JP3157445B2 - Antistatic agent and resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antistatic agent and a resin composition using the same. More specifically, the present invention relates to an anionic antistatic agent exhibiting excellent permanent antistatic properties with a small amount of addition, and a permanent antistatic resin composition using the same.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, and polystyrene resins are lightweight, tough, and inexpensive and easy to mold. Has been used as However, since these plastic molded products are insulative, the surface of the molded product is charged by static electricity and the like, and dust and dirt easily adhere to the molded product, and the appearance of the molded product deteriorates. In such a case, there is a major problem that a malfunction is caused by static electricity.

[0003] As a method for improving these disadvantages,
It is common to add a cationic, anionic, amphoteric, or other ionic surfactant or a nonionic surfactant to a thermoplastic resin. However, the method of adding the surfactant is that the surfactant added over time bleeds out to the surface of the plastic molded product and is easily detached by washing with water or wiping with a cloth. There is a major drawback that it only works.

As a method of solving this drawback, a method of adding a polymer type antistatic agent which is not easily detached from the surface of a molded plastic article; for example, (meth) acrylic acid having a hydrophilic group introduced therein such as polyethylene glycol A method of imparting an antistatic property by introducing an ester as an antistatic monomer into a plastic skeleton (JP-A-55-3623)
No. 7, etc.) A method for improving the antistatic property of a plastic molded article by using a copolymer of (meth) acrylamide or maleimide containing a quaternary ammonium base as one component and another vinyl monomer (particularly, Kaihei 5-32
No. 0526) is known.

[0005]

However, in the above-mentioned method, since a nonionic group having a low antistatic effect is used as an antistatic imparting group, it is necessary to use a monomer at a high concentration, and as a result, plastic There is a problem that the physical properties of the resin inherently deteriorate significantly. In addition, even when a cationic group having a high antistatic effect is introduced into the copolymer at random, the antistatic effect is small, and it is necessary to increase the cationic group content to a high concentration. In addition, since the heat resistance of the cationic group is poor, it is unavoidable to affect the resin properties, coloring, and the like of the plastic.

[0006]

The present inventors have conducted intensive studies to solve the above problems, and as a result, introduced an anion group having excellent heat resistance and an antistatic effect into a molecular chain;
Moreover, a large antistatic effect is obtained by regularly positioning the anionic groups at regular intervals, and as a result, with a small amount of addition, an excellent permanent property for various thermoplastic resins such as polyolefins. They have found that antistatic properties can be imparted, and have reached the present invention.

That is, the present invention provides an aromatic dicarboxylic acid having a sulfonic acid (salt) group or an ester-forming derivative thereof (a1), an alkanediol having 2 to 10 carbon atoms,
Polyester having one or more diols (a2) selected from the group consisting of polyoxyalkylene glycols and alkylene oxide adducts of bisphenols as essential structural units and having two or more sulfonic acid (salt) groups in the molecule An anionic antistatic agent comprising the compound (A);
And a resin composition containing the antistatic agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the aromatic dicarboxylic acid having a sulfonic acid (salt) group in (a1) includes, for example, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfo-2,6-
Naphthalenedicarboxylic acids and their salts (lithium,
Alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, organic amine salts such as alkylamine and alkanolamine, and ammonium salts). Of these, preferred are 5-sulfoisophthalic acid and salts thereof, and particularly preferred are sodium 5-sulfoisophthalate and
-Potassium sulfoisophthalate.

Examples of the ester-forming derivative of an aromatic dicarboxylic acid having a sulfonic acid (salt) group include lower alkyl esters (methyl ester, ethyl ester and the like) of the above-mentioned aromatic dicarboxylic acids, and ester salts ( Alkali metal salts, alkaline earth metal salts, ammonium salts and the like) and acid anhydrides. These (a1)
The aromatic dicarboxylic acid having a sulfonic acid (salt) group or an ester-forming derivative thereof may be used in combination of two or more.

The alkanediol having 2 to 10 carbon atoms in (a2) includes ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6- Hexanediol and the like, and other than these, a cyclic group such as cyclohexanediol, bis (hydroxymethyl) cyclohexane, xylylene glycol, bis (hydroxyethyl) benzene, 1,4′-bis (2-hydroxyethoxy) benzene, etc. May be used. As polyoxyalkylene glycol, polyoxyethylene glycol, polyoxypropylene glycol,
And polyoxybutylene glycol. Examples of the bisphenols of the alkylene oxide adduct of bisphenols include bisphenol A (4,4'-dihydroxydiphenyl-2,2-propane), bisphenol F (4,4'-dihydroxydiphenylmethane), and bisphenol S (4,4 ' -Dihydroxydiphenyl sulfone), 4,4'-dihydroxydiphenyl-2,2
-Butane and the like; and the alkylene oxides include ethylene oxide and propylene oxide. Two or more of those exemplified as (a2) may be used in combination. Preferred among these are ethylene glycol, diethylene glycol, polyethylene glycol and ethylene oxide adducts of bisphenols and mixtures thereof.

(A) is an esterification reaction product of the above (a1) and (a2), and is a compound having two or more sulfonic acid (salt) groups in the molecule.

As the production method of (A), a general production method of polyester can be applied as it is. The polyesterification reaction is usually performed under a reduced pressure in a temperature range of 150 to 240 ° C., and the reaction time is usually 0.5 to 20 hours.

In the polyesterification reaction, a usual esterification catalyst may be used. There is no limitation on the esterification catalyst. For example, antimony catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide and dibutyltin oxide; titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutylzirconate A metal acetate-based catalyst such as zinc acetate;

The number average molecular weight of (A) in the present invention is:
Usually 600 to 30,000, preferably 800 to 20,
000. If the molecular weight is less than 600, heat resistance is lowered and the effect of preventing permanent electrification is poor. If it is more than 30,000, the viscosity becomes too high at the time of melting, and handling becomes poor, which is not preferable. In order to exhibit an excellent antistatic effect, the number of sulfonic acid (salt) groups in (A) usually needs to be 2 or more in the molecule, and is preferably 3 or more.
More than one is good. If the number is less than 2, the effect of imparting antistatic properties is extremely poor, and the desired permanent antistatic effect cannot be obtained.

In the resin composition of the present invention, the thermoplastic resin (B) includes polyolefin resins such as polypropylene and polyethylene; polyamide resins such as nylon 6, nylon 66 and nylon 6/12; polyvinyl chloride resins; Acrylic resin such as polymethyl methacrylate; two or more copolymers selected from the group consisting of styrene, methyl methacrylate, acrylonitrile and butadiene (styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer) Coalesce and styrene / methyl methacrylate / acrylonitrile copolymer); polycarbonate; polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), polyacetal resin, thermoplastic polyurethane resin and the like. Of these, it may be used in combination of two or more. Of these, preferred is the polyolefin-based resin (B1).

The (B1) includes propylene and / or
Or (co) polymers of ethylene, and copolymers (random or block) of propylene and / or ethylene with one or more other α-olefins. Other α-
Examples of the olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene,
-Dodecene and the like.

The melt flow rate (MFR) of (B1)
Is usually 0.5 to 150, preferably 1 to 100. Melt flow rate is JIS K6758 (in the case of polypropylene resin; temperature 230 ° C, load 2.16)
kgf, polyethylene-based resin; temperature 190 ° C., load 2.16 kgf).

Particularly, in the resin composition mainly composed of (B1), at least one resin (B2) having a higher crystallization temperature than that of (B1) and selected from polyamide resins, polyester resins and polyacetal resins is combined. Thereby, an effective antistatic property can be imparted with a smaller amount of the antistatic agent added. The amount of (B2) to be used is generally 1 to 20% by weight, preferably 1 to 15% by weight, based on the weight of (B1). If it is less than 1%, the effect is small, and if it exceeds 20% by weight, the intrinsic physical properties of the polyolefin resin are impaired.

As (B2), the polyamide resin described above;
Polymers and oligomers selected from polyester-based resins and polyacetal resins can be used, and among these, particularly preferred are polymers and oligomers selected from nylon 6, nylon 66, nylon 12, and nylon 6/12 copolymerized polyamide.

In the resin composition of the present invention, the weight ratio of (A) to (B) is usually (1 to 50): (99 to 5).
0), preferably (3-20): (97-80). If the ratio of (A) is less than 1, no good antistatic effect can be obtained, and if it exceeds 50, the intrinsic physical properties of the resin are impaired.

The resin composition of the present invention can be obtained by kneading the components (A) and (B) using various known mixers. Mixers include, for example, extruders, Brabenders, kneaders and Banbury mixers.

In the present invention, in particular, a modified polyolefin compatibilizer (C) may be used for the purpose of improving the compatibility between (A) and the polyolefin resin. Examples of (C) include a polyolefin modified with an α, β-unsaturated carboxylic acid or an ester-forming derivative compound thereof, and a modified polyolefin having at least one functional group selected from a hydroxyl group and an epoxy group. As the polyolefin used for the above modification, polyethylene,
Examples include polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and copolymers containing a small amount of diene.

Specific examples of the modified polyolefin compatibilizer (C) include ethylene / (meth) acrylic acid copolymer, ethylene / fumaric acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate Copolymer, ethylene / glycidyl methacrylate copolymer, ethylene /
Vinyl acetate / glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, N-hydroxymaleimide grafted polyethylene, maleic anhydride grafted polypropylene,
N-hydroxymaleimide grafted polypropylene, maleic anhydride grafted ethylene / propylene copolymer, acrylic acid grafted ethylene / propylene copolymer, maleic anhydride grafted ethylene / propylene / diene monomer copolymer, acrylic acid grafted ethylene /
Examples include a propylene / diene monomer copolymer and an N-hydroxymaleimide grafted ethylene / propylene / diene monomer copolymer. These may be used in combination of two or more.

Particularly preferred among (C) are one or more modified polyolefins selected from the following (C1) to (C3). (C1): a number average molecular weight of 800 to 30,000;
Modified low molecular weight polyolefin having an acid value of 5-150. (C2): a number average molecular weight of 800 to 30,000;
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (C3): A part or all of (C1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 80.
0-30,000 modified low molecular weight polyolefins.

(C1) is a low molecular weight polyolefin having a number average molecular weight of 700 to 25,000 obtained by a polymerization method of propylene and / or ethylene or a thermal degradation method of high molecular weight polypropylene and / or polyethylene, and α, β -It can be obtained by reacting an unsaturated carboxylic acid and / or an anhydride thereof, if necessary, in the presence of an organic peroxide by a solution method or a melting method to modify. From the viewpoint of easy modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferable. The low-molecular-weight polyolefin obtained by the thermal degradation method can be obtained, for example, by the method described in JP-A-3-62804.

Examples of the α, β-unsaturated carboxylic acid or its anhydride used for the modification include (meth) acrylic acid, (maleic anhydride), maleic acid, fumaric acid, (anhydrous) itaconic acid and citraconic anhydride. No. Among these, maleic acid (anhydride) is preferred. These amounts used during the modification are usually 1 to 25% by weight, preferably 3 to 20% by weight, based on the weight of the low molecular weight polyolefin. The number average molecular weight of (C1) obtained by the above method is usually from 800 to 30,000, preferably from 1,000 to 20,000. Number average molecular weight is 80
If it is less than 0, the heat resistance is poor, and if it exceeds 30,000, the effect as a compatibilizer is poor, and the mechanical properties of the resin composition deteriorate. The acid value of (C1) (mgKOH / g)
Is usually 5 to 150, preferably 10 to 100.
When the acid value is less than 5, the effect as a compatibilizer is poor, and
If it exceeds 0, the hue deteriorates, which causes coloring of the resin composition.

(C2) can be obtained by subjecting the above (C1) to secondary modification with an alkanolamine or the like. Alkanolamines include, for example, monoethanolamine, monoisopropanolamine, diethanolamine and diisopropanolamine.
Of these, particularly preferred is monoethanolamine. The hydroxyl value (mgKOH / g) of (C1) is usually 5 to 150, preferably 10 to 100. When the hydroxyl value is less than 5, the effect of introducing the hydroxyl group is small,
If the ratio exceeds the above range, the hue deteriorates, which causes coloring of the resin composition.

(C3) can be obtained by esterifying a part or all of the (anhydride) carboxylic acid unit of (C1) with a polyoxyalkylene compound.
Examples of the polyoxyalkylene compound used for the esterification include a compound having a hydroxyl group at both terminals such as polyethylene glycol and polypropylene glycol, and a compound in which the above hydroxyl group is substituted with an amino group or an epoxy group. Further, alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol,
Polyoxyalkylene compounds having a hydroxyl group at one end, and the like, in which an alkylene oxide is added to a compound having active hydrogen, such as 2-ethylhexyl alcohol or a phenol (phenol, alkylphenol, naphthol, phenylphenol, or benzylphenol). Can be The number average molecular weight of these polyoxyalkylene compounds is usually from 300 to 5,000. Although the esterification ratio is not particularly limited, it is preferable that 10 to 100 mol% of the (anhydrous) carboxylic acid unit (C1) is esterified. The number average molecular weight of (C3) is usually 8
00 to 30,000, preferably 1,200 to 250,000
00. If it is less than 800, heat resistance is poor, and
If it exceeds 0, the effect as a compatibilizer will be poor.

The modified low molecular weight polyolefins (C1) to (C3) exemplified above may be used in combination of two or more. A modified low-molecular-weight polyolefin having all of a carboxyl group, a hydroxyl group and a polyoxyalkylene group in the molecule may be used.

The amount of (C) in the resin composition of the present invention is usually 0.2 to 15% by weight, preferably 0.5 to 10% by weight.
It is. When the amount of (C) is less than 0.2% by weight, the effect as a compatibilizer is reduced, so that the problem of phase separation is likely to occur. When the amount exceeds 15% by weight, the mechanical strength of the resin decreases.

Further, the resin composition of the present invention may contain a metal salt (D) comprising a halide of an alkali metal and / or an alkaline earth metal for the purpose of further improving the antistatic property. (D) includes lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide,
Examples thereof include magnesium bromide. Preferred among these are lithium chloride, sodium chloride and potassium chloride.

The amount of (D) used is usually 0.01 to 2% by weight, preferably 0.02 to 0.5% by weight, based on the total weight of the resin composition of the present invention. If the amount is less than 0.01% by weight, the effect is not exhibited. If the amount exceeds 2% by weight, the resin precipitates on the resin surface and may impair the appearance of the resin, which is not preferable.

There is no particular limitation on the method of adding (D), but from the viewpoint of easy dispersion in the composition,
It is preferable to disperse in advance in the compound (A) having a sulfonic acid (salt) group. When (D) is dispersed in (A), a method in which (D) is previously added and dispersed during polymerization of (A) is particularly preferable.

The antistatic resin composition of the present invention may be used as a molded product as it is, or may be molded in a state (master batch) mixed with (B) in advance.

The antistatic resin composition of the present invention further comprises:
According to various uses, other known additives for resins may be added as long as the properties of the resin are not impaired. Additives that can be blended include pigments, dyes, fillers, nucleating agents, glass fibers, surfactants, lubricants, plasticizers, release agents, antioxidants,
Flame retardants, ultraviolet absorbers and the like.

[0036]

EXAMPLES The present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In the following, “part” indicates “part by weight” and “%” indicates “% by weight”.

[Production of antistatic agent] Production Example 1 Polyethylene glycol having a number average molecular weight of 300 (PEG)
300) 333 parts, 274 parts of 5-sulfoisophthalic acid sodium salt dimethyl ester (SIMP) and 0.7 parts of dibutyltin oxide are charged into a reaction vessel, and 5 mmHg
The temperature was raised to 190 ° C. under reduced pressure, and transesterification was performed for 6 hours while distilling off methanol. The antistatic agent of the present invention having five sodium sulfonate groups in one molecule [A
-1] (PEG300: SIPM = 6: 5).

Production Example 2 171 parts of ethylene glycol (EG) and SIPM 163
And 0.3 part of dibutyltin oxide were charged into a reaction vessel, and a transesterification reaction was carried out at 170 ° C. for 3 hours under a nitrogen stream, and most of methanol was distilled off. Subsequently, polyethylene glycol having a number average molecular weight of 400 (PEG40
0) 147 parts and dibutyltin oxide 0.3 part were added, the temperature was raised to 220 ° C. under a reduced pressure of 5 mmHg, and a polycondensation reaction was carried out for 4 hours while EG was distilled off. Antistatic agent [A-2] of the present invention having three sodium sulfonate groups in one molecule (PEG400: EG: SIMP = 2: 2:
3) was obtained.

[Production of antistatic agent containing metal salt] Production Example 3 The same operation as in Production Example 2 was carried out except that 1.5 parts of lithium chloride was charged together with EG, SIPM and dibutyltin oxide. The antistatic agent of the present invention having three sodium sulfonate groups in one molecule and containing lithium chloride [A-
3] (PEG400: EG: SIMP = 2: 2: 3) was obtained. The content of lithium chloride measured by X-ray fluorescence analysis was 0.5%.

[Production of Comparative Antistatic Agent] Comparative Production Example 1 212 parts of diethylene glycol (DEG) and SIPM2
96 parts and 0.7 parts of dibutyltin oxide were charged into a reaction vessel, and a transesterification reaction was performed at 180 ° C. for 3 hours under a nitrogen stream, and most of methanol was distilled off. Then 5
The reaction was carried out for 3 hours while distilling off methanol under a reduced pressure of mmHg. Comparative antistatic agent [A-4] having one sodium sulfonate group in one molecule (DEG: SIPM =
2: 1).

[Production of Modified Low-Molecular-Weight Polyolefin] Production Example 4 A number-average molecular weight of 3,000 and a density of 0.
38 parts of low molecular weight polyethylene of 93 and maleic anhydride 2
Of xylene and 60 parts of xylene were dissolved under nitrogen at 140 ° C. under xylene reflux, and a 50% xylene solution in which 0.3 part of ditertiary butyl peroxide was dissolved was added to the solution.
After dropwise addition over a period of 2 minutes, and the reaction was carried out for 2 hours, the solvent was distilled off to obtain an acid-modified low molecular weight polyethylene. Its acid value (mgKOH / g) was 28.0 and number average molecular weight was 3,800. This modified product is abbreviated as [C-1] below.

Production Example 5 95 parts of a low-molecular-weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89, obtained by a thermal degradation method, and 5 parts of maleic anhydride were melted at 180 ° C. under nitrogen. Xylene in which 1.5 parts of dicumyl peroxide are dissolved
A 0% solution was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. It has an acid value of 25.7 and a number average molecular weight of 1
It was 5,000. This modified product is abbreviated as [C-2] below.

Production Example 6 95 parts of [C-2] obtained in Production Example 5 was replaced with xylene 100
Was dissolved under nitrogen at 120 ° C., and then 5 parts of monoethanolamine was added dropwise over 15 minutes, and the mixture was reacted for 1 hour. Thereafter, the solvent and unreacted monoethanolamine were distilled off to remove hydroxyl groups. To obtain a modified low molecular weight polypropylene. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000. This modified product is abbreviated as [C-3] below.

Production Example 6 95 parts of [C-2] obtained in Production Example 5 and 50 parts of an adduct of 24 mol of lauryl alcohol with ethylene oxide were melted at 180 ° C. under nitrogen, and then esterified under reduced pressure of 10 mmHg for 5 hours. The reaction was performed to obtain a polyoxyalkylene-modified low molecular weight polypropylene. This had a hydroxyl value of 0.5 and a number average molecular weight of 18,000.
In addition, NMR analysis confirmed that the esterification reaction was performed quantitatively. This modified product is referred to as [C-
4].

[Preparation of Masterbatch] Production Example 7 After blending the components (A) to (C) in the proportions shown in Table 1 for 3 minutes using a Henschel mixer, the mixture was mixed at 180 ° C. with a vented twin-screw extruder. [When using B1-1]) or 2
The mixture was melt-kneaded under the conditions of 30 ° C. (when using [B1-2]), 100 rpm, and a residence time of 5 minutes to form a master batch (M-
1) and (M-2) were obtained.

[0046]

[Table 1] (Note) [B1-1]; polyethylene [trade name “Lexlon J6”
9 ", manufactured by Nippon Petrochemical Co., Ltd.] [B1-2]; Polypropylene [trade name" Ube Polypro J609 ", manufactured by Ube Industries, Ltd.] [B2-1]; Nylon 12 [trade name" Ube Nylon 3 "
024U ”, manufactured by Ube Industries, Ltd.] [B2-2]; nylon 6 [trade name“ Ube nylon 10 ”
13B ", manufactured by Ube Industries, Ltd.)

Examples 1 and 2 The masterbatches (M-1) and (M-2) and the polyolefin-based resin (B1) shown in Table 2 were melt-kneaded under the same conditions as in Production Example 7, respectively. A resin composition was obtained. Table 2 shows the composition of the resin composition of the present invention via the masterbatch and the final ratio of each component.

[0048]

[Table 2]

Examples 3 to 9 and Comparative Examples 1 to 3 The ratios (A) to (D) shown in Table 3 were blended and kneaded under the same conditions as in Production Example 7 to obtain a resin composition of the present invention and a comparative sample. A resin composition was obtained.

[0050]

[Table 3] (Note) [B2-3]; polybutylene terephthalate (trade name “Duranex 2000”, manufactured by Polyplastics Co., Ltd.) [D-1]: Potassium chloride (added during kneading in a twin-screw extruder) [D-2] ]; Lithium chloride (added during production of antistatic agent)

Performance Test The resin composition of the present invention and the comparative resin composition were subjected to a cylinder temperature of 180 ° C. (when [B1-1] was used) or 230 ° C. (when [B1-2] was used) using an injection molding machine. Case), a test piece is prepared at a mold temperature of 50 ° C.,
The resin physical properties and compatibility were evaluated. Table 4 shows the results. In addition, evaluation of antistatic property and compatibility was performed by the following method. (1) Antistatic property: The test piece was subjected to the treatment and conditioning described below, and the surface resistivity was measured. (A) After molding, the test piece is kept at 23 ° C. and humidity 50% R
Leave for 24 hours under H atmosphere. (B) After molding, test specimens were washed with detergent (mama lemon; lion
After washing with an aqueous solution and then sufficiently washing with ion-exchanged water, the water on the surface was dried and removed, and then at 23 ° C.
Left in a 50% RH atmosphere for 24 hours. (2) Tensile yield point strength: ASTM D638 (3) Compatibility: The molded product was bent and its fracture surface was visually observed and evaluated according to the following evaluation criteria. Evaluation criteria ○: good △: slight delamination is observed ×: poor compatibility, delamination

[0052]

[Table 4]

As is apparent from Table 4, the thermoplastic resin compositions containing the antistatic agent of the present invention were prepared in Comparative Examples 1 to
Compared to No. 3, the permanent antistatic property is remarkably excellent, indicating that the composition has an excellent permanent antistatic property that has not been achieved conventionally.

[0054]

The antistatic agent of the present invention has the following effects. (1) Since the content of the ionic group is high, the effect of imparting the antistatic property is high even if a small amount is added. (2) Since the ionic portion and the non-ionic portion are not localized in a specific portion but form a certain repeating structure and the ionic portions are averaged, the antistatic effect is high. (3) Since a high antistatic effect is exhibited even with a small amount of addition, the original physical properties of the synthetic resin as a base are not impaired. (4) Since the ionic group concentration does not decrease even if the molecular weight is increased, the heat resistance of the antistatic agent itself can be improved without lowering the effect of imparting antistatic properties.

Because of the above-mentioned effects, the resin composition containing the antistatic agent of the present invention has excellent permanent antistatic properties which cannot be achieved by conventional techniques, and has mechanical properties and molding properties. It is also very useful as various molding materials that require antistatic properties for housing products for home appliances and OA equipment, various plastic containers, automobile parts, and the like.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (7)

(57) [Claims] 1. An aromatic dicarboxylic acid having a sulfonic acid (salt) group or an ester-forming derivative thereof (a1),
One or more diols (a2) selected from the group consisting of alkanediols having 2 to 10 carbon atoms, polyoxyalkylene glycols and alkylene oxide adducts of bisphenols are essential constituent units, and two or more diols in the molecule are used. Polyester compound having sulfonic acid (salt) group (A) {Aromatic dicarboxylic acid substituted with sulfonic acid salt group
Aromatic containing 3 to 40 mol% of acid and / or ester thereof
Dicarboxylic acids and / or their esters, poly (alkyl
Oxide) glycols and glycos having 2 to 10 carbon atoms
Polyether ester obtained by polycondensation of
Good. An anionic antistatic agent consisting of ｝ . 2. The antistatic agent according to claim 1, wherein (a2) is at least one member selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycol and an ethylene oxide adduct of bisphenols. 3. The antistatic agent (A) according to claim 1 or 2 and 1 to 50% by weight and the thermoplastic resin (B) 99 to 50.
% By weight of the resin composition. 4. (B) is a polyolefin resin (B1)
The resin composition according to claim 3, which is 5. The method according to claim 1, wherein (B) is a polyolefin resin (B).
The resin composition according to claim 3, which is a thermoplastic resin obtained by combining 1) 100 parts by weight and 1 to 20 parts by weight of at least one resin (B2) selected from a polyamide resin, a polyester resin, and a polyacetal resin. 6. The modified polyolefin-based compatibilizer (C) is added in an amount of 0.2 to the total weight of (A) and (B).
The resin composition according to any one of claims 3 to 5, wherein the content of the resin composition is from 15 to 15% by weight. 7. The resin composition according to claim 6, wherein (C) is at least one selected from the following (C1) to (C3). (C1): a number average molecular weight of 800 to 30,000;
A modified low molecular weight polyolefin having an acid value of 5 to 150 (C2); a number average molecular weight of 800 to 30,000;
Modified low molecular weight polyolefin having a hydroxyl value of 5 to 150 (C3); a part or all of (C1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 80.
0-30,000 modified low molecular weight polyolefin