JPH0745612B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention has an antistatic resin composition having a permanent antistatic property and excellent in balance of mechanical properties represented by impact resistance and heat resistance. Regarding things.

[Conventional technology]

Synthetic polymeric materials are used in a wide range of fields due to their excellent properties. If these materials are provided with antistatic properties and heat resistance in addition to the mechanical strength of the materials, their applications can be further expanded. That is, it is possible to expand the application to electronic machines such as copying machines, televisions, etc., electromechanical parts, various dustproof parts, etc., which are desired to prevent damage due to static electricity. Further, in these fields, the demand for heat resistance of synthetic resins is increasing year by year.

As a method for improving the antistatic property of a synthetic polymer material, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or / and an acrylic acid ester and a vinyl-based monomer having an alkylene oxide group is vinyl-based. A method obtained by graft-polymerizing a monomer or a vinylidene monomer (JP-A-55-3623)
No. 7), etc., and has achieved practical antistatic properties.

Further, as a component similar to the component of the present invention, there is disclosed in
A composition obtained by blending a polyamide elastomer with a styrene resin disclosed in JP-A-60-170646 is mentioned, which improves the abrasion resistance of the styrene resin.

[Problems to be solved by the invention]

In the method described in JP-A-55-36237, the antistatic resin obtained by graft-polymerizing a monomer to a hydrophilic rubber-like polymer uses a special hydrophilic rubber-like polymer. Therefore, the manufacturing method is complicated, and the mechanical properties and heat resistance of the obtained resin are inferior, which is not sufficient.

Further, only the resin composition described in JP-A-60-170646,
Although some antistatic property is obtained, the heat resistance is poor,
It is not possible to obtain a satisfactory composition.

Therefore, the present invention has an antistatic resin composition having a permanent antistatic property and having excellent balance of mechanical properties represented by impact resistance and heat resistance without depending on a complicated production method. The challenge is to provide.

[Means for solving problems]

As a result of earnest studies to solve the above problems, in order to solve the above problems, it was found that it is important to blend a relatively predominant amount of a polycarbonate resin into a specific polyether ester amide, and arrived at the present invention. .

That is, the present invention includes (A) (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and a dicarboxylic acid having 6 or more carbon atoms, (b) polyethylene glycol having a number average molecular weight of 200 to 6000, and (C) 1 to 50 parts by weight of a polyether ester amide composed of a dicarboxylic acid having 4 to 20 carbon atoms and having a polyether ester unit of 95 to 10% by weight (B) a polycarbonate resin 95 to 50 parts by weight and (C) styrene thermoplastic resin 4 to 49 parts by weight,
Further, it is a thermoplastic resin composition which is blended in such a proportion that the total amount of (A) + (B) + (C) is 100 parts by weight.

Hereinafter, the present invention will be specifically described.

(A) Aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of a diamine having 6 or more carbon atoms and a dicarboxylic acid, which is a constituent component of the polyether ester amide in the present invention, is ω-aminocaproic acid, ω
-Aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or caprolactam, enantolactam,
Lactams such as capryllactam and laurolactam and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, especially caprolactam, 12-amino acid. Dodecanoic acid and hexamethylenediamine-adipate are preferably used.

As the constituent component of the (A) polyether ester amide, (b) polyethylene glycol is used because of its excellent antistatic property. Polyethylene glycol has a number average molecular weight of 200 to 6,000, particularly used in the range of 250 to 4,000.When the number average molecular weight is less than 200, the obtained polyetheresteramide has poor mechanical properties, and the number average molecular weight is 6,
If it exceeds 000, the antistatic property becomes insufficient, which is not preferable.

Examples of the (C) dicarboxylic acid having 4 to 20 carbon atoms, which is a constituent component of the polyether ester amide, include terephthalic acid, isophthalic acid, phthalic acid, and naphthalene-2,6-
Aromatic dicarboxylic acids such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1 Alicyclic dicarboxylic acids such as 2,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid and succinic acid, oxalic acid, adipic acid,
Sebacic acid and dodecanedioic acid (decanedicarboxylic acid)
Examples of such aliphatic dicarboxylic acids include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanedioic acid, which are preferably used from the viewpoint of polymerizability, color tone and physical properties.

The (b) polyethylene glycol and the (c) dicarboxylic acid react at a molar ratio of 1: 1 in the reaction, but the charging ratio is usually changed depending on the kind of the dicarboxylic acid used.

Polyester glycol (b) polyester glycol and (c) dicarboxylic acid, which are the constituent components of the polyether ester, are constituent units of the polyether ester amide and are used in the range of 95 to 10% by weight. The mechanical properties of the amide are inferior, and if it is less than 10% by weight, the antistatic property of the obtained resin is inferior, which is not preferable.

The method for polymerizing the (A) polyether ester amide is not particularly limited. For example, (a) (a) an aminocarboxylic acid or lactam and (c) a dicarboxylic acid are reacted to obtain a polyamide prepolymer having carboxylic acid groups at both ends. Make up,
(B) Method of reacting polyethylene glycol under vacuum (b) Each compound of the above (a), (b) and (c) is charged into a reaction tank and added at high temperature in the presence or absence of water. A method of producing a carboxylic acid-terminated polyamide prepolymer by pressure reaction, and then proceeding the polymerization under normal pressure or reduced pressure; and (c) above (a), (b),
It is possible to use a known method such as a method in which the compound (c) is charged into a reaction vessel at the same time, melt-mixed, and then the polymerization is carried out all at once under high vacuum.

Examples of the (B) polycarbonate resin used in the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally, a polymer composed of bisphenols such as 2,2-bis (4-oxyphenyl) alkane type, bis (4-oxyphenyl) ether type, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide type,
Alternatively, it is a copolymer and is a polymer using bisphenols substituted with halogen according to the purpose.

The polycarbonate resin is produced by any method. For example, in the production of a polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane (commonly called bisphenol A), 4,4'-dihydroxydiphenyl-2,2-propane is used as a dioxy compound, and a caustic aqueous solution is used. And a phosgene method in which phosgene is blown in the presence of a solvent, or 4,4'-dihydroxydiphenyl-
A known method such as a method of transesterifying 2,2-propane and carbonic acid diester in the presence of a catalyst can be used.

In the present invention, in order to further improve the performance, (C) a styrene-based thermoplastic resin is further blended.

Examples of the (C) styrene-based thermoplastic resin used in the present invention include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubber polymer-acrylonitrile copolymer (ABS resin, AES resin, AA
S resin) and the like. Two or more of these may be used. Furthermore, a part of these styrene and / or acrylonitrile is α-methyl styrene, p-methyl styrene, pt-butyl styrene, (meth) acrylic acid or their ester compounds such as methyl, ethyl, propyl and n-butyl. , Unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, maleimides, N-methylmaleimide, N-phenylmaleimide and other maleimide monomers, acrylamide and other styrene copolymerizable vinyl monomers Some of them are included. Here, as the styrene-based thermoplastic resin, particularly ABS resin, AES resin,
AAS resin, MBS resin and the like are preferably used.

The resin composition of the present invention comprises (A) 1 to 50 parts by weight of polyether ester amide, preferably 5 to 40 parts by weight, and (B) 95 to 50 parts by weight of polycarbonate resin, preferably 95 to 55 parts by weight and (C) styrene type. Thermoplastic resin 4 to 49 parts by weight, preferably 4 to 40 parts by weight, and (A) + (B) +
It is mixed in such a proportion that the total amount of (C) becomes 100 parts by weight.
When the amount of the polyether ester amide (A) is less than 1 part by weight, the antistatic property of the resin composition is insufficient, and when it exceeds 50 parts by weight, the resin composition becomes soft and the mechanical properties are inferior, which is not preferable.

Further, when the content of the (B) polycarbonate resin is more than 99 parts by weight, the antistatic property of the resin composition is insufficient, and when it is less than 50 parts by weight, the heat resistance of the resin composition is poor, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (a) (A) polyether ester amide, (B) polycarbonate resin, and (C) styrene-based thermoplastic resin, which are collectively melt-kneaded. B) In advance (A)
And (C) are melt-kneaded, and then (B) is added to perform melt-kneading, and (C) (A) and (B) are collectively melt-kneaded. As the melt-kneading method, a Banbury mixer, roll, extruder or the like can be used.

The resin composition of the present invention is mixed with another thermoplastic polymer compatible with the resin composition of the present invention, for example, polyamide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether, etc., to improve performance as a molding resin. Can be improved. It is also possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant, and further, if necessary, to prevent oxidation. It is also possible to add various stabilizers such as agents and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers, and flame retardants.

[Action]

In the present invention, a resin composition obtained by mixing a specific amount of polyether ester amide with a polycarbonate resin and a styrene-based thermoplastic resin has excellent permanent antistatic properties, high mechanical properties and heat resistance. This phenomenon is presumed to be due to the fact that the polyether ester amide, the polycarbonate resin, and the styrene-based thermoplastic resin all have an affinity.

〔Example〕

In order to more specifically describe the present invention, examples and comparative examples will be described below. The finally obtained resin composition was molded by an injection molding method, and then the physical properties were measured by the following test methods.

Izod impact strength ASTM D256-56A Flexural elasticity rate ASTM D790 Thermal deformation temperature ASTM D648 (18.56kg / cm ² load) Volume specific resistance value: 2 ² × 40 ^φ disk, room temperature 23 ℃,
The humidity was measured in an atmosphere of 50% RH. A super insulation resistance meter SM-10 type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

Flame resistance: Vertical combustion test according to UL94 standard 1/16 ″
The test was conducted with a combustion test piece of × 1/2 ″ × 5 ″.

In addition, parts and% in the examples and comparative examples indicate parts by weight and% by weight.

Reference Example (1) Preparation of (A) Polyether Esteramide A-1: 50 parts of caprolactam, 47.4 parts of polyethylene glycol having a number average molecular weight of 2,000 and 3.8 parts of adipic acid were added to 0.2 parts of "Irganox" 1098 (antioxidant). And 0.1 parts of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon impeller, and after heating and stirring for 90 minutes while flowing a small amount of nitrogen at 240 ° C. as a nitrogen replacement to obtain a transparent homogeneous solution, 260 ° C., 0.5 mmHg Polymerization was carried out for 3 hours under the following conditions to obtain a viscous and transparent polymer. The polymer was discharged onto a cooling belt in a gut shape and pelletized to prepare a pelletized polyether ester amide (A-1).

A-2: Using exactly the same method as (A-1) except that 60 parts of nylon 6.6 salt (AH salt), 33.8 parts of polyethylene glycol having a number average molecular weight of 600 and 8.7 parts of adipic acid were used and the polymerization time was 4 hours. Polyether ester amide (A-2) was prepared.

A-3: Polyether ester in the same manner as in (A-1) except that 30 parts of ω-aminodecanoic acid, 14.2 parts of dodecanedioic acid and 58.6 parts of polyethylene glycol having a number average molecular weight of 1000 were used, and the polymerization time was 4 hours. The amide (A-3) was prepared.

A-4: Polyether ester amide (A-4) was prepared in the same manner as in (A-1) except that 95 parts of ω-aminodecanoic acid, 4.2 parts of polyethylene glycol having a number average molecular weight of 1000 and 1.0 part of dodecanedioic acid were used. Prepared.

(2) Preparation of (B) Polycarbonate Resin B-1: Lexan 121-111 (manufactured by EPL) was used.

B-2: Lexan 141-111 (manufactured by EPL) was used.

(3) Preparation of (C) Styrenic Thermoplastic Resin C-1: Polybutadiene Latex (Rubber Particle Diameter 0.25 μ,
Styrene in the presence of 60 parts (gel content 80%) (solid content conversion)
40 parts of a monomer mixture consisting of 70% and 30% acrylonitrile was emulsion polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (C-1).

C-2: Polybutadiene latex used in C-1 In the presence of 40 parts (as solid content), 60 parts of a monomer mixture consisting of 72% of methyl methacrylate, 24% of styrene and 4% of acrylonitrile was emulsion-polymerized and then C A powdery graft copolymer (C-2) was prepared in the same manner as in -1.

C-3: 72 parts of styrene and 28 parts of acrylonitrile were copolymerized to prepare a copolymer (C-3).

C-4: Dailark 232 (manufactured by ARCO) (copolymer of styrene and maleic anhydride) was used.

C-5: 70 parts of styrene, 25 parts of acrylonitrile and 5 parts of methacrylic acid were copolymerized to prepare a copolymer (C-5).

C-6: JSR-AES110 (manufactured by Nippon Synthetic Rubber Co., Ltd.) (styrene-EPDM-acrylonitrile copolymer) AES resin was used.

Examples 1 to 5 and 7 to 8 (A) polyether ester amide, (B) polycarbonate resin and (C) styrenic thermoplastic resin prepared in Reference Example were mixed at the compounding ratio shown in Table 1 in advance (B).
Other than the above, mixed with a 40mmφ extruder with vent, resin temperature 210 ℃
The pellets (B) melt-kneaded and extruded in (1) were mixed and melt-kneaded and extruded at a resin temperature of 240 ° C. to produce pellets. Then, using an injection molding machine, the cylinder temperature is 24
A test piece was molded at 0 ° C and a mold temperature of 60 ° C, and each physical property was measured.

The volume resistivity value uses a 2 mm thick disc molded by injection molding,
The measurement was performed under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Oil and Fats Co., Ltd.), then thoroughly wash with distilled water to remove surface water, and then 24 at 50% RH and 23 ° C. The humidity was measured with time.

(2) After molding, leave it in 50% RH, 23 ℃ for 200 days,
After washing with detergent "Mama Lemon" aqueous solution and then with distilled water thoroughly to remove surface moisture, 50% RH, 23 ℃
The humidity was measured for 24 hours.

The measurement results are shown in Table 2.

Comparative Examples 1 to 9 The (A) polyether ester amide, (B) polycarbonate resin, and (C) styrene-based thermoplastic resin prepared in Reference Examples were melt-kneaded at the compounding ratios shown in Table 1 in the same manner as in Examples. Then, the material was extruded and molded, and each physical property was measured.

The measurement results are shown in Table 2.

The following is clear from the results in Table 2. The resin compositions (Examples 1 to 8) of the present invention are excellent in impact strength, mechanical properties typified by flexural modulus and heat resistance,
It also has a low volume resistivity value. Moreover, the resistance value hardly changes due to surface cleaning or aging, and excellent permanent antistatic property is exhibited.

That is, the resin composition of the present invention has excellent mechanical properties, heat resistance, and permanent antistatic property.

On the other hand, the polyether ester amide (A) content is 1
Antistatic property (resistance value) when less than parts by weight (Comparative Example 1)
When the polyether ester amide (A) exceeds 50 parts by weight (Comparative Examples 2 and 7), heat resistance and flexural modulus are poor.

When the polyether ester amide (A) having a polyether ester unit of less than 10% by weight is used (Comparative Example 3), the antistatic property is poor.

When the compounding amount of the polycarbonate resin (B) is less than 50 parts by weight (Comparative Example 4), the heat resistance is poor, and when the polycarbonate resin (B) exceeds 99 parts by weight (Comparative Examples 5 and 8), the antistatic property is low. Inferior.

When the blending amount of the styrene-based thermoplastic resin (C) exceeds 49 parts by weight (Comparative Example 6), the heat resistance is poor. The resin composition containing no polyether ester amide (A) (Comparative Example 9) has a high resistance value and is inferior in antistatic property, which is not preferable.

〔The invention's effect〕

The thermoplastic resin composition of the present invention is excellent in both permanent antistatic properties, mechanical properties such as impact resistance, and heat resistance.

Claims (1)

[Claims] 1. (A) (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (b) number average molecular weight of 200.
1 to 50 parts by weight of a polyether ester amide composed of polyethylene glycol of about 6000 and (c) a dicarboxylic acid of 4 to 20 carbon atoms, wherein the polyether ester unit is 95 to 10% by weight. B) 95 to 50 parts by weight of polycarbonate resin and (C) 4 to 49 parts by weight of styrene thermoplastic resin, and the total amount of (A) + (B) + (C) is 100.
A thermoplastic resin composition which is blended in a proportion of parts by weight.