JPH0680138B2 - Antistatic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antistatic resin composition having a permanent antistatic property and having excellent mechanical properties represented by impact resistance.

[Conventional technology]

Synthetic polymeric materials are used in a wide range of fields because of their excellent properties. If these materials are provided with antistatic properties in addition to the mechanical strength of the materials, their applications can be further expanded. In other words, the application can be expanded to a copying machine, various dustproof parts, etc., which are desired 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 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 vinylidene monomer (JP-A-55-36237)
No.), etc., and has achieved practical antistatic properties.

[Problems to be solved by the invention]

However, since these antistatic resins use a special hydrophilic rubber-like polymer, there is a drawback that the production method is complicated, and the mechanical properties of the obtained resin are inferior. Absent.

The present inventors have conducted intensive studies for the purpose of providing an antistatic resin having permanent antistatic properties and excellent in mechanical properties represented by impact resistance, and as a result, a specific polyether ester amide was obtained. The inventors have found that the above object can be efficiently achieved by mixing a graft copolymer obtained by graft-polymerizing a specific vinyl-based monomer with a rubber-like polymer.

[Means for solving problems]

That is, the present invention provides (A) (a) an aminocarboxylic acid having 6 or more carbon atoms or a lactam, or 6 carbon atoms.
Polyether ester amide composed of the above diamine and dicarboxylic acid salt, (b) poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6000, and (c) a dicarboxylic acid having 4 to 20 carbon atoms, and a polyether 95 to 35% by weight of (meth) acrylic acid ester monomer in the presence of 5 to 80 parts by weight of polyether ester amide having an ester unit of 95 to 10% by weight and (B) 5 to 80 parts by weight of rubbery polymer. 95 to 20 parts by weight of a monomer or monomer mixture selected from 5 to 50% by weight of an aromatic vinyl monomer and 0 to 60% by weight of another vinyl monomer copolymerizable therewith. 2 to 95 parts by weight of polymerized graft copolymer and 100 to 40% by weight of (C) (meth) acrylic acid ester monomer and / or aromatic vinyl monomer and 0 to 40 vinyl cyanide monomer Monomer selected from wt% Others obtained by polymerizing a monomer mixture (co) polymer 0 to 90 parts by weight (A) +
(B) + (C) is blended so as to be 100 parts by weight, and is blended so that the amount of the rubbery polymer in the whole is 1-30% by weight. .

Hereinafter, the present invention will be specifically described.

The composition of the present invention comprises (A) a polyether ester amide (B) graft copolymer and (C) a vinyl monomer copolymer.

(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, enanthlactam, capryllactam and laurolactam Lactams and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, especially caprolactam, 12-aminododecanoic acid or hexamethylenediamine. -Adipate is preferably used.

Examples of the (b) poly (alkylene oxide) glycol, which is a constituent component of the polyether ester amide (A), include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (1,3-propylene oxide) glycol. (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 are used. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic property. Number average molecular weight of poly (alkylene oxide) glycol 200
~ 6,000 especially used in the range of 250-2,000, the number average molecular weight is less than 200 mechanical properties of the obtained polyetheresteramide is inferior, if the number average molecular weight exceeds 6,000, antistatic property is insufficient, it is preferable. Absent.

Examples of the dicarboxylic acid having 4 to 20 carbon atoms (c) which is a constituent component of the polyether ester amide (A) 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, Alicyclic dicarboxylic acids such as 1,2-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, sebacic acid, adipic acid and dodecanedioic acid, which are preferably used from the viewpoint of polymerizability, color tone and physical properties.

The polymerization method of (A) polyether ester amide is not particularly limited. For example, (a) (a) aminocarboxylic acid or lactam and (c) dicarboxylic acid are reacted at about an equimolar ratio to form carboxylic acid groups at both ends. Polyamide prepolymer of (b) poly (alkylene oxide)
Method of reacting glycol under vacuum (b) Charge each of the compounds (a), (b) and (c) into a reaction tank,
A method of producing a carboxylic acid-terminated polyamide prepolymer by pressure-reacting at high temperature in the presence or absence of water, and then proceeding the polymerization under normal pressure or reduced pressure, and (c) above (a), ( A known method such as a method in which the compounds b) and (c) are simultaneously charged into a reaction tank and melt-mixed and then the polymerization is carried out all at once under a high vacuum can be used.

The rubbery polymer that is a constituent of the (B) graft copolymer used in the present invention has a glass transition temperature of 0 ° C.
The following are preferable, specifically, polybutadiene, polystyrene-butadiene, polyacrylonitrile-butadiene and other diene rubbers, polyisoprene, polychloroprene, polybutyl acrylate and other acrylic rubbers and ethylene-propylene-diene. Rubbery polymers such as monomeric terpolymers can be used. Polybutadiene or a butadiene copolymer is particularly preferable.

Examples of the (meth) acrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl acrylate and the like, but methyl methacrylate is particularly preferable.

Aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, o-ethylenestyrene, o-
Examples thereof include p-dichlorostyrene, and styrene is particularly preferable.

Other vinyl-based monomers copolymerizable with them include vinyl cyanide-based monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile, maleimide, N.
Examples thereof include maleimide-based monomers such as -methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide, but acrylonitrile is particularly preferable.

Further, (B) the graft copolymer comprises 5 to 80 parts by weight of a rubbery polymer, preferably 10 to 60 parts by weight, and 95 to 20% by weight of a (meth) acrylic acid ester monomer, and an aromatic vinyl monomer 1. ~ 50
95% to 20 parts by weight, preferably 90 to 40 parts by weight of a monomer or monomer mixture selected from the range of 0% to 60% by weight and other vinyl monomers copolymerizable therewith. Polymerization method of, for example, a method of emulsion-grafting polymerization by continuously supplying the monomer or monomer mixture and the polymerization initiator in the above proportions in the presence of the rubbery polymer latex. .

The composition ratio of the monomers in this polymerization is 95 to 35% by weight of (meth) acrylic acid ester monomer, preferably 90 to 40% by weight, 5 to 50% by weight of aromatic vinyl monomer, and preferably 5%.
~ 45% by weight. When the content of the (meth) acrylic acid ester monomer is more than 95% by weight, the impact resistance of the obtained resin composition is poor, and when it is less than 35% by weight, the affinity with the polyether ester amide is poor and the layered peeling is caused. It is not preferable because it causes the appearance of the molded product to be lost.

Examples of the (meth) acrylic acid ester monomer which is a constituent component of the (C) copolymer used in the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate and methyl acrylate. Is preferred.

Aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, pt
-Butyl styrene, o-ethyl styrene, op-chloro styrene and the like can be mentioned, but styrene and α-methyl styrene are particularly preferable.

Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile, with acrylonitrile being particularly preferred.

Further, the (C) copolymer is a (meth) acrylic acid ester monomer and / or an aromatic vinyl monomer 60 to 100% by weight.
Further, a monomer or a mixture of monomers selected from the range of 0 to 40% by weight of vinyl cyanide-based monomer can be obtained by a known polymerization method.

The composition ratio of the monomers in this polymerization is 60 to 100 parts by weight, preferably 65 to 100 parts by weight, based on the total monomers used for the (meth) acrylic acid ester monomer and / or the aromatic vinyl monomer. % By weight. The ratio of the (meth) acrylic acid ester monomer and / or the aromatic vinyl monomer is 60.
If the proportion of vinyl cyanide monomer is less than 40% by weight, the compatibility with the polyether ester amide and the graft copolymer will be poor and sufficient impact strength will not be obtained, and the color tone of the molded product will not be obtained. And the appearance is not good, which is not preferable.

The resin composition of the present invention is 5 to 80 parts by weight of the thus obtained (A) polyether ester amide, particularly preferably 5
To 60 parts by weight of (B) the graft copolymer is 2 to 95 parts by weight, particularly preferably 5 to 80 parts by weight and (C) the copolymer of 0 to 90 parts by weight, particularly preferably 0 to 80 parts by weight. And (A), (B) and (C) are added in a proportion of 100 parts by weight.

If the amount of the polyether ester amide (A) is less than 5 parts by weight, the antistatic property of the resin composition will be insufficient, and if it exceeds 80 parts by weight, the resin composition will be soft and the mechanical properties will be poor, such being undesirable.

Further, if the content of the (B) graft copolymer is less than 2 parts by weight, the impact resistance of the resin composition will be poor, and if it exceeds 95 parts by weight, the antistatic property and mechanical properties of the resin composition will be poor, such being undesirable.

Further, the amount of the rubbery polymer in the resin composition is 1 to 30.
If the amount is less than 1% by weight, the impact resistance of the resin composition is poor, and if it exceeds 30% by weight, the resin composition becomes soft and unusable.

There is no particular limitation on the method for producing the resin composition of the present invention, but for example, a (B) graft copolymer and (C) copolymer may be prepared from (A) polyether ester amide with a Banbury mixer, roll, extruder or the like. It is made into a product by kneading.

The resin composition of the present invention is mixed with another thermoplastic polymer compatible with the resin composition of the present invention, such as polyamide, polybutylene terephthalate, polyethylene terephthalate, or polycarbonate, to improve the performance as a molding resin. can do.

It is also possible to further improve the antistatic property by adding an antistatic agent such as an anionic or cationic surfactant, and if necessary, various stabilizers such as an antioxidant and an ultraviolet absorber. Pigments, dyes, lubricants and plasticizers can also be added.

[Action]

In the present invention, the resin in which a graft copolymer obtained by graft-polymerizing a mixture of a polyether ester amide and a predominant amount of a (meth) acrylic acid ester monomer and an aromatic vinyl monomer has a permanent antistatic property. And exhibits high mechanical properties. This phenomenon is caused by grafting a specific amount of (meth) acrylic acid ester monomer and aromatic vinyl-based monomer to a rubbery polymer having no affinity with polyether ester amide, thereby grafting with polyether ester amide. It is presumed that this is an effect of increasing the affinity with the copolymer.

〔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 Tensile strength ASTM D638 Flexural modulus ASTM D790 Volume specific resistance value: 2 ^t × 40 ^φ disk, room temperature 23 ° C, humidity
It was measured in a 50% RH atmosphere. A super insulation resistance meter SM-10 type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

The appearance of the molded product was evaluated by visually observing the test piece, and ⊚-extremely good appearance, ◯ -good, × -the surface of the molded product was damaged and the defect was used as a criterion.

Further, the parts and% in the examples mean parts by weight and% by weight.

Reference Example (1) Preparation of (A) Polyether Esteramide A-1: 40 parts of aminododecanoic acid, 48.3 parts of polyethylene glycol having a number average molecular weight of 2000 and 11.7 parts of adipic acid were added to “Irganox” 1098 (antioxidant). Charge to a reaction vessel equipped with a helical ribbon stirring blade together with 0.2 part and 0.05 part of tetrabutyl titanate catalyst.
After heating and stirring for 0 minutes to form a transparent homogeneous solution, 260 ° C at 0.
Polymerization was performed for 6 hours under conditions of 5 mmHg or less to obtain a viscous colorless transparent polymer. A pellet-shaped polyether ester amide (A-1) was prepared by discharging the polymer in a gut shape onto a cooling belt and pelletizing.

A-2: Nylon 6.6 salt (AH salt) 20 parts, number average molecular weight 600
Polyethylene glycol 69.8 parts and adipic acid 10.2
Parts were used to prepare a polyetheresteramide (A-2) by the same method as in (A-1) except that the polymerization time was 4 hours.

A-3: Polyetheresteramide in the same manner as in (A-1) except that 30 parts of ω-aminodecanoic acid, 19.4 parts of dodecanedioic acid and 50.6 parts of polyethylene glycol having a number average molecular weight of 1000 were used, and the polymerization time was 5 hours. (A-3) was prepared.

(2) Preparation of (B) graft copolymer B-1: Polybutadiene latex (manufactured by Toray Industries, Inc., particle size)
Graft copolymer by emulsion polymerization of 70 parts of a monomer mixture consisting of 75% methyl methacrylate, 21% styrene and 4% acrylonitrile in the presence of 0.36μ, gel content 90%) and 30 parts (solid content conversion). (B-1) was prepared.

B-2: Graft copolymer by emulsion-polymerizing a monomer mixture consisting of 90% of methyl methacrylate and 10% of styrene in the presence of 50 parts (solid content) of polybutadiene latex used in B-1 ( B-2) was prepared.

B-3: Monomer mixture composed of 35% styrene, 30% N-phenylmaleimide and 35% acrylonitrile in the presence of 40 parts (as solid content) of the polybutadiene latex used in B-1.
Emulsion polymerization of 60 parts was performed to prepare a graft copolymer (B-3).

B-4: Graft copolymer (B-4) was prepared by emulsion polymerization of 10 parts of methyl methacrylate in the presence of 90 parts of polybutadiene latex used in B-1 (solid content conversion).

(3) Preparation of (C) Copolymer C-1: Copolymer (C-1) was prepared by copolymerizing 80 parts of methyl methacrylate and 20 parts of styrene.

C-2: Methyl methacrylate was polymerized to prepare (C-2).

C-3: 76 parts of styrene and 24 parts of acrylonitrile were copolymerized to prepare a copolymer (C-3).

C-4: 55 parts of styrene and 45 parts of acrylonitrile were copolymerized to prepare a copolymer (C-4).

Example 1 (A) Polyether ester amide prepared in Reference Example, (B) graft copolymer and (C) copolymer were mixed at the compounding ratio shown in Table 1, and the resin was mixed with a vented 40 mmφ extruder. Pellets were produced by melt-kneading and extruding at a temperature of 220 ° C. Then, an injection molding machine was used to mold a test piece at a cylinder temperature of 220 ° 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, detergent Mama Lemon (Lion Yushi Co., Ltd.)
The product was washed with an aqueous solution, then thoroughly washed with distilled water, to remove surface water, and then conditioned at 50% RH and 23 ° C. for 24 hours for measurement.

(2) After molding, leave it in 50% RH, 23 ℃ for 200 days,
Detergent Mama Washed with lemon aqueous solution, then thoroughly washed with distilled water to remove surface moisture, then 50% RH, 23 ° C for 24 hours
The humidity was measured with time.

The measurement results are shown in Table 1.

Comparative Example 1 (A) Polyether ester amide prepared in Reference Example was mixed with (B) graft copolymer and (C) copolymer at the compounding ratio shown in Table 1, and the same method as in Example 1 was conducted. Each physical property was measured. Further, (A) polyether ester amide,
The physical properties of the (B) graft copolymer and the (C) copolymer alone were measured in the same manner. The results are also shown in Table 1.

The following is clear from the results of Table 1. The resin compositions (No. 1 to No. 8) of the present invention all have excellent mechanical properties typified by tensile strength at break, flexural modulus and impact strength,
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. The appearance of the molded product is also very good.

That is, the resin composition of the present invention is a composition having both excellent mechanical properties and permanent antistatic properties, and a molded product having an extremely good appearance.

On the other hand, the amount of polyether ester amide (A) is 5
When it is less than 10 parts by weight (No. 9), the antistatic property (resistance value) is inferior, and when it is more than 80 parts by weight (No. 10, 16, 17), tensile breaking strength and bending Poor elastic modulus.

When the graft copolymer (B) in which the ratio of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer is less than 40% by weight is used (No. 11), the impact strength is inferior and the molded product is Looks bad. When the graft copolymer (B) in which the proportion of the rubbery polymer exceeds 80 parts by weight is used (NO.12), the dispersion of the graft copolymer is poor and the surface of the molded article is damaged, which is not preferable. Further, when the graft copolymer (B) is not included (No. 13), the impact strength is poor, and when the graft copolymer (B) exceeds 95 parts by weight (No. 14), the antistatic property is poor.

Graft copolymer (B) containing less than 40% by weight of (meth) acrylic acid ester monomer and aromatic vinyl monomer, and (meth) acrylic acid ester monomer and / or aromatic vinyl monomer. Even if a copolymer (C) having a proportion of a monomer of less than 60% by weight is mixed with a polyether ester amide (A), the impact strength is inferior, and the appearance of a molded article is impaired to obtain a desirable resin composition. I can't. Resin composition containing no polyether ester amide (A) (No. 18 to 2)
0) is not preferable because it has a high resistance value and inferior antistatic property.

〔The invention's effect〕

The composition of the present invention has excellent antistatic property as well as mechanical properties, particularly impact resistance and flexural modulus.

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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.
A polyether ester amide composed of 6000 to 6000 poly (alkylene oxide) glycol and (c) a dicarboxylic acid having 4 to 20 carbon atoms, wherein the polyether ester unit is 95 to 10% by weight. In the presence of 80 parts by weight and (B) 5 to 80 parts by weight of a rubbery polymer, 95 to 35% by weight of a (meth) acrylic acid ester monomer,
Polymerize 95 to 20 parts by weight of a monomer or a monomer mixture selected from 5 to 50% by weight of an aromatic vinyl monomer and 0 to 60% by weight of another vinyl monomer copolymerizable therewith. 2 to 95 parts by weight of the graft copolymer and 100 to 40% by weight of the (C) (meth) acrylic acid ester monomer and / or the aromatic vinyl monomer and the vinyl cyanide monomer 0 to 40
(A) + (B) + 0 to 90 parts by weight of a (co) polymer obtained by polymerizing a monomer or a mixture of monomers selected from the weight percent.
An antistatic resin composition, which is blended so that (C) is 100 parts by weight and the amount of the rubbery polymer is 1 to 30% by weight based on the whole.