other thermoplastic polyester resin is, for example, a polycondensation product of polyethylene terephthalate, which is a polycondensation product of terephthalic acid and ethylene glycol, a polycondensation product of terephthalic acid, polytetraoxymethylene glycol, and 1,4-butanediol. Certain polyester elastomers, polyethylene naphthalate which is a polycondensation product of 2,6-naphthalenedicarboxylic acid and ethylene glycol, and polybutylene naphthalate which is a polycondensation product of 2,6-naphthalenedicarboxylic acid and 1,4-butanediol. Etc.

Further, terephthalic acid, isophthalic acid,
2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, p-oxybenzoic acid, sebacic acid, adipic acid, dimer acid, etc. Group dicarboxylic acid or its ester-forming derivative component and glycols such as 1,4-butanediol, ethylene glycol, ethylene oxide, trimethylene glycol, hexamethylene glycol, decamethylene glycol, and cyclohexanedimethanol are used in combination. A polycondensation product with a glycol component is also included.

The ABS resin used in the present invention is obtained by graft-polymerizing acrylonitrile and aromatic vinyl or acrylonitrile, aromatic vinyl and methacrylic acid ester to a polymer mainly containing a conjugated diolefin as a rubber component and mainly butadiene. Which is usually a polybutadiene latex or a styrene / butadiene copolymer (S
BR) It is obtained by polymerizing monomers in the presence of latex in an emulsified state and solidifying and drying. However, other various production methods can be adopted, and the present invention is limited to specific production methods. It is not something that will be done. In addition, there is no restriction by containing a small amount of a monomer other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, acrylic acid and its ester.

The graft copolymer of ethylene-glycidyl methacrylate copolymer and acrylonitrile-styrene copolymer used in the present invention is obtained by either emulsion polymerization using bulk polymerization, bulk polymerization or suspension polymerization. The resulting ethylene-glycidyl methacrylate copolymer, acrylonitrile-styrene copolymer, and the graft copolymerized by any method such as the above-mentioned emulsion polymerization.

A preferred specific example is MODIPER A4400 (copolymerization composition ratio: ethylene / glycidyl methacrylate / acrylonitrile / styrene = made by NOF CORPORATION).
42.5 / 7.5 / 15/35 (wt%)).

Thermoplastic polyester resins (A) and A mainly composed of polybutylene terephthalate used in the present invention.
The blending amounts of the BS resin (B) and the graft copolymer (C) of the ethylene-glycidyl methacrylate copolymer and the acrylonitrile-styrene copolymer are as follows.
0.1 ≦ (B) / ((A) + (B) + (C)) ≦ 0.
4, 0.02 ≦ (C) / ((A) + (B) + (C)) ≦
It is essential that it is 0.1. 0.1> (B) /
In the case of ((A) + (B) + (C)), the low warpage property is insufficient, while (B) / ((A) + (B) + (C))>
In the case of 0.4, the heat resistance becomes poor.

Further, 0.02> (C) / ((A) +
In the case of (B) + (C)), the impact strength is insufficient, while in the case of (C) / ((A) + (B) + (C))> 0.1, the heat resistance is poor. is there.

The glass fibers used in the present invention are those used for ordinary glass fiber reinforced thermoplastic resins, and generally have a diameter of 5 to 20 μm and a length of 1 to 25 mm. The surface of the glass fiber used in the present invention is, for example,
It may be surface-treated with aminosilane, epoxysilane, borane, vinylsilane, methacrylosilane, etc.,
Furthermore, due to the handling properties during kneading, urethane, P
You may use together a converging agent, such as ET and EVA.

The glass flakes used in the present invention have a major axis of 50 to 1000 μ and a thickness of 1 to 10 μ.
From the viewpoint of handleability at the time of kneading, it is possible to use a sizing agent which has been converged into several hundred sheets.

The blending amount of the glass fiber (D) and the glass flake (E) used in the present invention is polybutylene terephthalate or a thermoplastic polyester resin 1 mainly containing this.
It is important that the total amount of both the glass fiber (D) and the glass flakes (E) is 10 to 150 parts by weight, and particularly preferably 15 to 130 parts by weight, relative to 00 parts by weight. When the amount is less than 10 parts by weight, the strength and rigidity are insufficient, and when the amount is more than 150 parts by weight, the fluidity of the composition at the time of melting is remarkably lowered, and injection molding becomes difficult.

The compounding ratio of the glass fibers (D) and the glass flakes (E) used in the present invention is (D) / (E) = 4/1.
It is important that it is ~ 1/4. (D) / (E)> 4 /
In the case of 1, the warp suppressing effect of the glass flakes is insufficient, and the obtained molded product has a large warp. On the other hand, (D) /
When (E) <1/4, the reinforcing effect of the glass fiber becomes small, and the strength and rigidity are insufficient.

The brominated acrylate oligomer used in the present invention is shown below.

[0027]

Embedded image

The antimony trioxide, sodium antimony pentaoxide, and zinc borate used in the present invention are usually used as flame retardant aids for resins. Any one kind or a mixture of two or more kinds is used. .

The brominated acrylate oligomer (F) used in the present invention and antimony trioxide, antimony pentoxide,
The compounding amount of any one type or two or more types (G) of zinc borate is 100 parts by weight of polybutylene terephthalate or a thermoplastic polyester resin mainly containing this, and a brominated acrylate oligomer (F) and antimony trioxide, Total amount of one or more of sodium antimonate pentoxide and zinc borate (G) 10
It is essential that the amount is 100 parts by weight, and particularly 15 to 80
It is preferably part by weight. If it is less than 10 parts by weight, the flame retardancy is insufficient, and if it exceeds 100 parts by weight, the mechanical properties become poor.

The compounding ratio of the brominated acrylate oligomer (F) used in the present invention and one or more of antimony trioxide, sodium antimonate pentoxide and zinc borate (G) is (F) / ( G) = 1/1 to 5/1
It is essential that When (D) / (E) <1/1, mechanical properties are poor, and when (F) / (G)> 5/1, flame retardancy is insufficient.

The composition of the present invention contains conventional additives such as antioxidants and heat stabilizers (eg hindered phenols, hydroquinones, thioethers, phosphites and their substitutions) within a range not impairing the object of the present invention. Body and combinations thereof), UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents (eg montanic acid and its salts, stearic acid and its salts, stearyl alcohol,
Stearyl amide, silicone resin, etc.), dye (eg, nitrocin, etc.) and pigment (eg, cadmium sulfide, phthalocyanine, carbon black, etc.), a coloring agent, an additive impregnating solution (eg, silicone oil, etc.), etc. are added. Can be done.

In the thermoplastic resin composition of the present invention, it is preferable that all components are sufficiently dispersed. As a method for this, for example, there is a method in which a pellet-shaped resin is produced by using a different-direction rotating twin-screw extruder and is subjected to an injection molding process.

[0033]

INDUSTRIAL APPLICABILITY The present invention relates to a polyester resin composition having mechanical properties, low warpage and flame retardancy, and is suitable for automobile parts, industrial parts and the like.

[0034]

The present invention will be specifically described below with reference to examples. The physical properties were evaluated according to the following methods.

Tensile Strength: ASTM D638 Flexural Modulus: ASTM D790 Impact Strength: ASTM D256 Izod Notched 1/4 inch Heat Deformation Temperature: ASTM D648 Warpage Evaluation Method: 150 × 150 × 2 Plate (Direct Center Gate) Sled Measurement Flammability: UL94 vertical burning test

(Production Example of Polyester Resin (Polybutylene Naphthalate Resin) Obtained with 2,6-Naphthalenedicarboxylic Acid as Acid Component and 1,4-Butanediol as Glycol Component) Dimethyl 2,6-naphthalene 12. Four
kg (100 mol), 1,4-butanediol 12.6
kg (140 mol) and 10 g (0.03 mol) of tetra-n-butyl titanate as a transesterification and polymerization catalyst were placed in an autoclave with a capacity of 100 L equipped with a stirrer, and after being sufficiently replaced with nitrogen, gradually added in a nitrogen atmosphere. The resulting methanol was heated to 210 ° C. for 1 hour to distill off the produced methanol to the outside of the system, and transesterification was performed. After the distillation of methanol was almost completed, the reaction product was transferred to a polycondensation reaction tank having a vacuum pump and a capacity of 100 L, and the temperature was reduced to 250 ° C. and the degree of vacuum was reduced to 0.5 mmHg over 1 hour. Then, a polybutylene naphthalate resin was obtained.

(Production Example of Polyester Resin Copolymerized with Dimer Acid) Dimethyl terephthalate 9.9 kg (80 mol), hydrogenated dimer acid (PRIKPL manufactured by Unichema)
AST3008) 10.0 kg (20 mol), 1,4-
Butanediol 12.6 kg (140 mol) and tetra-n-butyl titanate 10 g (0.03 mol) as a transesterification and polymerization catalyst were equipped with a stirrer and a capacity of 100.
After charging in an L autoclave and thoroughly replacing with nitrogen,
After gradually heating in a nitrogen atmosphere at 210 ° C. for 1 hour, methanol produced was distilled out of the system to perform transesterification. After further reacting at 210 ° C. for 1 hour, after the distillation of methanol was almost completed, the reaction product was transferred to a polycondensation reaction tank having a vacuum pump and a capacity of 100 L, and the temperature was gradually raised to 250 ° C. at a vacuum degree for 1 hour. The temperature was reduced to 0.5 mmHg under reduced pressure, and then polycondensation reaction was performed for 2 hours to obtain a polyester resin copolymerized with dimer acid.

Examples 1 to 4, Comparative Examples 1 to 4 Polybutylene terephthalate resin (PBT7 manufactured by Kanebo Co., Ltd.)
19) 82 parts by weight, ABS resin (manufactured by Monsanto Kasei Co., Ltd.
15 parts by weight of TFX-610), 3 parts by weight of a graft copolymer of ethylene-glycidyl methacrylate copolymer and acrylonitrile-styrene copolymer (Modifier A4400 manufactured by NOF CORPORATION), and glass fiber (manufactured by Nippon Electric Glass Co., Ltd.). ECS03T-187 / P, diameter 13μ, length 3mm), glass flake (Nippon Sheet Glass REF
G-101, major axis 600 μ, thickness 4-5 μ) was blended in the composition shown in Table 1 and further brominated acrylate oligomer (Dead Sea Bromine PBB-P).
A) 24 parts by weight and antimony trioxide (manufactured by Nippon Seiko Co., Ltd.)
ATOX-B) 12 parts by weight, screw diameter 30
mm bi-directional twin-screw kneading extruder (TEX-made by Nippon Steel Co., Ltd.)
30) was melt-kneaded at 250 ° C. to obtain pellets.

The obtained pellets were dried under reduced pressure and then subjected to injection molding (using Sumitomo Heavy Industries Ltd. Nestal SG-75, injection molding temperature 250 ° C., mold temperature 80 ° C.) to obtain test pieces.
It was subjected to a physical property test. The results are also shown in Table 1.

[0040]

[Table 1]

Examples 5 and 6, Comparative Examples 5 to 8 Polybutylene terephthalate resin used in Example 1,
52 parts by weight, 15 parts by weight and 3 parts by weight of an ABS resin and a graft copolymer of an ethylene-glycidyl methacrylate copolymer and an acrylonitrile-styrene copolymer, respectively.
40 parts by weight of the glass fibers used in Example 1, 20 parts by weight of the glass flakes used in Example 1, and 30 parts by weight of the polybutylene naphthalate resin obtained in Production Example, and bromine used in Examples. Acrylate oligomer and sodium pentoxide antimonate (San Epoch NA-1030 manufactured by Nissan Chemical Co., Ltd.) are compounded in the composition shown in Table 2, and a biaxial kneading extruder having different screw diameters of 30 mm (TEX-30 manufactured by Nippon Steel). Melt kneading at 250 ℃,
Pellets were obtained.

The pellets thus obtained were dried under reduced pressure and then subjected to injection molding to obtain test pieces, which were then subjected to a physical property test. Table 2 shows the results.
It is shown together with.

[0043]

[Table 2] * Not applicable to V-2

Examples 7 and Comparative Examples 9 and 10 Polybutylene terephthalate resin (PBT7 manufactured by Kanebo Co., Ltd.)
20) 52 parts by weight, 15 parts by weight and 3 parts by weight of the ABS resin used in Example 1 and a graft copolymer of an ethylene-glycidyl methacrylate copolymer and an acrylonitrile-styrene copolymer, respectively, were obtained in a production example. To 30 parts by weight of the polyester resin obtained by copolymerizing the obtained dimer acid, 40 parts by weight of the warpage suppressing material shown in Table 3, glass fiber (ECS03T-123H / P manufactured by Nippon Electric Glass Co., Ltd.,
40 parts by weight (diameter 11 μ, length 3 mm), 24 parts by weight of brominated acrylate oligomer used in Example 1, 6 parts by weight of antimony trioxide used in Example 1 and zinc borate (HA-1 manufactured by Sakai Chemical Industry Co., Ltd.). 6 parts by weight were mixed and melt-kneaded at 250 ° C. with a biaxial kneading extruder of different directions having a screw diameter of 30 mm (TEX-30 manufactured by Nippon Steel Co., Ltd.) to obtain pellets.

The pellets thus obtained were dried under reduced pressure and then subjected to injection molding to obtain test pieces, which were then subjected to a physical property test. The results are also shown in Table 3.
It is shown together with.

[0046]

[Table 3]

Examples 8 and 9, Comparative Examples 11 to 14 Polybutylene terephthalate resin used in Example 1,
ABS resin and a graft copolymer of an ethylene-glycidyl methacrylate copolymer and an acrylonitrile-styrene copolymer were blended in a composition shown in Table 4, and the total amount was 100.
40 parts by weight of the glass fiber used in Example 1, 20 parts by weight of glass flakes, 24 parts by weight of brominated acrylate oligomer and 12 parts by weight of antimony trioxide were mixed with the parts by weight, and biaxial biaxial kneading with a screw diameter of 30 mm was performed. It was melt-kneaded at 250 ° C. with an extruder (TEX-30 manufactured by Nippon Steel Co., Ltd.) to obtain pellets.

The pellets thus obtained were dried under reduced pressure and then subjected to injection molding to obtain test pieces, which were then subjected to a physical property test. Table 4 shows the results.
It is shown together with.

[0049]

[Table 4] * Graft copolymer of ethylene-glycidyl methacrylate copolymer and acrylonitrile-styrene copolymer

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[Procedure amendment]

[Submission date] March 25, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Title: Thermoplastic resin composition

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/101 KJV C08K 5/101 KJV 7/14 KKF 7/14 KKF 7/28 7/28 C08L 55/02 LLX C08L 55/02 LLX

Claims (1)

[Claims] 1. From a thermoplastic polyester resin (A) mainly composed of polybutylene terephthalate, an ABS resin (B) and a graft copolymer (C) of an ethylene-glycidyl methacrylate copolymer and an acrylonitrile-styrene copolymer. 10 to 150 of a mixture of glass fiber (D) and glass flake (E) per 100 parts by weight of the mixture.
10 to 150 parts by weight of a mixture of 1 part by weight or one or more kinds of antimony trioxide, antimony pentoxide and zinc borate (G) with a brominated acrylate oligomer (F) shown below, each of which is used The compounding ratio of 0.
1 ≦ (B) / ((A) + (B) + (C)) ≦ 0.4,
0.02 ≦ (C) / ((A) + (B) + (C)) ≦ 0.
1, (D) / (E) = 4/1 to 1/4, (F) / (G)
= 1/1 to 5/1, The thermoplastic resin composition characterized by the above-mentioned.