JP3202415B2 - Antistatic agent and resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetheresteramide having excellent heat resistance and permanent antistatic properties, and further having excellent compatibility with a thermoplastic resin, and a resin composition using the polyetheresteramide. is there.

[0002]

2. Description of the Related Art Various types of antistatic agents for plastics have been proposed. Among them, polyetheresteramide is known to impart excellent antistatic properties as an antistatic agent for some thermoplastic resins,
(1) Since polyoxyalkylene glycol such as polyethylene glycol is used for the polyether component, heat resistance is low and there is a problem in molding at high temperature. (2)
Poor compatibility between polyetheresteramide and other thermoplastic resins causes problems such as delamination or poor impact strength, making it impossible to obtain a resin composition having desirable mechanical properties. Was. In order to solve the problem (2), a method using a modified vinyl polymer having a carboxyl group in polyetheresteramide as a compatibilizer (Japanese Patent Publication No. 4-72855), a vinyl monomer having a hydroxyl group (Japanese Patent Laid-Open No. 2-70739) is known which uses a rubber-modified styrene-based thermoplastic resin having a copolymer component as a compatibilizer. Although the compatibility problem has been improved by these methods, a large amount of a compatibilizer must be added and the antistatic property is lower than that obtained by kneading only two other thermoplastic resins. Was. Also, in JP-A-1-144417,
It is disclosed that the polyetheresteramide and the resin composition obtained by using a polyoxyalkylene glycol having a specific molecular weight are transparent and have excellent permanent charging properties, but the problem of heat resistance (1) is still solved. It has not been.

[0003]

At present, the heat resistance is excellent.
And polystyrene, polymethyl methacrylate, styrene / acrylonitrile copolymer (SAN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin) and styrene / methacrylic A polyetheresteramide having good compatibility with a thermoplastic resin such as a methyl acid / acrylonitrile copolymer is desired.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, polyetheresteramide having a specific group introduced therein has higher heat resistance and chargeability than conventional polyetheresteramide. The present invention has been found that the resin composition comprising the polyetheresteramide and the thermoplastic resin has excellent heat resistance, permanent antistatic properties and mechanical strength.

That is, the present invention relates to a polyamide component (a1) having carboxyl groups at both ends and having a number average molecular weight of 500 to 5,000 and a number average molecular weight of 1,500 to 3,000.
(A2) derived from the polyetherdiol component (a2) A thioether - antistatic agent consisting of polyether ester amide (A) containing ether groups; mosquitoes at both ends
Number average molecular weight having a ruboxyl group of 500 to 5,000
With the polyamide component (a1) having a number average molecular weight of 1,500 to
Induced from 3,000 polyetherdiol components (a2)
And the component (a2) is a thioether group-containing low molecular
-Alkylene oxides of methyl or mercaptan compounds
From the adduct polyetheresteramide (A).
And a resin composition comprising the antistatic agent and the thermoplastic resin (B).

The polyamide component (a1) having carboxyl groups at both terminals in the present invention includes (1) a lactam ring-opening polymer, (2) a polycondensate of an aminocarboxylic acid or (3) a polycondensate of a dicarboxylic acid and a diamine. Known polyamides such as condensates include carboxyl groups at both ends. Examples of the lactam (1) include caprolactam, enantholactam, laurolactam, undecanolactam and the like. As the aminocarboxylic acid (2), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω
-Aminocapric acid, 11-aminoundecanoic acid, 12
-Aminododecanoic acid and the like. As the dicarboxylic acid (3), thiodiacetic acid, thiodipropionic acid, adipic acid, azelaic acid, sebacic acid, undecandioic acid,
Examples of the acid include dodecane diacid, isophthalic acid and the like, and examples of the diamine include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, thiodiethylamine, diaminodiphenylthioether and the like. Two or more of those exemplified as the amide-forming monomers may be used. Preferred of these are caprolactam, 12-aminododecanoic acid, and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

The component (a1) is obtained by subjecting the amide-forming monomer to ring-opening polymerization or polycondensation of the amide-forming monomer in the presence of a dicarboxylic acid component having 4 to 20 carbon atoms as a molecular weight modifier. Can be Carbon number 4 ~ 2
Examples of the dicarboxylic acid 0 include aliphatic dicarboxylic acids such as thiodiacetic acid, thiodipropionic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, and dodecanediacid, and terephthalic acid. Aromatic dicarboxylic acids such as acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; and sodium 3-sulfoisophthalate. Alkali metal salts of 3-sulfoisophthalic acid such as -potassium sulfoisophthalate;
Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are thiodiacetic acid, thiodipropionic acid, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. And sodium 3-sulfoisophthalate.

The number average molecular weight of the component (a1) is from 500 to
It is 5,000, preferably 500-3,000. 5
If it is less than 00, the heat resistance of the polyetheresteramide itself decreases, and if it exceeds 5,000, the reactivity decreases, so that it takes a lot of time to produce the polyetheresteramide.

The introduction of a thioether group into the component (a1) can be achieved by using a thiodicarboxylic acid as an acid component including a molecular weight regulator during the production of a polyamide, or using a diaminosulfide compound as an amine component. You. Such thiodicarboxylic acids include thiodiacetic acid and thiodipropionic acid. Diaminosulfide compounds include thiodiethylamine and diaminodiphenylthioether.

The component (a2) includes alcohols, phenols and alkylene oxide adducts of carboxylic acids. As the alcohol, ethylene glycol
And aliphatic, alicyclic or aromatic group-containing glycols such as toluene, propylene glycol, butanediol, thiodiethylene glycol, cyclohexanediol, cyclohexanedimethanol, and xylylene glycol. Can be Examples of phenols include hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether, and substituted alkyl or halogen nuclei thereof.

Examples of the carboxylic acid include the dicarboxylic acids described for the polyamide component (a1).

Of these, preferred are phenols,
Particularly preferred is bisphenol A.

[0013] Alkylene oxides include ethylene oxide, propylene oxide, butylene oxide and styrene oxide. Preferred is ethylene oxide. Further, other alkylene oxides (such as propylene oxide) can be used together with ethylene oxide, but the amount of the other alkylene oxide is usually 10% by weight or less based on the amount of ethylene oxide.

The introduction of a thioether group into the component (a2) can be achieved by using an alkylene oxide adduct of a thioether group-containing low molecular weight diol or a mercaptan compound. Examples of such thioether group-containing low molecular diols include dihydroxydiphenyl ether.
Ter and dihydroxydiphenylthioether; and mercaptan compounds include hydrogen sulfide and mercaptoethanol.

The number average molecular weight of the component (a2) is 1,50
0 to 3,000. If it is less than 1,500, the antistatic property becomes insufficient, and if it exceeds 3,000, the reactivity decreases, so that a great amount of time is required in producing the polyetheresteramide.

(A2) is used in a range of 20 to 80% by weight based on the total weight of (a1) and (a2). If less than 20%, polyetheresteramide (A)
Is inferior in antistatic properties, and if it exceeds 80% by weight, the heat resistance of (A) is undesirably reduced.

Examples of the method for producing the polyetheresteramide (A) include, but are not particularly limited to, the following methods and methods. Production method: The component (a1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and the component (a) is added thereto.
A method in which 2) is added and a condensation reaction is carried out at a high temperature under reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and a component (a2) are simultaneously charged into a reaction vessel, and a pressure reaction is performed at a high temperature in the presence or absence of water to produce a component (a1) as an intermediate, Then, a method of performing a condensation reaction between the components (a1) and (a2) under reduced pressure. In any method, it is necessary to use a thioether group-containing compound as a component of the component (a1) or (a2).

In the above-mentioned polymerization reaction, a generally known esterification catalyst is used. Examples of the catalyst include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate, zirconium catalysts such as tetrabutylzirconate, and metal acetate salts such as zinc acetate. Catalysts and the like. These amounts are usually used as the component (a1)
And 0.1 to 5% by weight based on the total weight of (a2) and (a2).

The relative viscosity of (A) is usually 0.5 to 4.0 (0.5% by weight m-cresol solution at 25 ° C.), preferably 0.6 to 3.0, from the viewpoint of heat resistance and moldability. It is.

In the resin composition of the present invention, the thermoplastic resin (B) may be selected from polystyrene, polymethyl methacrylate, and two or more copolymers selected from the group consisting of styrene, methyl methacrylate, acrylonitrile, and butadiene (styrene). / Acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer and styrene / methyl methacrylate / acrylonitrile copolymer), polyolefins such as polypropylene and polyethylene, polycarbonate, acrylic resin And the like.
Of these, preferred are polystyrene, polymethyl methacrylate, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, and styrene / methyl methacrylate / acrylonitrile copolymer. It is united.

In the resin composition of the present invention, the weight ratio of the antistatic agent of the present invention to the thermoplastic resin (B) is (5 to 4).
0): (95 to 60).

In the resin composition of the present invention, in order to further improve the compatibility between the antistatic agent of the present invention and (B), carboxyl groups, epoxy groups, amino groups, hydroxyl groups described in JP-A-3-258850, etc. Group, a polymer having at least one functional group selected from the group consisting of a polyalkylene oxide group and a derivative thereof, and a vinyl polymer having a sulfonic acid group, a polyolefin portion and an aromatic vinyl polymer portion. (C) may be contained. The amount of (C) used is usually 0.1 to 10% based on the total weight of the antistatic agent of the present invention and (B).
It is 15% by weight, preferably 1 to 10% by weight.

For the purpose of further improving the antistatic effect, a metal salt (D) comprising a halide of an alkali metal and / or an alkaline earth metal may be contained. (D)
Examples thereof include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, and magnesium bromide. Particularly preferred among these are sodium chloride and potassium chloride. (D)
It is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of (A), (B) and (C). If the content is less than 0.01% by weight, no effect is exhibited, and if it exceeds 5% by weight, it precipitates on the resin surface and impairs the appearance of the resin.

The resin composition of the present invention can be obtained by kneading the above components using various known mixers. Examples of the mixer include an extruder, a Brabender, a kneader, and a Banbury mixer.

The order of addition of each component during kneading is not particularly limited. 1. A method of blending and kneading (A) to (C); 2. A method of blending and kneading a small amount of (B) with (A) and (C) and then kneading the remaining (B).
After blending and kneading (A) and (C), there is a method of kneading (B). 2. And 3. Is a method called master batch or master pellet. 1. It has good dispersibility, and is excellent in permanent antistatic properties and mechanical strength.
Is preferred.

The method for obtaining the composition of the present invention via a masterbatch generally comprises 50 to 90 parts by weight of the antistatic agent of the present invention, (B) 50 to 10 parts by weight, preferably 30 to 10 parts by weight and ( C) 2 to 30 parts by weight are blended and kneaded to form a master batch, and this master batch and (B) are further blended and kneaded to obtain the composition of the present invention. In particular, since the method can uniformly disperse a small amount of the antistatic agent of the present invention in a large amount of (B), the composition of the present invention is preferably formed via a masterbatch.

The resin composition of the present invention may optionally contain other resin additives as long as the properties of the composition are not impaired, depending on various uses. Examples of the additives include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers and the like. The amount of the additive to be used is generally 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of (A), (B) and (C). If the content is less than 0.01% by weight, no effect is exhibited, and if it exceeds 5% by weight, it precipitates on the resin surface and impairs the appearance of the resin.

[0028]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in Examples are parts by weight. After the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods.

Surface specific resistance: A square test piece having a thickness of 2 mm was measured at 20 ° C. using a super insulation meter (manufactured by Advantest)
The measurement was performed in a 65% RH atmosphere. Izod impact strength: ASTM D256-56A Tensile strength: ASTM D638 Heat loss starting temperature: Measured by TG-DTA under air (indicator of heat resistance).

[Production of Polyetheresteramide] Production Example 1 In a 3 L stainless steel autoclave, 105 parts of ε-caprolactam, 17.4 parts of thiodiacetic acid, and Irganox 1
010 (Antioxidant manufactured by Ciba-Gaiky) 0.3 parts and water 6 parts were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours under pressure and airtight, and a polyamide oligomer having an acid value of 110 having a carboxyl group at both ends. 117 parts were obtained. Next, 225 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 of zirconyl acetate were added.
Then, polymerization was performed for 5 hours under reduced pressure of 245 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a thioether group-containing polyetheresteramide. Its relative viscosity was 2.15 (0.5% by weight m-cresol solution, 25 ° C.). This polyetheresteramide is abbreviated as (A-1) below.

Production Example 2 Into a 3 L stainless steel autoclave, 105 parts of ε-caprolactam, 17.1 parts of adipic acid, Irganox 1
010 (Antioxidant manufactured by Ciba-Gaiky) 0.3 parts and water 6 parts were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours under pressure and airtight, and a polyamide oligomer having an acid value of 110 having a carboxyl group at both ends. 117 parts were obtained. Next, an ethylene oxide adduct 225 of 4,4'-dihydroxydiphenylthioether having a number average molecular weight of 1,500.
Parts of the mixture and 0.5 part of zirconyl acetate are added,
Polymerization was performed at 5 ° C. under reduced pressure of 1 mmHg or less for 5 hours,
A viscous polymer was obtained. The polymer was taken out in a strand form on a belt and pelletized to obtain a thioether group-containing polyetheresteramide. Its relative viscosity was 2.20 (0.5% by weight m-cresol solution, 25 ° C.). This polyetheresteramide is abbreviated as (A-2) below.

Production Example 3 In a 3 L stainless steel autoclave, 105 parts of ε-caprolactam, 17.1 parts of adipic acid, Irganox 1
010 (Antioxidant manufactured by Ciba-Gaiky) 0.3 parts and water 6 parts were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours under pressure and airtight, and a polyamide oligomer having an acid value of 110 having a carboxyl group at both ends. 117 parts were obtained. Next, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 parts of zirconyl acetate were added, and 2
Polymerization was performed at 45 ° C. under reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide. This has a relative viscosity of 2.20 (0.5 wt% m-cresol solution, 25
° C). This polyetheresteramide is abbreviated as (A-3) below. [Production of Graft Copolymerization Reaction Product] Production Example 4 In the presence of 40 parts of polybutadiene latex, 60 parts of a monomer mixture composed of 72% by weight of methyl methacrylate, 24% by weight of styrene, and 4% by weight of acrylonitrile were emulsion-polymerized. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymerization reaction product (C-1).

Production Example 5 After blending the components (A) to (C) at the ratios shown in Table 1 for 3 minutes using a Henschel mixer, the mixture was subjected to a twin-screw extruder equipped with a vent at 240 ° C., 30 rpm, and a residence time of 5 minutes. To obtain masterbatches (M-1) to (M-5).

[0034]

[Table 1]

Examples 1 to 5 A master batch (M-1) to (M-5) and an acrylonitrile-butadiene-polystyrene terpolymer (B) shown in Table 2 were blended under the same conditions as in Production Example 4. It was kneaded to obtain the composition of the present invention. Table 2 shows the composition and ratio of the composition of the present invention via the masterbatch.

[0036]

[Table 2]

Examples 6 to 12 and Comparative Examples 1 to 5 (A) to (C) shown in Table 3 were blended and kneaded under the same conditions as in Production Example 4 to obtain the compositions of the present invention and comparative compositions. Was.

[0038]

[Table 3]

Next, the cylinder temperature was set to 2 by the injection molding machine.
A test piece was molded at 20 ° C. and a mold temperature of 60 ° C., and each physical property was measured. Table 4 shows the results. The surface resistivity was determined by the following method. (A) After molding, the square test piece is kept at 20 ° C. and a humidity of 65%.
Leave in RH atmosphere for 24 hours. (B) After molding, the square test piece is washed with an aqueous solution of a detergent (Mama Lemon; manufactured by Lion Corporation), and then sufficiently washed with ion-exchanged water.
It was left for 24 hours in an atmosphere of 65 ° C. and a relative humidity of 65%.

[0040]

[Table 4]

[0041]

As is clear from the above, the thioether of the present invention can be used.
An antistatic agent comprising a ter group-containing polyetheresteramide is superior in heat resistance, mechanical strength, and antistatic properties to a conventional antistatic agent comprising a polyetheresteramide. The resin composition comprising the polyetheresteramide and the thermoplastic resin has excellent heat resistance, permanent antistatic properties, and mechanical strength. Therefore, the antistatic agent of the present invention is particularly useful as an antistatic agent for heat-resistant plastics.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 77/12 C08L 77/12 101/00 101/00 C09K 3/16 108 C09K 3/16 108B (56) References JP 63-227628 (JP, A) JP-A-2-70739 (JP, A) JP 4-72855 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 69/00 -69/50 C08L 1/00-101/16 C09K 3/06

Claims (5)

(57) [Claims] 1. A polyamide component (a1) having carboxyl groups at both ends and having a number average molecular weight of 500 to 5,000 and a polyetherdiol component (a2) having a number average molecular weight of 1,500 to 3,000. , Component (a1) An antistatic agent comprising a polyetheresteramide (A) containing a thioether group. 2. Number average having carboxyl groups at both ends
A polyamide component (a1) having a molecular weight of 500 to 5,000
Polyetherdiene having a number average molecular weight of 1,500 to 3,000
Derived from an all component (a2), wherein the component (a2) is
Ether group-containing low molecular diols or mercaptans
Polyether ether which is an alkylene oxide adduct of the compound
An antistatic agent composed of a steramide (A). 3. A polyetherester relative viscosity of the amide (A) is 0.5 to 4.0 (0.5 wt% m-cresol solution, 25 ° C.) antistatic agent according to claim 1 or 2 wherein the. 4. Polyamide component (a1) having carboxyl groups at both ends and having a number average molecular weight of 500 to 5,000 and polyetherdiol component (a2) having a number average molecular weight of 1,500 to 3,000. , Component (a1) A polyetheresteramide containing a thioether group ,
Or, when the component (a2) is a thioether group-containing low molecular di-
Or alkylene oxide with mercaptan compound
A resin composition comprising an antistatic agent comprising a polyetheresteramide (A) , which is an additive, and a thermoplastic resin (B). Wherein (B) is polystyrene and / or polymethyl methacrylate and / or, according to claim 4 wherein the two or more copolymers selected from the group consisting of styrene and methyl methacrylate and acrylonitrile and butadiene Resin composition.