JPS62116652A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title resin compsn. having permanent antistatic properties and excellent impact resistance, etc. and suitable for use in the field of duplicators, etc., containing a polymether-ester-amide and a specified graft copolymer contg. a rubbery polymer as essential components. CONSTITUTION:The titled resin compsn. having a rubbery polymer content of 1-40wt% contains 1-90pts.wt. polyether-ester-amide (A) having a polyether- ester unit content of 95-10wt%, composed of a 6C or higher amino carboxylic acid or lactam or a salt of a 6C or higher diamine and a dicarboxylic acid, a poly(alkylane oxide) glycol having a number-average MW of 200-6,000 and a 4-20C dicarboxylic acid and 99$2pts.wt. graft polymer (B) obtd. by grafting 95-20pts.wt. monomer mixture of 40-90wt% arom. vinyl monomer amd 60-10wt% vinyl cyanide monomer onto 5-80pts.wt. rubbery polymer as essential components.

Description

[Detailed Description of the Invention] [Field of Industrial Application] Is the present invention permanent? The present invention relates to an antistatic resin composition that has anti-J71 properties and is excellent in mechanical customization as typified by impact resistance.

[Conventional technology]

Synthetic polymeric materials are used in a wide variety of fields due to their immediate properties. The applications of these materials can be further expanded if they are added to the mechanical strength of the material and are provided with temperature band prevention properties. In other words, it is possible to expand the application to copying machines, various dustproof parts, etc. where it is desired to prevent troubles caused by cold air.

One way to improve the antistatic properties of synthetic polymer materials is to use a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and acrylic ester with a vinyl monomer having an alkylene oxide group. A method obtained by graft polymerizing vinyl monomers or vinylidene monomers (Japanese Patent Application Laid-Open No. 55-3
No. 6237, etc., have achieved practical antistatic properties.

A method of obtaining an antistatic resin by mixing an amide elastomer is disclosed in Japanese Patent Application Laid-Open No. 60-23435, and by mixing a modified vinyl polymer containing a carboxy)V group with an amide elastomer, a semi-permanent resin can be obtained. It is disclosed that a resin having excellent antistatic properties can be obtained.

In addition, as a composition similar to the constituent components of the present invention, there is a composition prepared by blending a styrene resin e and a polyamide elastomer disclosed in JP-A-60-170646. Improving sex.

JP-A No. 60-170646 aims to improve the Lf wear resistance of styrene cold resin, and the composition of the present study of a specific polyamide elastomer and ABS resin polymer has the following properties:
There is no description or suggestion regarding the existence of permanent antistatic properties.

[Problem that the invention seeks to solve]

The antistatic resin obtained by graft polymerizing a monomer onto a hydrophilic rubbery polymer uses a special hydrophilic rubbery polymer, so the manufacturing method is complicated, and the resulting resin It has the disadvantage of poor mechanical properties and is not fully satisfactory.

The present inventors have conducted extensive studies with the aim of providing an antistatic resin that has permanent antistatic properties and excellent mechanical properties such as impact resistance! Is it possible to mix a graft copolymer obtained by graft polymerizing a specific vinyl monomer with a specific polyether ester amide and a rubbery polymer? From this, the inventors have found that the above object can be efficiently achieved and have arrived at the present invention.

[Means for solving problems]

In other words, the present invention! A) fal aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of cyamine and dicarboxylic acid having 6 or more carbon atoms, (b) number average molecular weight 200-60
Bore ether ester amide composed of 00 poly (alkynon oxide) glycol and (cl dicarboxylic acid having 4 to 20 carbon atoms), containing 95 to 10% by weight of polyether ester units. ]iii and Bl (a) Rubbery polymer 5 l8 0 Monomer mixture consisting of 40 to 90% by weight of vinyl monomer and 60 to 10% by weight of vinyl cyanide monomer 95 to 2
Graft copolymer 99 obtained by graft polymerizing 0 parts by weight
~2 parts by weight and icl aromatic vinyl monomer 40-90 weight XJk%
, 60-10% by weight of vinyl cyanide spinning wheel and 0-40% of other vinyl monomer copolymerizable therewith. ! Ii
A copolymer obtained by polymerizing a monomer mixture consisting of %
This is a P-cho plastic degreasing composition consisting of 97 parts by weight and containing 7 to 40% by weight of a rubbery polymer (aluminium).

The present invention will be specifically explained below.

The composition of the present invention comprises N polyetheresteramide, 0
31 graft copolymer and C) vinyl spinning wheel consists of a copolymer.

It is a constituent component of the N polyether ester amide in Rikoo of the present invention (al aminocarbon having 6 or more carbon atoms)
Or as salts of lactams or diamines having 6 or more carbon atoms and dicarboxylic acids, ω-aminocaproic acid, ω-aminoenanthanoic acid, ω-aminecagrilic acid, ω-aminopergone, ω-aminecapric acid and 11-aminoundecanoic acid, 12-7minododecane Aminocarboxylic acids such as acids or caprolactam, enantlactam,
Lactams such as capryllactam and laurolactam and xamethylene diamine-adipate, hexamethylene diamine-sebacin J salt and hexamethylene diamine-adipate
Salts of diamine-dicarboxylic acids such as diamine-isophthalate are used, especially caprolactam.

12-7 minododecane, hexamethylenediamine-
Adipates are preferably used.

(A salt of 7-minocarboxylic carbon having 6 or more carbon atoms or lactam or diamine having 6 or more carbon atoms and dicarbonate is a constituent unit of polyether ester amide with 5 to
It is preferable to use the polyether ester amide in a range of 90% by weight; if it is less than 5% by weight, the mechanical properties of the polyether ester amide are poor;
If it exceeds 20%, the antistatic properties of the obtained monosodium will be poor, which is not preferable.

■Poly (alkylene oxide) glycol, which is a constituent component of polyether ester amide, includes polyethylene glycol, poly (1゜2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol.

Poly(hexamethylene oxide) glycol, Glock or random copolymers of ethylene oxide and propylene oxide, and block or random copolymers of ethylene oxide and tetrahydrofuran are used. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of poly(alkylene oxide) glycol is 200~
6. OOO especially 250~2. OOO, and if the number average molecular weight is less than 200, the mechanical properties of the resulting polyether ester amide will be poor, and if the number average molecular weight exceeds 6.000, the antistatic properties will be insufficient, which is not preferred.

Constituent components of N polyether ester amide (C)
Examples of dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid A/#, phthalic acid, and naphthalene-2,6-
Aromatic dicarboxylic acids such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexane dicarboxylic acid, l , 2-cyclohexanedicarboxylic acid and dicyclohexy/L7-4.

Examples include alicyclic dicarboxylic acids such as 4'-dicarboxylic acid and aliphatic dicarboxylic acids such as succinic acid, nylic acid, ampic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid), in particular terephthalic acid, isophthalic acid, 1.4-Cyclohexanedicarboxylic acid, sepasine, ampic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

(bl poly (alkylene oxide) glycol and tc
The dicarboxylic acid is reacted at a molar ratio of 1:1, but it is usually supplied at a different charging ratio than the dicarboxylic acid to be used.

(2) Polymerization method of polyether ester amide (t) There are no limitations in this respect, and for example, (i) (a) aminocarbon or lactam is reacted with (Cl dicarbonate) to form a polyamide having carboxylic acid groups at both ends. A method of making a prepolymer and reacting it with poly(alkylene oxide) glycol under vacuum (b) The above (al, f)
bl, (C1) is charged into a reaction tank and reacted under pressure at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then polymerized under normal pressure or reduced pressure. A known method can be used, such as (g) charging the above compounds of tal, (bl, and FC+) simultaneously into a reaction tank, melting and mixing them, and then proceeding with polymerization all at once under high vacuum.

The rubbery polymer (a) which is a constituent component of B) the graft copolymer used in the present invention has a glass transition temperature of 0.
℃ or less, specifically polybutadiene, polystyrene-butadiene, polyacrylonitrile-
Diene thread rubber such as butadiene, acrylic rubber such as polyisoprene, polychloroprene, polybutyl acrylate, etc. Rubbery polymers such as ε-yohyethylene-propylene-diene monomer terpolymer can be used.

Particularly preferred are butadiene or butadiene copolymers.

+bl aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 0-ethylstyrene,
Examples include 0-p-dichlorostyrene, with styrene being particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and acrylonitrile is particularly preferred.

In addition, (B) the graft copolymer is (a) rubbery polymer 5-
80 parts by weight, preferably 10-60 parts by weight, 40-90% by weight, preferably 50-85% by weight of aromatic vinyl monomer, and 60-10% by weight, preferably 50% by weight of vinyl cyanide monomer. Single mass mixture 95-2 consisting of ~15% by weight
0 parts by weight.

Preferably, 90 to 40 layers are emulsified by a known method, for example, by continuously supplying the above-mentioned proportions of a polymeric mixture and a polymerization initiator in the presence of a rubbery polymer latex. It can be obtained by a method such as graft polymerization.

The proportion of the (Al rubbery polymer) in this (81 graft copolymer) is 5 to 80 parts by weight, preferably 1 to 60 parts by weight, and if it is less than 5i parts, the resulting resin will have poor impact resistance. If the amount exceeds 80 parts by weight, the rubbery polymer will be poorly dispersed and the appearance of the molded product will be impaired, so it cannot be used.

In addition, the composition ratio of vinyl monomers needs to be 10 to 60% by weight of vinyl cyanide monomers based on the total monomers,
Preferably it is 15 to 50% by weight. If the proportion of the vinyl cyanide monomer is less than 10% by weight, the resulting resin will have poor impact resistance, which is not preferred. Moreover, if it exceeds 60% by weight, the stability of the graft copolymer will be significantly reduced, resulting in a molded product with poor color tone, which is not preferable.

Aromatic vinyl monomers that are constituent components of C) copolymer used in the present invention include styrene, α-methylstyrene, vinylocitoluene% p-methylstyrene, p-t
Examples include -butylstyrene, 0-ethylstyrene, and 0-p-chlorostyrene, with styrene and α-methylstyrene being particularly preferred.

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

Other vinyl monomers that can be copolymerized with these include (meth)acrylic acid ester monomers such as methyl, ethyl, propyl, n-butyl, and i-butyl, maleimide, Examples include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide monomers, acrylamide, and the like.

However, α, β unsaturated carboxylic acids and α, β unsaturated dicarboxylic acids are excluded. Copolymerization of a, β-unsaturated carboxylic acid, etc. is not preferable because it is reactive with polyether ester amide, resulting in poor antistatic properties and inability to obtain desired physical properties with good reproducibility.

(b) The proportion of the cyanated vinyl spinning wheel body, which is a constituent component of the copolymer, should be 10 to 60% by weight, preferably 15 to 50% by weight, based on the total monomers. If the proportion of the vinyl cyanide monomer is less than 10% by weight, the resulting resin will have poor impact resistance, which is not preferred. Moreover, if it exceeds 60% by weight, the thermal stability of the copolymer will be significantly reduced, resulting in a molded article with poor color tone, which is not preferable.

The thus obtained polymer is composed of (3) polyether ester amide l~9o heavy B part B) graft copolymer 99~
2 parts by weight and C) copolymer 0 to 1 part by weight,
A rubbery polymer is added in an amount of 7 to 40% by weight.

If the amount of polyether ester amide is less than 1 part by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 90 parts by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferred.

In addition, the sum of ta+g of the rubbery polymer in the resin composition is 4
If it exceeds 0%, the resin composition will become soft and the mechanical properties will be poor, which is not preferable.

(a) If the λ content of the rubbery polymer is less than 7% by weight, the resulting resin will have poor impact resistance, which is not preferred.

There are no particular limitations on the method for producing the resin composition of the present invention, and for example, the mixture of N polyether ester amide and (8) graft copolymer and/or C) copolymer may be prepared using a Banbury mixer, a roll, an extruder, etc. It is made into a product by melting and kneading it.

The resin composition of the present invention can be prepared by mixing other thermoplastic polymers compatible with the resin composition of the present invention, such as polyamide, polybutylene terephthalate, polybutylene terephthalate, polycarbonate, etc., to improve its performance as a molding resin. It can be improved. It is also possible to further improve antistatic properties by adding antistatic agents such as metal salts of sulfonic acids, anionic or cationic surfactants, and oxidation resistance can be further improved as needed. Various stabilizers such as inhibitors and ultraviolet absorbers, pigments, dyes, lubricants, and plasticizers may also be added.

[Effect]

In the present invention, the resin that uses a specific polyether ester amide in combination with a graft copolymer obtained by graft polymerizing a vinyl monomer mixture containing a vinyl cyanide monomer has permanent antistatic properties and has high mechanical strength. Demonstrate the characteristics of

This phenomenon can be achieved by grafting a rubbery polymer P-cyanated vinyl monomer that has no affinity with a specific polyetheresteramide that has antistatic properties. This is presumed to be an effect of increasing affinity.

〔Example〕

In order to explain the present invention more specifically, the present invention will be described below with reference to Examples and Comparative Examples. The finally obtained resin composition was molded by injection molding and then tested using the following test method. Various physical properties were measured from this.

Izotsu impact strength ASTM D256-56
A Tensile strength ASTM 0638 Flexural modulus ASTM D790 Volume resistivity: 2”X
The measurement was performed using a 40φ disc at a room temperature of 23° C. and a humidity of 50% R)I atmosphere. A super insulation resistance meter S+vl-10 manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

The appearance of the molded product was determined by visual inspection of the test piece, and the appearance was ◎ to extremely good.

The criteria for evaluation were ○: Good, and X: The surface of the molded product was damaged and was defective.

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

Reference example (1) (Preparation A of At polyether ester amide
-1: 40 parts of caprolactam, number average molecular weight is 2000
56.9 parts of polyethylene glycol and 4.4 parts of adipic acid were charged together with 0.2 parts of 11 Irganox I + 1098 (antioxidant) and 0.1 part of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon pill.
The mixture was replaced four times and heated and stirred at 240°C for 40 minutes to obtain a transparent homogeneous solution, and then polymerized at 260°C for 6 hours at 0.5 mg or less to obtain a viscous and transparent polymer. Pelletized polyether ester amide (A-1) was prepared by discharging the polymer onto a cooling belt and pelletizing it.

A-2: Except that 60 parts of nylon 6.6 salt (AH salt), 33.8 parts of polyethylene glyco-tv with 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 in the same manner as in -1).

A-3: 30 parts of ω-aminodecanoic acid, 19 parts of dodecanedioic acid
．． Polyether ester amide (A-3) was prepared in the same manner as (A-1), except that 4 parts of polyethylene glycol tv and 50.6 parts of polyethylene glycol tv with a number average molecular weight of 1000 were used for one polymerization time of 5 hours. .

(2) (B) Preparation of graft copolymer B-1: Polybutadiene latex (rubber particles 40.
70 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 30 parts (in terms of solid content) of 25 tt (KetV content 80%).

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to prepare a powdery graft copolymer (B-1).

8-2: Polybutadiene latex 5 used in B-1
After emulsion polymerizing 50 parts of a monomer mixture consisting of 60% styrene and 40% acrylonitrile in the presence of 0 parts (in terms of solid content), a powdery graft copolymer (B-2) was obtained in the same manner as B-1. was prepared.

B-3: Polybutadiene latex 4 used in B-1
After emulsion polymerizing 60 parts of a monomer mixture consisting of 95% styrene and 15% acrylonitrile/I in the presence of 0 parts (solid content), a powdery graft copolymer (B-1) was prepared in the same manner as B-1. 3) was prepared.

B-4: Polybutadiene latex 9 used in B-1
After emulsion polymerizing 10 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile in the presence of 0 parts (solid content equivalent), powder-like graft copolymer 1 was obtained in the same manner as B-1. -4) was prepared.

B-5: Acrylonitrile/butadiene = 10/90 (
Styrene 70 parts by weight (in terms of solid content) of copolymer rubber (NBR) latex having a composition of
% and acrylonitrile 30% monomer mixture 40%
After emulsion polymerization, a powdery graft copolymer (B-5) was prepared in the same manner as B-1.

B-6: Polybutadiene latex 6 used in B-1
Methyl methacrylate/L/in the presence of 0 parts (solid content)
After emulsion polymerization of 40 parts, a powdery graft copolymer (B-6) was prepared in the same manner as B-1.

L3) Preparation of C1 copolymer C-1: A copolymer (C-1) was prepared by copolymerizing 65 parts of styrene and 25 parts of acrylonitrile.

C-2: A copolymer (C-2) was prepared by copolymerizing 70 parts of styrene, 27 parts of acrylonitrile, and 3 parts of acrylamide.

C-3: 65 parts of styrene, 10 parts of N-phenylmaleimide
part, and 25 parts of acrylonitrile to form a copolymer (C
-3) was prepared.

c-4: Polystyrene (Styron 666 Asahi Kasei Corporation)
) C-5: Polymethyl methacrylate (Acrivet V
HE Hishi Rayon (manufactured by Co., Ltd.) Example 1 N polyether ester amide prepared in the reference example and B)
The graft copolymer and C) copolymer were mixed at the compounding ratio shown in Table 1e, and the mixture was melt mixed and extruded at a resin temperature of 220°C using a vented 40-inch φ extruder to obtain PEVt. rushed forward.

Next, a test piece was molded using an injection molding machine at a cylinder temperature of 220°C and a mold temperature of 60°C, and each physical property was measured.

The volume resistivity value was determined using an injection molded disk with a thickness of 2H.
Measurements were made under the following conditions.

(1) Immediately after forming the Im, it was washed with an aqueous solution of the detergent Mama Lemon (manufactured by Lion Yushi Co., Ltd.), thoroughly washed with distilled water, and the surface moisture was removed.
The humidity was adjusted for 24 hours and measured.

(2) After molding, leave it at 23℃ for 200 days, wash it with a mama lemon aqueous solution, lay it down, thoroughly wash it with distilled water, remove surface moisture,
The humidity was controlled at 0% RH and 123° C. for 24 hours.

The measurement results are shown in Table 1.

Comparative Example 1 N polyether ester amide prepared in Reference Example and [F
]) Graft copolymer and C) copolymer were mixed at the blending ratio shown in Table 1, and each physical property was measured in the same manner as in Example 1. In addition, the physical properties of the N polyether ester amide, (B) graft copolymer, and C) copolymer alone were measured in the same manner. The results are also shown in Table 1.

The following is clear from the results in Table 1. The resin compositions of the present invention (Melons 1 to 8) all have excellent mechanical properties represented by tensile properties 1 flexural modulus and impact strength, and low volume resistivity values. Furthermore, the resistance value hardly changes even after surface cleaning or aging, and exhibits excellent permanent antistatic properties. Moreover, the appearance of the molded product is also extremely good.

That is, the resin composition of the present invention has both excellent mechanical properties and permanent antistatic property, and the appearance of molded products is extremely good.

On the other hand, when blend 2 of polyether ester amide ■ is less than 1 part by weight (7fL9), the antistatic property (resistance value) is poor;
(410, 19), the tensile yield stress and flexural modulus are inferior.

When the amount of graft copolymer (8) is 2 parts by weight or less (&11.18), the impact resistance is poor, and when it is 99 parts by weight or more (412, 20), the antistatic property is poor.

The rubbery polymer in the resin composition (the proportion of Al is 40% by weight)
If it exceeds (13.22.23), the tensile yield stress and flexural modulus are inferior.

When a graft copolymer (B) containing more than 80 parts by weight of the rubbery polymer is used (414), the graft copolymer is poorly dispersed and the appearance of the molded article is impaired. When a graft copolymer (B+ or co-31f copolymer C) in which the proportion of vinyl cyanide monomer is less than 10% by weight is mixed with polyether ester amide (415 to 17), the impact resistance is poor, The appearance of the molded product may be impaired, or a desired resin composition may not be obtained. Resin composition not containing polyetheresteramide N (Engineering 20.21)
) It is not preferable because it has a high It resistance value and poor antistatic properties.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has excellent mechanical properties such as permanent antistatic properties and impact resistance.

Claims (1)

Scope of Claims: (A) (a) 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, (b) a poly( alkylene oxide) glycol and (c) carbon number 4~
A polyether ester amide composed of 20 dicarboxylic acids, containing 1 to 90 parts by weight of a polyether ester amide containing 95 to 10% by weight of polyether ester units, and (B) 5 to 80 parts by weight of (a) rubbery polymer. A graft copolymer obtained by graft-polymerizing (b) 95 to 20 parts by weight of a monomer mixture consisting of 40 to 90% by weight of an aromatic vinyl monomer and 60 to 10% by weight of a cyanated vinyl monomer. 99 to 2 parts by weight of the combination, (C) 40 to 90% by weight of aromatic vinyl monomer, 60 to 10% by weight of vinyl cyanide monomer, and 0 of other vinyl monomers copolymerizable with these. A thermoplastic resin composition comprising 0 to 97 parts by weight of a copolymer obtained by polymerizing a monomer mixture comprising 1 to 40 parts by weight, and 1 to 40 parts by weight of a rubbery polymer (a).