JPH09188792A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the above composition composed of a styrene resin and a specific modified polyamide elastomer, exhibiting permanent antistaticity, having excellent mechanical properties such as impact resistance, giving an injection-molded article having excellent appearance and useful as electronic and mechanical parts of a copying machine, etc. SOLUTION: This resin composition contains (A) a styrene resin and (B) a modified polyamide elastomer produced by the graft-polymerization of (B1 ) a 1,2-alkylene oxide (e.g. ethylene oxide or 1,2-propylene oxide) to (B2 ) a polyamide elastomer consisting of a polyether ester amide or a polyester amide. The grafting ratio of the component B1 to the component B2 is e.g. 1-300wt.%, especially 5-200wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic resin composition having permanent antistatic properties, excellent mechanical properties such as impact resistance, and excellent moldability.

[0002]

2. Description of the Related Art Thermoplastic resins represented by polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyester resins, styrene resins, polyoxymethylene resins and the like are used in copiers, televisions and the like. It is widely used for electronic and electromechanical parts. Conventionally, the resin used for these components has a problem in products because static electricity is easily generated.

Accordingly, as a resin having improved antistatic properties, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylic acid ester with a vinyl monomer having an alkylene oxide group, There is a resin composition obtained by graft polymerization of a vinyl monomer or a vinylidene monomer (JP-A-55-36237) and the like, which has reached a practical antistatic property.

Japanese Patent Application Laid-Open No. 1-163234 discloses that a modified olefin polymer containing 1 to 40 parts by weight of a polyetheresteramide, 20 to 98 parts by weight of a polyolefin, and a functional group containing a functional group such as a carboxyl group. It is disclosed that by mixing parts by weight, a resin composition having permanent antistatic properties can be obtained.

Japanese Patent Application Laid-Open No. 2-58566 discloses a modified polyamide obtained by polyaddition of ethylene oxide to 1 to 99% by weight of a thermoplastic resin and aliphatic polyamide.
It discloses that a resin composition having a permanent antistatic property can be obtained by mixing up to 1% by weight.

However, the above-mentioned Japanese Patent Application Laid-Open No. 55-362 discloses
The antistatic resin obtained by graft-polymerizing a hydrophilic rubber-like polymer with a monomer described in Japanese Patent No. 37 uses a special hydrophilic rubber-like polymer. It is not sufficiently satisfactory because it is complicated and the resulting resin has poor mechanical properties.

Further, the antistatic resin composition disclosed in Japanese Patent Application Laid-Open No. 1-163234 has a problem that the melt viscosity of the constituent polyetheresteramide is low, so that the compatibility with the polyolefin is not sufficient. is there.

Further, in the antistatic resin composition disclosed in Japanese Patent Application Laid-Open No. 2-58566, when ethylene oxide is polyadded to the polyamide, the melt viscosity of the modified polyamide obtained becomes abnormally high. . When the modification ratio is increased, this is particularly remarkable, and thus there is a drawback that the compatibility and fluidity of the resin composition are poor, and the moldability is not sufficiently satisfactory.

The present invention provides a resin composition having a permanent antistatic property, excellent mechanical properties typified by impact resistance, excellent color tone, and excellent moldability, regardless of a complicated production method. The purpose is to provide.

The present inventor has previously found that a resin composition of a styrene resin and a specific modified polyetheramide solves the above problems, and has already filed an application (Japanese Patent Application No. 3-1).
No. 2399).

As a result of further research on this point, the inventors have found that a resin composition of a styrene resin and a new specific modified polyamide elastomer can solve the above problems, and arrived at the present invention.

[0012]

[Means for solving the problems]

[Constitution of the Invention] The present invention relates to a polyamide elastomer selected from (A) styrene resin, (B) polyether ester amide and polyester amide.
And a modified polyamide elastomer obtained by graft-polymerizing 1,2-alkylene oxide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. As the styrene resin (A) in the present invention,
Polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubbery copolymer, methyl methacrylate-styrene copolymer (MS resin), styrene-rubbery polymer-acrylonitrile copolymer (A
BS resin, AES resin, AAS resin) and the like. Further, these styrene resins may be used as a mixture of two or more kinds. Further, some of these styrenes and / or acrylonitriles may be copolymerized with styrene such as α-methylstyrene, acrylic acid ester, methacrylic acid ester, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride and phenylmaleimide. Those substituted with a monomer are also included.

The (B) modified polyamide elastomer in the present invention is formed by graft-polymerizing (B ₂ ) 1,2-alkylene oxide onto a polyamide elastomer selected from (B ₁ ) polyether ester amide and polyester amide. Alkylene oxide grafted polyetheresteramides and alkylene oxide grafted polyesteramides.

The (B ₁ ) polyether ester amide and polyester amide are produced by known methods.
A method for producing a polyether ester amide is described in, for example, JP-B-56-45419, JP-B-57-24808, JP-B-63-32090, JP-B-63-456 and JP-B-S6-6.
3-20254. That is, basically, (a) a polyamide-forming monomer, (b ₁ ) a polyether having a hydroxy end group, and (c ₁ ) (b ₁ ) a substantially equivalent amount of an aliphatic or alicyclic group in the end group. It is produced by polycondensation using a dicarboxylic acid selected from group and aromatic dicarboxylic acids as a starting material.

Examples of the (a) polyamide-forming monomer include ω-lactam, ω-aminocarboxylic acid and salts of diamine and dicarboxylic acid. Specific examples of ω-lactams include caprolactam, enanthlactam,
Examples include decalactam, undecalactam and dodecaractam. Specific examples of ω-aminocarboxylic acid include 6-aminocaproic acid, 10-aminodecanoic acid and 1
1-aminoundecanoic acid and 12-aminododecanoic acid are mentioned. Specific examples of the salt of diamine and dicarboxylic acid, ethylenediamine, trimethylenediamine,
Tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine,
2,2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3- / 1,4-bis (aminomethyl) cyclohexane, bis (4,4'-aminocyclohexyl) methane, m- / p Diamines such as xylylenediamine and oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Salts with dicarboxylic acids such as acids are mentioned.

Specific examples of the (b ₁ ) polyether having a hydroxy end group include polyethers formed from polyether-forming monomers such as ethylene oxide, propylene oxide and tetrahydrofuran (polyether structural units having a chain length of 2 to 2). 60).

Specific examples of the dicarboxylic acid (c ₁ ) selected from aliphatic, alicyclic and aromatic dicarboxylic acids include:
Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, 1,
Examples thereof include 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, and a dimerized fatty acid (dimer acid) obtained by coupling oleic acid, linoleic acid, linolenic acid or the like or coupling and subsequent hydrogenation.

Polycondensation using each of the above raw materials is carried out by a conventional method (for example, disclosed in the above cited publication). In the case of a polyether ester amide, the components (a), (b ₁ ) and (c ₁ ) are charged together (the concentration of each end group of (b ₁ ) and (c ₁ ) is equivalent) and melt polycondensation is performed. Alternatively, the polycondensation of the components (a) and (c ₁ ) is first performed to obtain a polyamide having a carboxyl end group, and then the component (b ₁ ) and the polyamide are mixed so that the concentration of each end group is substantially equivalent. It may be charged and melt polycondensed. The polycondensation is performed under reduced pressure in the presence of a known catalyst if necessary.

The proportion of the polyether segment in the polyether ester amide is preferably 5 to 85% by weight, preferably 10 to 80% by weight.

Further, the method for producing polyesteramide is as follows:
For example, JP-A-51-151798 and JP-B-61-368.
58. That is, (a) the above-mentioned polyamide-forming monomer, (c ₁ ) hydrogenated dimerized fatty acid (dimer acid) or liquid polybutadiene having a carboxyl end group, and (b ₂ ) (c ₁ ) substantially equivalent to the end group. It is produced by a conventional polycondensation method using a diamine selected from the aliphatic, alicyclic and aromatic diamines as a starting material.

Specific examples of (b ₂ ) diamines selected from aliphatic, alicyclic and aromatic diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Dimer diamine,
Aliphatic diamines such as 2,2,4- / 2,4,4-trimethylhexamethylenediamine; 1,3- / 1,4-
Bis (aminomethyl) cyclohexane, bis (4,4 '
Alicyclic diamines such as -aminocyclohexyl) methane; aromatic diamines such as m- / p-xylylenediamine. The dimer diamine is an amination product of a dimer of unsaturated fatty acid such as oleic acid, linoleic acid and linolenic acid, and the following production examples can be mentioned.

HOOCCH ₂ (C ₃₂ H _X ) CH ₂ COO
H (dimer acid) + NH ₃ → NCCH ₂ (C
₃₂ H _X ) CH ₂ CN + H ₂ → H ₂ NCH ₂ CH
₂ (C ₃₂ H _X ) CH ₂ CH ₂ NH ₂ (dimer diamine)

Examples of the (B ₂ ) 1,2-alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, and the like. , 1,2-Propylene oxide is preferred.

In the present invention, the graft polymerization of (B ₂ ) to (B ₁ ) is carried out by a method known as the graft polymerization of (B ₂ ) to nylon 6 (for example,
H. C. Haas et al. Polym. Sci. , 1
5 , 427 (1955); Ger. 956400; US
2835653; Belg. 6665018; Ikemura, Koka, 18 , 71 (1961); Yamaguchi et al., Koka, 30 , 3.
31 (1973)). For example, it can be easily achieved by heating (B ₁ ) and (B ₂ ) to 60 to 150 ° C. in the absence of a catalyst or in the presence of an alkali catalyst, if necessary. If necessary, (B ₂ ) 1,2-alkylene oxide is used by dissolving it in a hydrocarbon solvent such as hexane, heptane, or toluene. (B ₁ ) may be in any form such as powder and pellets. According to the research by the inventors,
Graft polymerization of (B ₁₎ with respect to (B ₂₎ takes place as follows relative to the amide bond predominantly (B _1).

[0027]

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Homopolymerization of (B ₂ ) may also occur depending on the reaction conditions. In that case, after the reaction, washing with the solvent of the homopolymer (B ₂ ) (for example, hot water, hot alcohol, chloroform) is carried out. To be done. Of course, this operation is not necessary unless the coexistence of the homopolymer of (B ₂ ) causes substantially any adverse effect. Graft ratio of (B ₁₎ with respect to (B ₂₎ as the ((B ₁₎ was grafted per 100 parts by weight (weight of B _2)), but preferably 1 to 300%, especially preferably from 5 to 200% Is. When the graft ratio is less than 1%, the antistatic property of the final resin composition is poor. Also, 3
If it is more than 00%, grafting is extremely difficult and not practical.

The polymer obtained in this manner is (A)
The styrene resin is generally 1 to 99% by weight, preferably 2
The content of the modified polyamide elastomer (B) is 0 to 95% by weight, generally 99 to 1% by weight, preferably 80 to 5% by weight.

The resin composition of the present invention can be further improved in antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant. Further, if necessary, various stabilizers such as a compatibilizer such as an oligomer, an antioxidant, and an ultraviolet absorber, a pigment, a dye, a lubricant, a plasticizer, a glass fiber, an inorganic filler, and a flame retardant are added. You can also do it.

[0031]

The thermoplastic resin composition of the present invention comprising a styrene resin and a new specific modified polyamide elastomer is a resin composition of a styrene resin previously applied and a specific modified polyetheramide (special Wishhei 3-12399
Similar to No. 1), it has permanent antistatic properties and is excellent in mechanical properties such as impact resistance, and has no problem of appearance defects such as "unevenness" and "waviness" on the surface that occur during injection molding. have. Therefore, the antistatic resin composition of the present invention is extremely useful as a material for electronic and electromechanical parts such as copying machines.

[0032]

EXAMPLES In order to specifically explain the present invention, reference examples, examples and comparative examples will be described below. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods. Izod impact strength (kg-cm / cm): ASTM
D256 surface specific resistance value (Ω): 3.2 mm ^t × 100 mm × 1
Room temperature 23 ° C, humidity 65% RH using a 00mm molded product
It measured under the atmosphere of. Half-life of charged voltage (sec): 3.2 mm ^t × 100 mm
Room temperature 23 ° C, humidity 65% RH on a × 100mm molded product
An initial voltage of 8000 V was charged in the atmosphere of, and the time until this voltage became 1/2 was measured by a static crossing waveform of a static Honest meter. Surface condition of molded product: A molded product having a size of 30 mm × 100 mm × 3 mm was molded by injection molding, and the presence or absence of a poor surface condition such as “unevenness” and “waviness” on the surface was visually observed and judged.

Reference Example (A-1): Preparation of Styrenic Resin An ABS resin was obtained by emulsion polymerization using the following formulation. Formulation Styrene (ST) 64 parts by weight Acrylonitrile (AN) 21 parts by weight Polybutadiene latex (solid content) 15 parts by weight Disproportionated potassium rosinate 1 part by weight tert-dodecyl mercaptan (t-DM) 0.1 parts by weight cumene hydro Peroxide 0.3 parts by weight Ferrous sulfate 0.007 parts by weight Sodium pyrophosphate 0.1 parts by weight Crystal glucose 0.3 parts by weight Distilled water 190 parts by weight

Distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutadiene latex were charged into an autoclave, and after heating to 60 ° C, ferrous sulfate, sodium pyrophosphate and crystalline glucose were added and kept at 60 ° C. As it was, ST, AN, t-DB and cumene hydroperoxide were continuously added over 2 hours, then the temperature was raised to 70 ° C. and the temperature was kept for 1 hour to complete the reaction. An antioxidant was added to the ABS latex obtained by such a reaction, then coagulated with sulfuric acid, thoroughly washed with water and dried to obtain a powdery ABS resin.

Synthesis of ethylene oxide-grafted polyether ester amide (B-1): 50 parts by weight of ε-caprolactam and 9.35 parts by weight of dodecanedioic acid were charged in an autoclave, the atmosphere was replaced with N _2, and the mixture was heated at 240 ° C. for 3 hours. A carboxyl group polyamide 6 prepolymer was obtained. Then number average molecular weight 10
The polycondensation was completed by charging 40.65 parts by weight of polybutylene glycol of 00 and 0.1 parts by weight of antimony trioxide as an esterification catalyst to a temperature of 270 ° C. for about 1 hour and further heating for 5 hours. The molten resin was extruded into strands from the lower part of the autoclave, and cut into pellets with a pelletizer. This gave a polyether ester amide with η _r 1.92. 100 parts by weight of the pelletized polyetheresteramide was added at 80 ° C.
-Disperse in hexane and add ethylene oxide to 5
The mixture was charged with 0% by weight and reacted under pressure for 8 hours. After the reaction,
After filtration, washing and drying, ethylene oxide grafted polyether ester amide was obtained. From the increase in the weight of the obtained polymer, the graft ratio of ethylene oxide was 47%.

(C): Synthesis of ethylene oxide grafted nylon 6 Nylon 6 pellets (1013B manufactured by Ube Industries, Ltd.)
Was used in the same manner as in the procedure of B-1 to obtain grafted nylon 6 having an ethylene oxide graft ratio of 89%. Melt flow rate of this product (235 ° C, load 2160)
g, JIS D1238R) was 0.

Example 1 (A-1) Styrenic resin prepared in Reference Example, (B-
1) Ethylene oxide grafted polyether ester amide elastomer was mixed in the compounding ratio shown in Table 1 and melt-kneaded at a resin temperature of 240 ° C. with a vented 30 mmφ extruder.
Pellets were produced by performing extrusion.

[0038]

[Table 1] Then, a test piece was molded by an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C., and each physical property was measured. The measurement results are shown in Table 1.

Comparative Example 1 By the same treatment as in Example 1, the compounding ratios shown in Table 1 were mixed, melt-kneaded into pellets, and the respective physical properties were measured. Table 1 shows the measurement results
It was shown to.

Claims (1)

[Claims] 1. A modified polyamide elastomer obtained by graft-polymerizing a 1,2-alkylene oxide onto a polyamide elastomer selected from (A) styrene resin, (B) polyether ester amide, and polyester amide.
A thermoplastic resin composition comprising: