JPS6023447A - Antistatic resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having permanent antistaticity and excellent mechanical properties such as impact strength, etc., by compounding a specific polyether ester amide with a polyglutarimide. CONSTITUTION:The objective composition is produced by compounding (A) 5- 80(wt)%, preferably 10-60% polyether ester amide composed of (i) a >=6C aminocarboxylic acid or lactam, or a >=6C salt of a diamine and a dicarboxylic acid, (ii) a poly(alkylene oxide)glycol having a number-average molecular weight of 200-6,000, and (iii) a 4-20C dicarboxylic acid with (B) 95-20%, preferably 90-40% polyglutarimide. The component A is preferably a resin composed of hexamethylenediamine-adipic acid, polyethylene glycol, and terephthalic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a conductive resin All composite acid having permanent band resistance prevention properties and excellent global properties.

Synthetic polymer materials are used in a wide range of fields due to their excellent properties, but they generally have good electrical resistivity and are easily charged, leading to various problems caused by static electricity.

Conventionally, for the purpose of imparting antistatic properties to synthetic polymer materials, two methods have been proposed: (1) incorporating water-absorbing compounds such as polyalkylene oxide and antistatic agents into polymers, and (2) adding surfactants, etc. Generally, methods such as applying it to the surface are used, but none of these methods have achieved a 1-minute core prevention performance, and washing with water or wiping the surface does not improve the antistatic property. There are problems such as the components disappearing, the kneaded components bleed out to the surface and the quality of the material deteriorates, and the antistatic property deteriorates over time.

Compared to these additive-type polymers, polyamide and polyether are ester bonded via dicarboxylic acid, so-called polyether ester amide, which has excellent rubber elasticity and is itself a polymer with good antistatic properties. Are known. However, since it is polyether ester amide and has insufficient mechanical strength, it is not rigid or strong.
It has the disadvantage that it cannot be used as a structural material that requires J properties. Moreover, polyether esteramide can be used with other thermoplastic resins such as polystyrene, styrene-acrylonitrile copolymer (SAN resin), polymethyl methacrylate, styrene-methyl meccrylate copolymer, acrylonitrile-butadiene-styrene ternary copolymer, etc. Polymer (A
It has poor compatibility with vinyl/silicone polymers such as BS-resin), and even when mixed with these ordinary thermoplastic resins,
Layer peeling occurs and impact strength is poor, making it impossible to obtain a resin composition with desirable mechanical properties. Therefore, it has not yet been possible to utilize polyether ester amide as an antistatic resin by taking advantage of its properties.

On the other hand, in recent years, JP-A No. 52-63989, etc.? Polyglutarimide, which was proposed as a new imide-based polymer with excellent antistatic properties, has a high heat distortion temperature.
Currently, its use as a molding material is limited due to poor mechanical properties, typified by impact strength.

The present inventors conducted extensive research on polyether ester amide with the aim of developing an antistatic resin with permanent anti-static properties and excellent mechanical properties. has specific compatibility with the above-mentioned polyglureimide, and it has been discovered that the above object can be efficiently achieved by mixing the two in a specific ratio, and the present invention has been achieved based on this discovery.

That is, the present invention provides (A) (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a lactam having 6 or more carbon atoms;
Salts of the above diamines and dicarboxylic acids, (1) poly(alkylene oxide) glycols with several thousand M molecules i2oo to 6ooo, and (C) polyether ester amides 5 to 5 consisting of dicarboxylic acids having 4 to 20 carbon atoms. 80
The present invention provides an antistatic resin composition containing 95 to 20% by weight of (B) polyglycoleimide.

Polyetheresteramide styrene-acrylonitrile copolymer (SAN
It has poor compatibility with ordinary thermoplastic resins such as 4J (fat), and even if they are mixed, only a thermoplastic resin composition with poor mechanical properties can be obtained, but it has a specific compatibility with polyglutarimide. By mixing polyether ester amide having the above composition and Borig I Retalimide, a resin composition with excellent mechanical properties and permanent antistatic properties can be obtained, and the effects of the present invention can be efficiently exhibited. .

In the present invention, (A) aminocarboxylic acid or lactam having 6 or more carbon atoms or diamine having 6 or more carbon atoms, which is a constituent component of (A) polyether ester amide, and θJ-7 minocafrebonic acid are θJ-7 minocaproic acid. , ω-aminoenanthate, ω-aminocaprylic acid, θ
lactams such as aminoperboxylic acid, ω-am, enanthoctam, cabryl octam and laurolactam and hexamethylenediamine-adipate, hexamethylenediamine-sinate and hexamethylenediamine-isophthalate. Salts of diamine-dicarboxylic acids are used, and hexamethylenediamine-adipate is particularly preferably used.

(b) Poly(alkylene oxide) glycol, which is a constituent component of (A) polyetheramide, includes polyethylene coulicol, poly(1,2-propylene oxide) glycol, poly(1,5-propylene oxide) glycol, and poly(alkylene oxide) glycol. (Tetramethinone oxide)
Glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. are used. Among these, polyethylene V glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of poly(alkylene oxide) glycol is used in the range of 200 to 6,000, especially 250 to 2,000. If the number average molecular weight is less than 20'0, the mechanical properties of the polyether ester amide obtained are poor, If the average molecular weight exceeds 6,000, antistatic properties will be insufficient, which is not preferable.

(A) Constituent component of polyether ester amide (
C) Dicarboxylic acid having 4 to 20 carbon atoms (C) and L are prephthalic acid, isophthalic acid, fucuric acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2, fudicarboxylic acid, diphenyl-4,4' -Cicafrebonic acid, diphenoxyethanedicarboxylic acid and 6-sulfoisophthalcarboxylic acid 6i2, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and hiscyclohexyl-4,4'-dicarboxylic acid i
group dicarboxylic acids and succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decanedicarboxylic group 2)
), among which terephthalic acid, isophthalic acid, L4-cyclohexanedicarboxylic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

(A) Polyether ester Not particularly limited, for example, (a) polyamide prepolymer having carboxylic acid groups at both ends by reacting (a) aminocarboxylic acid or lactam with (C) dicarboxylic acid in an approximately equal ratio. (1) A method of reacting poly(alkylene oxide) Getacol with this under vacuum. A method of producing a carboxylic acid-terminated polyamide prepolymer by pressurizing reaction at high temperature in the presence or absence of a column, and then proceeding with polymerization under normal pressure or reduced pressure, and H (a), (b) ) and (C) can be simultaneously introduced into the reactants, melt-mixed, and then polymerized all at once under high vacuum, which is a known method.

(B) polyglutarimide used in the present invention is the following formula (
(2) A polymer or copolymer containing a cyclic imide unit.

R.

However, R1 in the formula. R2 and R3 each represent 4 hydrogen atoms or a substituted or unsubstituted alkyl or aryl group having 1 to 20 carbon atoms. If it contains the above cyclic imide unit,
Polyglutarimide may have any chemical structure, but usually R and R2 in the cyclic imide unit are hydrogen or a methyl group, and R3 is hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. are commonly used. Regarding polyglutarimide, for example, there is a method of forming glutarimide by reacting polymethyl methacrylate with ammonia or a primary amine such as methylamine or ethylamine in an extruder, which is described in JP-A No. 52-63989. Useful.

The blending ratio of the resin composition of the present invention is (A) 10 to 60% by weight of polyetheresteramide to (B) 9% by weight of polyglutarimide.
5 to 20% by weight, particularly preferably 90 to 40% by weight. (A) Polyetheresteramide If it is less than the weight ratio, the antistatic property and impact strength of the resin composition will be insufficient, and if it exceeds 80 weight ratio, the resin composition will become flexible and have poor mechanical properties, which is not preferable.

There are no particular restrictions on the method for producing the resin composition of the present invention, but usually (A) polyetherester reamide and (
B) Premixing polyglue IV imide by an appropriate method,
It can be produced by melt-kneading with an extruder and forming pellets.

The resin composition of the present invention further includes styrene-acrylonitrile copolymer (SAllil resin), y-y-vn-methyl methacrylate-acrylonitrile α-methylnutyrene-acrylonitrile cofi combination, α-methylstyrene-
Methyl methacrylate-ac IJ O = l-lyl copolymer, d-methylnutylene-styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-nutyrene copolymer (ABS
By adding various thermoplastic resins such as methyl tuacrylate-getadiene-styrene copolymer (MBS resin), polyamide, polyethylene terephthalate, and polyethylene terephthalate, the performance as a molding resin was improved. can do. Also, anionic,
It is also possible to further improve the antistatic property by adding an antistatic agent such as a cationic surfactant, and if necessary, various stabilizers such as antioxidants and ultraviolet absorbers may be added. Pigments, dyes, lubricants, plasticizers, etc. can also be added.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The specific volume resistivity was measured using an injection molded square plate with a thickness of 3 mm at room temperature of 26 parts and humidity of 5Q%RH.
Measured under ambient air. A super insulation resistance meter 5M-1Q manufactured by Toa Denpa Kogyo (I→) was used for the measurement.The tensile strength at break was 8STM D66B, and the flexural modulus was ASTM D7.90.
．． Izod impact strength was measured according to AsTM D256. Parts and ratios indicate parts by weight and weight %.

Reference example (1) (A) Preparation of polyether ester amide Δ-
10 parts of nylon 6.6 salt (AH salt) prepared in advance from hexamethylene diamine and adipic acid, 1/72.4 parts of polyethylene glycol having a number average molecular weight of 600, and 17.6 parts of adipic acid were added to 1 Irganox. ” 1098
(Antioxidant) 0.2 parts and 1 part tetrabutyl titanate
, with 0.05 part of catalyst? Charge Rikkafre Ribbon 1 into a reactor equipped with stirring blades, exchange with nitrogen and heat to 240°C.
After heating for 40 minutes at
Polymerize for 6 hours at 60°C and below 0.5m+aHg,
A viscous, colorless and transparent molten polymer was obtained. By discharging the polymer onto a cooling belt and pelletizing it, pelletized polyether ester amide (A-
1) was prepared.

A-2, except that 20 parts of nylon 6.6 salt (AH salt), 69.8 parts of polyethylene glycol with a number average molecular weight of 11,000, and 10.2 parts of adipic acid were used, and the polymerization time was 4 hours (A-1 ) Polyether ester amide (A-5) was prepared in the same manner as (A-1) except that the polymerization time was changed to 5 hours.

(2> (B) Pellets of polyglutarimide polymethyl methacrylate were charged into an extruder together with ammonia or methylamine, and while degassing the generated gas from the exhaust port attached to the extruder, the resin temperature was 280°C. Extrusion was carried out to prepare two types of polyglucurimides (when the imidizing agent was ammonia) and B-2 (when the imidizing agent was methylamine).

(3) (C) Preparation of thermoplastic polymer The following polymers (C-1 to C-
6) was prepared.

A thermoplastic polymer (C-1) was prepared by polymerizing C- with methyl methacrylate (C-1).

C-2: A thermoplastic polymer (C-2) was prepared by copolymerizing 70 parts of styrene and 60 parts of acrylonitrile.

C-3: Acrylonitrile/gutanene-10/90
Copolymer rubber (NBR) 60 having the composition (weight ratio)
70 parts of styrene and 30% of acrylonitrile in the presence of
A graft copolymer (C-1) was prepared by polymerizing 40 parts of a monomer mixture consisting of:

Example 1 Pellets were produced by mixing (A) polyether ester amide prepared in Reference Example and (B) polyglutarimide, and melting and mixing and extruding at a resin temperature of 260°C using a vented 40+++ mφ extruder. . Next, a test piece was molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 50°C, and each physical property was measured.

The volume resistivity was measured under the following two conditions using an injection molded square plate with a thickness of 3 mm.

(1) Immediately after molding, use the detergent Mama Lemon (Lion Oil also →
After washing with an aqueous solution (manufactured by Mimaki Co., Ltd.) and thoroughly washing with distilled water to remove surface moisture, the humidity was adjusted at 5.0% RH for 24 hours and measured.

(2) After molding, 50q6RH, 23tE medium 20
After leaving it for a day, wash it with Mama Lemon detergent solution.
Subsequently, the surface was thoroughly washed with distilled water to remove moisture from the surface, and then the humidity was adjusted at 50% RH at 126° C. for 24 hours and measured.

The measurement results are shown in Table 1. (Boiled 1 to A8) Comparative Example The (A) polyether ester amide and (B) polyglutarimide or (C) thermoplastic polymer prepared in the reference example were mixed at the blending ratio shown in Table 1. Each physical property was measured in the same manner as described above. In addition, the physical properties of (A) polyether ester amide, (B) polyglutarimide, and (C) thermoplastic polymer alone were also measured in the same manner.

The results are also shown in Table 1. (A9-A2'0) Example 2 (A) Polyether ester amide-imide The physical properties of the composite composition were measured in the same manner as in Example 1.

The blending ratio and measurement results are shown in Table 1.

(Blank below on this page) The following is clear from the results in Table 1. The resin compositions of the present invention (Nos. 1 to 8) all have excellent mechanical properties such as tensile strength at break, flexural modulus, and impact strength, and low specific volume resistivity. Moreover, its resistivity hardly changes even after surface cleaning or aging, and exhibits excellent permanent antistatic properties. That is, the resin composition of the present invention has both excellent mechanical properties and permanent antistatic properties.

On the other hand, (A) polyether ester amide alone (thickness 14
~16) or (A) polyether ester amide breaking strength and flexural modulus are poor. (B) In the case where polyglutarimide steramide is not dropped in 5 layers (Ivy 9), the impact strength and antistatic property are insufficient. Also, methacrylic acid
Methyl (jf6.19), S. AN
Ordinary thermoplastic resins such as Tsukiji Itsuki (Kama 20) have high resistivity (and poor antistatic properties).

Furthermore, the resin composition of the present invention comprising (A) polyether ester amide and (B) polyglypimide is further added with t.
By mixing other (C)M plastic polymers (A21 to A26), an antistatic resin composition with even better mechanical properties can be obtained.

As explained above, the resin composition of the present invention has permanent antistatic properties and excellent mechanical properties, and is expected to be used as antiperspirant in various fields in the future. .

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] (A) (a) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 6 or more carbon atoms, (1)) Number average molecular weight 200-60
00 poly(alkylene oxide) glycol and (
C) Polyether ester amide 1:5 to 80% by weight composed of dicarboxylic acid having 4 to 20 carbon atoms and (
B) An antistatic resin composition containing 95 to 20% by weight of polyglutarimide (B).