JPH0593118A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having permanent antistatic properties by compounding a thermoplastic styrene resin, a polyetheresteramide, and a specific styrenesulfonic acid polymer. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. resin component consisting of 10-99wt.% thermoplastic styrene resin and 90-1wt.% polyetheresteramaide with 0.01-50 pts.wt. styrenesulfonic acid polymer of the formula (wherein R is H, alkyl, or aryl; X is H, an alkali metal, an alkaline earth metal, or ammonium; and n is 10,000-20,000).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition of the present invention, and more particularly to a styrenic thermoplastic resin having a permanent antistatic property.

[0002]

BACKGROUND OF THE INVENTION Synthetic polymeric materials are used in a wide variety of fields due to their excellent properties. These materials are
If the material is provided with an antistatic property in addition to the mechanical strength of the material, its application can be further expanded. In other words, the application can be expanded to a copying machine, an electronic / electromechanical component such as a television, various dust-proof components, and the like, which are required to prevent damage due to static electricity.

As a method for improving the antistatic property of a synthetic polymer material, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylate ester and a vinyl monomer having an alkylene oxide group. In addition, there is a method (JP-A-55-362375) in which a vinyl-based monomer or a vinylidene monomer is graft-polymerized to obtain a practical antistatic property.

As a component similar to the component of the present invention, there is a composition of JP-A-60-170646 in which a polyamide elastomer is blended with a styrene resin. Has been improved. On the other hand, JP-A-63-97653 discloses a composition in which a polyamide elastomer is finely dispersed in a styrene resin in the form of particles of 0.01 to 10 μm to prevent delamination and to impart antistatic properties. ing.

Further, JP-A-2-7335 discloses a composition obtained by blending a thermoplastic resin with a mixture of a water-soluble thermoplastic polymer having a hydroxyl group or a polyhydric alcohol compound and polystyrene sulfonate. Are disclosed to have antistatic properties.

[0006]

However, the antistatic resin obtained by graft-polymerizing the hydrophilic rubber-like polymer described in JP-A-55-36237 is a special hydrophilic rubber-like polymer. However, since it is used, the method for producing the resin is complicated and the mechanical properties of the obtained resin are inferior.

The composition described in JP-A-60-170646 is intended to improve wear resistance.
The antistatic property is insufficient as an antistatic resin. Further, the composition described in JP-A-63-97653 is disadvantageous in cost because a relatively large amount of expensive polyamide elastomer is blended in order to achieve antistatic property as an antistatic resin.

On the other hand, the composition described in JP-A-2-7335 has a problem in water resistance since it uses a water-soluble thermoplastic polymer or a polyhydric alcohol compound. The present invention is intended to solve the problems in the above conventional examples, and an object thereof is to provide a styrene-based thermoplastic resin composition having a permanent antistatic property.

[0009]

The above object of the present invention is to: (A) a styrene type thermoplastic resin; (B) a polyether ester amide; and (C) a styrene sulfonic acid compound represented by the following formula (I).

[0010]

(Wherein R represents hydrogen, an alkyl group or an aryl group, X represents hydrogen alkali metal, alkaline earth metal or ammonium, and n represents an integer of 1 to 20000). The weight blending ratio (A) / (B) of (A) and component (B) is 10 to 99/90 to 1, and the blending amount of component (C) is that of component (A) and component (B). This is achieved by the thermoplastic resin composition being 0.01 to 50 parts by weight based on 100 parts by weight in total.

The present invention will be specifically described below. The styrene-based thermoplastic resin (A) in the present invention refers to a styrene polymer or copolymer having a styrene content of 50% by weight or more. Specific examples of the styrene-based thermoplastic resin include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-rubber polymer-acrylonitrile copolymer (ABS resin, AES resin, AAS resin, ACS resin), Examples thereof include styrene-modified polyphenylene ether resin, and two or more kinds of these can be used. Further, a part of styrene of the styrene-based thermoplastic resin is α-methylstyrene, p-methylstyrene, pt
-Butylstyrene can be substituted.

As a preferable styrene type thermoplastic resin,
They are polystyrene, rubber-modified polystyrene, and ABS resin. The polyether ester amide (B) in the present invention is a block copolymer composed of a hard component having a polyamide unit and a soft component having a polyether ester unit.

The monomer constituting the hard component of the polyether ester amide is preferably an 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, specifically, ω.
-Aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid, or caprolactam, enantolactam, capryllactam And lactams such as laurolatum and hexamethylenediamine-
Examples thereof include diamine-dicarboxylic acid salts such as adipic acid salts hexamethylenediamine-sebacic acid and hexamethylenediamine-isophthalic acid salt, with caprolactam, 12-aminododecanoic acid and hexamethylenediamine-adipic acid salt being particularly preferably used.

The polyether constituting the soft component of the polyether ester amide is preferably poly (alkylene oxide) glycol, specifically, polyethylene glycol, poly (1,2-propylene oxide) glycol, (1,3-propylene). Oxide, glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic property. The number average molecular weight of poly (alkylene oxide) glycol is 200 to 6000,
Particularly, those having a range of 250 to 4000 are used, and when the number average molecular weight is less than 200, the obtained polyether ester amide has poor mechanical properties, and when the number average molecular weight is more than 6000, the antistatic property is insufficient, which is preferable. Absent.

Further, the diol compound represented by the general formula (II) can be copolymerized within a range that does not impair the effects of the present invention.

[0017]

(In the formula, Ar represents an aromatic group having 6 to 20 carbon atoms and an alicyclic group, R ¹ and R ² represent an ethylene oxide group or a propylene oxide group, and m and n are 1 to 15 respectively. The diol compound represented by the above general formula (II) is represented by the following formula (I
II)-(V) and the halogen derivatives thereof are included.

[0019]

[0020]

[0021]

(Wherein R ¹ and R ² represent an ethylene oxide group or a propylene oxide group, Y represents a covalent bond, an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylidene group, an arylalkylidene group,
It represents O, SO, SO ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH. Further, m and n each represent an integer of 1 to 15. ) Specifically, preferred diol compounds are ethylene oxide adduct of hydroquinone, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of brominated bisphenol A, ethylene oxide adduct of bisphenol S, ethylene oxide adduct of dihydroxynaphthalene and its block weight. In particular, an ethylene oxide adduct of bisphenol A and a block polymer thereof are preferable.

The dicarboxylic acid connecting the polyether of the polyether ester amide and the polyamide is preferably a dicarboxylic acid having 4 to 20 carbon atoms, and specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6.
An aromatic dicarboxylic acid such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid) And the like. Particularly, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

The poly (alkylene oxide) glycol and the dicarboxylic acid theoretically react at a molar ratio of 1: 1, but the charging ratio is usually changed depending on the kind of the dicarboxylic acid used. Poly (alkylene oxide) glycol and dicarboxylic acid are 90 to 10 in polyetheresteramide.
It is used in the range of wt%, and when it exceeds 90 wt%, the mechanical properties of the polyetheresteramide are inferior, and when it is less than 10 wt%, the antistatic property of the obtained resin is inferior, which is not preferable.

The method for polymerizing the polyether ester amide is not particularly limited. For example, (a) (a) aminocarboxylic acid or lactam and (c) dicarboxylic acid are reacted to give a polyamide prepolymer having carboxylic acid groups at both ends. Make up,
A method of reacting this with (b) a poly (alkylene oxide) glycol and / or a diol compound under vacuum,
(B) The compounds (a), (b), and (c) are charged into a reaction tank and subjected to a pressure reaction at high temperature in the presence or absence of water to give a carboxylic acid-terminated polyamide prepolymer. A method of producing and then proceeding the polymerization under normal pressure or reduced pressure, and (c) Compounds of (a), (b), and (c) above are charged into a reaction vessel at the same time, melt-mixed, and then polymerized at once under high vacuum. You can use the method to proceed.

The polymerization catalyst is also not limited, and examples thereof include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate, and zirconate catalysts such as tetrabutyl zirconate. It is also possible to use one kind or two or more kinds. The styrenesulfonic acid compound (C) in the present invention is represented by the following formula (I).

[0027]

(Wherein R represents hydrogen, an alkyl group or an aryl group, X represents hydrogen alkali metal, alkaline earth metal or ammonium, and n represents an integer of 1 to 20000) Styrenic thermoplastic N is 1 to 20 in terms of compatibility with the resin.
00 is preferable, and more preferably 3 to 500.

Specific examples of styrene sulfonic acid compounds include sodium styrene sulfonate, sodium styrene sulfonate oligomer, sodium polystyrene sulfonate, potassium polystyrene sulfonate, lithium polystyrene sulfonate, ammonium polystyrene sulfonate, and poly α-styrene. Examples thereof include sodium sulfonate. Two or more of these may be used.

The styrene sulfonic acid compound also includes a copolymer obtained by copolymerizing these with a small amount of another copolymerizable monomer. Here, as the styrene sulfonic acid compound, sodium styrene sulfonate, ammonium polystyrene sulfonate and the like are particularly preferably used. The method for producing the styrene sulfonic acid compound is not particularly limited,
For example, a method of neutralizing a styrenesulfonic acid monomer obtained by a dehydrobromination reaction of bromoethylbenzenesulfonic acid with an alkali, a method of polymerizing the same under heating,
Polystyrene sulfonic acid obtained by reacting polystyrene with a sulfonating agent such as sulfuric anhydride and chlorosulfonic acid in a solvent is neutralized with an ionic alkali metal compound, an ionic alkaline earth metal compound or an ammonium compound. A commonly known method such as a method can be used.

The blending ratio of the (A) styrene type thermoplastic resin and the (B) polyether ester amide in the present invention is 99 to 10% by weight, preferably 97 to 20 of the (A) component.
% By weight, particularly preferably 95-60% by weight, component (B) is 1-90% by weight, preferably 3-80% by weight, particularly preferably 5-40% by weight. If the content of the polyether ester amide (B) is less than 1% by weight, the antistatic property of the resin composition will be insufficient, and if it exceeds 90% by weight, the resin composition will be flexible and the mechanical properties will be poor, such being undesirable. The addition amount of the (C) styrene sulfonic acid compound is 1 in total of (A) styrene-based thermoplastic resin and (B) polyether ester amide.
0.01 to 50 parts by weight, preferably 0.01 to 50 parts by weight,
0.05 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight. If the amount of the styrene sulfonic acid compound is less than 0.01 part by weight, the effect of improving the antistatic property is insufficient, and if it exceeds 50 parts by weight, the physical properties of the composition are deteriorated, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited. For example, a mixture of (A) a styrene-based thermoplastic resin, (B) a polyether ester amide and (C) a styrene sulfonic acid compound is used in a Banbury mixer,
It is made into a product by melt-kneading with a roll or an extruder. The resin composition of the present invention is another thermoplastic polymer such as vinyl chloride resin, polyolefin resin, polyamide, polybutylene terephthalate, polyethylene terephthalate, within a range that does not impair the object of the present invention.
By mixing with polycarbonate, polyphenylene sulfide, etc., the performance as a molding resin can be improved. Further, 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 or cationic surfactant, and further a compatibilizer such as an oligomer, if necessary, Various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, glass fibers, inorganic fillers, conductive agents and plasticizers, flame retardants and the like can also be added.

[0033]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below. The parts and% in the examples are parts by weight and% by weight, respectively. Reference Example (1) (A): Preparation of Styrenic Thermoplastic Resin A-1: A styrene monomer was heated to perform bulk polymerization to prepare polystyrene (A-1). A-2: 10 parts of Diene NF35A (manufactured by Asahi Kasei Corporation) was dissolved in 90 parts of styrene, and then bulk polymerization was performed to prepare a graft polymer (A-2). A-3: Polybutadiene latex (rubber particle size 0.25
80 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 20 parts (μ, gel content 80%) (solid content conversion).

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (A-3). A-4: Polybutadiene latex 1 used in A-3
Methyl methacrylate 7 in the presence of 0 parts (fixed amount equivalent)
After emulsion-polymerizing 90 parts of a monomer mixture consisting of 2%, styrene 24%, and acrylonitrile 4%, a powdery graft copolymer (A-4) was prepared in the same manner as A-3. (2) (B): Preparation of polyether ester amide B-1: 50 parts of caprolactam, number average molecular weight is 100
04.2 Polyethylene glycol 44.2 parts and terephthalic acid 7.6 parts "IRGANOX" 1098 (antioxidant)
After charging 0.2 parts and 0.1 part of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon stirring blade, nitrogen substitution, heating and stirring at 260 ° C. for 60 minutes to obtain a transparent homogeneous solution, and then 260 ° C. Polymerize for 4 hours under 0.5 mmHg or less,
A viscous and transparent polymer was obtained.

The polymer was discharged onto a cooling belt in a gut form and pelletized to prepare a pelletized polyether ester amide (B-1). (B-
The polyetherester unit in 1) was 45% by weight. B-2: 40 parts of nylon 6.6 salt (AH salt), ethylene oxide adduct of bisphenol A (“New Ball”)
BPE-20, manufactured by Sanyo Kasei Co., Ltd., 6.3 parts, polyethylene glycol 41.9 parts having a number average molecular weight of 1000, and dodecadioic acid 14.3 parts are added to "Irganox" 1098
0.2 parts and antimony trioxide 0.02 parts were charged into the reaction vessel used in A-1, the atmosphere was replaced with nitrogen, the mixture was heated and stirred at 260 ° C. for 60 minutes to obtain a transparent homogeneous solution, and the pressure was reduced to 500 mmHg. Water in the gas phase of the reaction vessel was removed, and 0.08 part of tetrabutyl zirconate was added. Then 260 ℃, 0.5mm
Polymerization was performed for 3 hours and 30 minutes under a condition of Hg or less to obtain a viscous and transparent polymer. Thereafter, the polyether ester amide (B-2) was prepared in the same manner as in B-1. The polyether ester unit in (B-2) was 40% by weight. B-3: 30 parts of ω-aminodecanoic acid, dodecanoic acid 14.2
Parts and 58.6 parts of polyethylene glycol having a number average molecular weight of 1000 were used to prepare a polyetheresteramide (B-3) in the same manner as in (B-1) except that the polymerization time was 3 hours. The polyether ester unit in (B-3) was 60% by weight. (3) Preparation of (C) Styrene Sulfonic Acid Compound C-1: Sodium styrene sulfonate is dissolved in water and heated at 50 ° C. using potassium persulfate as a catalyst, and solution polymerization is carried out to obtain sodium polystyrene sulfonate (C). -1) was prepared. C-2: Using ammonium styrene sulfonate (C
Ammonium polystyrene sulfonate (C-2) was prepared in the same manner as in -1). Examples 1 to 6 (A) Styrenic thermoplastic resin prepared in Reference Example,
(B) polyether ester amide and (C) styrene sulfonic acid compound were mixed in the compounding ratio shown in Table 1, and melt-kneaded at a resin temperature of 220 ° C. in a vented 40 mmφ extruder.
Pellets were produced by carrying out extrusion.

Then, using an injection molding machine, a test piece was molded at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C., and its physical properties were measured. The surface specific resistance value was measured under the following conditions using a 2 mm thick disc that was injection molded (1) Immediately after molding, it was measured in an absolutely dry state. (2) Immediately after molding, washing with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Oil and Fats Co., Ltd.), followed by thorough washing with distilled water to remove surface moisture, and then adjusting at 50% RH and 23 ° C. for 24 hours. Wet and measured. (3) After molding, leave it in 50% HR, 23 ° C. for 200 days, then wash with an aqueous solution of a detergent “Mama Lemon”, and then sufficiently wash with distilled water to remove water from the surface.
The humidity was measured at 0% RH and 23 ° C. for 24 hours.

The measurement results are shown in Table 2. Comparative Examples 1 to 4 (A) Styrenic thermoplastic resin prepared in Reference Example,
The (B) polyether ester amide and the (C) styrene sulfonic acid compound were melt-kneaded and molded at the compounding ratios shown in Table 1 in the same manner as in Examples, and the physical properties were measured. The measurement results are shown in Table 2.

[0038]

[0039]

From the results shown in Table 2, the following is clear.
The resin compositions of the present invention (Examples 1 to 6) all have excellent appearance of molded articles and have low surface resistivity values.
Moreover, the resistance value hardly changes even when the surface is washed or changes with time, and excellent permanent antistatic property is exhibited. on the other hand,
(A) Styrene-based thermoplastic resin and (C) Styrene sulfonic acid compound resin molded product (Comparative Example 1) and (A) Styrene-based thermoplastic resin and (B) polyether ester amide resin molded product (Comparison In Example 2), the antistatic properties in all cases are inferior, and it is clear that it is essential to add two components of (B) polyether ester amide and (C) styrene sulfonic acid compound in combination.

When the blending amount of the (B) polyether ester amide is less than 1 part by weight (Comparative Example 3), the antistatic property (resistance value) is poor, and the (B) polyether ester amide is 9 parts.
If it exceeds 0 parts by weight (Comparative Example 4), the molded product becomes flexible and the mechanical properties are poor. When the amount of the styrene sulfonic acid compound (C) is less than 0.01 parts by weight (Comparative Example 5), the effect of improving the antistatic property is insufficient, and the antistatic property (resistance value) is particularly poor during absolutely dry conditions, which is a desirable resin composition. Can't get (C)
When the amount of the styrene sulfonic acid compound exceeds 50 parts by weight (Comparative Example 6), mechanical properties are deteriorated, which is not preferable.

[0042]

As can be seen from the examples, according to the present invention, a thermoplastic resin composition excellent in permanent antistatic property can be obtained.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical display location C08L 55/02 LME 7142-4J LMF 7142-4J 77/12 LQS 9286-4J LQY 9286-4J C09K 3/16 102 B 6917-4H // (C08L 25/02 25:18 77:12) (C08L 55/02 77:12 25:18)

Claims (1)

[Claims] 1. A styrene thermoplastic resin (A), a polyether ester amide (B), and a styrene sulfonic acid compound (C) represented by the following formula (I). (In the formula, R represents hydrogen, an alkyl group or an aryl group, X represents hydrogen alkali metal, alkaline earth metal or ammonium, and n represents an integer of 1 to 20000), and the component (A). And the component (B) have a weight ratio (A) / (B) of 10 to 99/90 to 1, and the amount of the component (C) is 100 weights of the total of the component (A) and the component (B). The thermoplastic resin composition is 0.01 to 50 parts by weight based on parts.