JPH0881534A - Permanetly antistatic composite resin molding - Google Patents

Abstract

PURPOSE: To obtain a molding excellent in permanent antistatic properties, mechanical properties and moldability by mixing a thermoplastic resin with an antistatic agent comprising a polyurethane containing a metal benzenesulfonate derivative. CONSTITUTION: This molding is made from a mixture comprising a permanent antistatic agent (A) for a thermoplastic resin, comprising a polyurethane comprising units of the formula (wherein Ar is a trivalent aromatic hydrocarbon group; X is a bivalent group selected from among O-CO, NH-CO and O; Z is a bivalent group selected from among COO, CO-NH and O or H; and M is a monovalent or bivalent metal ion) and a thermoplastic resin (B). It is desirable that the molecular weight of component A is 6000-200000, that the mixture comprises 3-40wt.% component A and 60-97wt.% component B and that the total amount of the units of the formula contained in component A is 0.5-40wt.% based on the total weight of the units of component A. This molding has such high permanent antistatic properties as not to be attainable by any prior art, can be obtained at a molding temperature in a range boadened to lower temperatures and has excellent molding appearance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent antistatic agent, a composite resin molding containing the same, and an antistatic method therefor.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting antistatic properties to a resin, a method of adding a surfactant having a polyhydric alcohol fatty acid ester as a main component (Japanese Patent Publication No. 6-21198, Japanese Patent Publication No. 43104, etc.). )It has been known.

However, these methods have a problem in the durability of the antistatic property such that the antistatic property disappears when washed with water.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies to obtain a composite resin molded article having good permanent antistatic properties and resin properties.

That is, the present invention relates to a permanent antistatic agent for blending a thermoplastic resin comprising a polyurethane (A) having a unit of the formula (1); a permanent antistatic composite obtained by incorporating the antistatic agent into a thermoplastic resin. Resin molded product: A permanent antistatic composite resin molded product comprising the composite resin molded product, in which at least a part of the (A) phase is dispersed in a streak form in the composite resin surface layer portion;
And a complex formed by reacting the active hydrogen-containing polyfunctional compound (A-1) with the polyisocyanate (A-2) in the melted (B) to form (A), or (B) and (A)
Add at least 10 ² sec ^-1 to the composite obtained by melting and kneading
Is applied to disperse at least a part of the phase (A) in the form of stripes in the surface layer portion of the composite resin.

[0006]

Embedded image

(In the formula, Ar is a trivalent aromatic hydrocarbon group;
-X- is -O-CO-, -NH-CO- or -O-;
-Z- is -COO-, -CO-NH-, -O- or-.
H; M represents a monovalent or divalent metal ion. )

In the formula (1) of the present invention, Ar is a trivalent aromatic hydrocarbon group (benzene nucleus), for example, 3,5.
Or a residue of 2,5-di (carboxy) benzenesulfonic acid. Preferred among X is -OC.
Preferred among O-, -NH-CO-, and Z-
COO- and -CO-NH-. As M, ions of alkali metals (lithium, sodium, potassium, rubidium, cesium, etc.), alkaline earth metals (magnesium, calcium, strontium, barium, etc.) and other metals (iron, copper, silver, zinc, manganese, etc.) can give. Of these, preferred are lithium, sodium, potassium, magnesium, calcium and zinc.

In the present invention, the polyurethane (A) having the unit of the formula (1) is a polyfunctional compound containing an active hydrogen (A).
-1) and / or polyisocyanate (A-2) having at least part of the unit of the formula (1) can be used to polymerize (A-1) and (A-2). Among (A-1) and (A-2), those having a unit of the formula (1) include, for example, di (carboxy) benzenesulfonic acid metal salt [3,5-di (carboxy) benzenesulfonic acid sodium salt, 2,5-di (carboxy) benzene sulfonate sodium, 3,5-di (carboxy) benzene sulfonate lithium, 3,5-di (carboxy) benzene sulfonate calcium, etc.], bis (hydroxyethoxy) benzene sulfonate metal Salt [2,5-bis (hydroxyethoxy) benzenesulfonic acid potassium salt], carbo- (β-hydroxyethoxy) -hydroxyethoxy-benzenesulfonic acid metal salt [2-carbo- (β-hydroxyethoxy) -hydroxyethoxy- Lithium benzene sulfonate etc.] Further, these and polyols [ethylene glycol, polyethylene glycol (hereinafter abbreviated as PEG), diethanolamine, dihydroxymethylpropionic acid, etc.],
Compounds derived from polyamines (ethylenediamine, hexamethylenediamine, monoethanolamine, diethylenetriamine, etc.) and polycarboxylic acids (succinic acid, adipic acid, terephthalic acid, etc.) [3,5-bis (carbo-β hydroxyethoxy) -Sodium benzenesulfonate, polycondensate of sodium 3,5-di (carboxy) benzenesulfonate and polyethylene glycol, polycondensate of sodium 3,5-di (carboxy) benzenesulfonate and ethylenediamine, 3,5 -Poly (condensation product of sodium bis (carbo-β-hydroxyethoxy) -benzenesulfonate and adipic acid). Furthermore, in order to adjust the reactivity of the end of these derived compounds, the end is treated with polyamine (such as ethylenediamine), polyisocyanate [diphenylmethane diisocyanate (hereinafter abbreviated as MDI)], epihalohydrin (epichlorohydrin etc.) or epoxy resin or the like. It may be a reacted product.

The molecular weight of the compound having the unit of the formula (1) is usually 250 to 6000, preferably 250 to 25.
00.

The total amount of units of the formula (1) in (A) is usually 0.5 to 40% by weight, preferably 0.5 to 2
It is 5% by weight. If it is less than 0.5% by weight, the antistatic property becomes insufficient, and if it exceeds 25% by weight, the resin properties become insufficient, which is not preferable.

In the present invention, the active hydrogen-containing polyfunctional compound (A-1) optionally used for the production of (A) is, for example, a low molecular weight diol [ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol etc.]; polyether diol [alkylene oxide (ethylene oxide, propylene oxide, butylene oxide etc.) adduct of the low molecular weight diols exemplified above, ring-opening polymer of alkylene oxide (polytetramethylene glycol etc.)]; Polyester diol [condensed polyester diol of aliphatic dicarboxylic acid (adipic acid, maleic acid, dimerized linoleic acid, etc.) or aromatic dicarboxylic acid (phthalic acid, terephthalic acid, etc.) with the low molecular weight diols exemplified above, ε
-Polylactone diol, etc. by ring-opening polymerization of caprolactone]; Diamines (isophoronediamine, 4,4 '
-Diamino-3,3'-dimethyldicyclohexylmethane, polyetherdiamine, etc.); trivalent or higher alcohols (trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher amines (diethylenetriamine, triethylenetetramine, etc.) Amino alcohol (such as triethanolamine); and an active hydrogen-containing urethane prepolymer obtained by reacting the above active hydrogen-containing compound with the following polyisocyanate.

The molecular weight of (A-1) is usually 62 to 2000.
It is 0, preferably 62 to 6000.

Examples of the polyisocyanate (A-2) optionally used in the production of (A) in the present invention include aromatic diisocyanates (MDI, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, etc.), alicyclic rings. Formula diisocyanate (isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate,
Diisocyanate methylcyclohexane etc.), aliphatic diisocyanate (hexamethylene diisocyanate etc.), trifunctional or higher functional polyisocyanate [triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, hexamethylene diisocyanate cyclic trimer etc.], and these And an isocyanate group-containing urethane prepolymer obtained by the reaction of the compound with the active hydrogen-containing compound.

Two or more kinds of these compounds having at least two active hydrogens and polyisocyanate may be used in combination.

At this time, the ratio of the isocyanate group to the active hydrogen is usually 1: 2 to 2: 1, the terminal group may be either the isocyanate group or the active hydrogen, and the terminal isocyanate group has one active hydrogen. You may block it with.

The molecular weight of (A) in the permanent antistatic resin molding obtained in the present invention is usually 6,000 to 5 on a weight average basis.
It is 0,000. If the molecular weight is less than 6,000 or more than 500,000, the permanent antistatic property is not sufficiently exhibited.

It is also possible to use a mixture of the active hydrogen-containing polyfunctional compound and / or polyisocyanate having the unit of the formula (1) with another polymerizable functional group-containing compound.

As (B) in the resin composition of the present invention,
Examples thereof include thermoplastic resins such as (co) polymers of vinyl compounds, polyesters, polyamides, polyimides, polyurethanes, and poly (thio) ethers.

Of these, vinyl compounds constituting the (co) polymer of vinyl compounds include olefins (ethylene, propylene, butene-1, isobutene, 4-methylpentene-1, octene, etc.); aromatic vinyl Hydrocarbons or their substitution products (styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, vinyltoluene, etc.); (meth) acrylic acid and its alkyl (C 1-18) esters (methyl acrylate) , Ethyl acrylate, butyl acrylate, methyl methacrylate, etc.); vinyl ether (methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, etc.); vinyl alcohol derivative (vinyl acetate, vinyl butyrate, etc.); (meth) acrylonitrile; (meth) acrylic Bromide and N-substituted derivatives thereof;
Dienes (butadiene, isoprene, etc.); halogen-substituted compounds of ethylene (vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride, etc.); unsaturated polycarboxylic acids (maleic acid, fumaric acid, etc.) or their anhydrides, halogens Compounds, alkyls (C1-C1
8) Examples include esterified products.

Examples of polymers or copolymers of these vinyl compounds include polyolefin thermoplastic resins [polyethylene, polypropylene, ethylene-α-olefin copolymer (ethylene-propylene copolymer, ethylene-butene-1 Copolymers, etc.), olefin-diene copolymers (EPDM, etc.), ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, chlorinated polypropylene, maleic acid-modified polypropylene, etc.] Thermoplastic resins (polystyrene, ABS resin, AS resin), polyacrylic acid, polymethylmethacrylate, polyacrylonitrile, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polybutadiene, polyvinyl chloride, polytetrafluoroethylene, etc. You can

As the polyester, aromatic polyesters [polymers of aromatic dicarboxylic acid esters (polyethylene terephthalate, polybutylene terephthalate,
Polycondensation products of bisphenol A with terephthalic acid and / or isophthalic acid, etc.), polycondensation products of paraoxybenzoic acid, etc.]; Etc.]; Polycarbonate; and compounds of these two or more kinds of co-esterified products and these polymers, and alkylene oxides (ethylene oxide, propylene oxide, etc.) or polyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.) The copolycondensation product of

As the polyamide, 6-nylon, 6,
6-nylon, 6,10-nylon, 11-nylon,
12-nylon, 4,6-nylon and the like and their 2
Examples include co-amidated products of at least one kind, compounds forming these polymers, compounds forming polyester, and copolycondensates of alkylene oxides (ethylene oxide, propylene oxide, etc.) or polyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.). To be

As the polyimide, pyromellitic acid and 1,
Examples thereof include polycondensates with 4-diaminobenzene; copolycondensates of compounds forming polyimide with the compounds forming the polyamide, that is, polyamideimide.

Polyurethanes include active hydrogen-containing polyfunctional compounds (polyethylene glycol, polytetramethylene glycol, polylactone diol, etc.) and polyisocyanates (MDI, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, etc.). Examples thereof include polyester-based polyurethanes and polyether-based polyurethanes that do not have the unit of the formula (1) obtained.

Examples of the poly (thio) ether include polyphenylene ether, polyether ether ketone, polyphenylene sulfide, polysulfone and the like, and co-etherified products of two or more of these.

Of these thermoplastic resins (B), preferred are (co) polymers of vinyl compounds, particularly polyolefin thermoplastic resins and styrene thermoplastic resins.

Two or more kinds of those exemplified above as the thermoplastic resin (B) can be used in combination.

The weight average molecular weight of the thermoplastic resin (B) is usually 10,000 to 7,000,000, preferably 10,000 to 3,000,000. If the molecular weight is less than 10,000 or exceeds 7,000,000, molding becomes difficult, which is not practical.

The amount of this thermoplastic resin (B) is 60 to 9
It is 7% by weight, preferably 80 to 97% by weight. 60
If it is less than 100% by weight, the mechanical strength will be poor, and if it exceeds 97% by weight, the antistatic property will be deteriorated.

The melting temperature of (B) is 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 to 230 ° C. If the melting temperature is less than 80 ° C, the heat resistance is poor and it is not practical.

In the present invention, a dispersant may be present in the composite resin molded product in order to assist the dispersion of the respective constituent components.

The preferred dispersant (C) is
When the thermoplastic resin (B) is a polyolefin, it is a polyolefin having active hydrogen, (anhydrous) carboxylic acid group, or carboxylic acid halide group, or a copolymer-based dispersant of polyolefin and polyurethane. Of these, preferred are hydroxyl group-, epoxy group-, and acid anhydride group-containing polyolefins. More specific examples include hydroxyl group-modified polyolefin and maleic anhydride graft-modified polyolefin. When (B) is polystyrene, preferred (C) is a styrene (co) polymer containing a hydroxyl group, an epoxy group and an acid anhydride group. More specific examples thereof include a styrene-hydroxyethyl methacrylate copolymer, a styrene-glycidyl methacrylate copolymer, a styrene-maleic anhydride copolymer, and a terminal hydroxypolystyrene. The resin properties of the molded product containing these dispersants (C) are improved. (B) is an aromatic polyester, polycarbonate, polyamide,
In the case of polyimide, polyamide imide, polyphenylene oxide, polyether ether ketone, polyphenylene sulfide, and polysulfone, styrene maleic anhydride copolymer, SBS resin, SEBS resin, terminal amino type and / or carboxylic acid type polyamide oligomer, terminal carboxylic acid Acid-type and / or hydroxyl-type polyester oligomers are mainly used.

The number average molecular weight of (C) is usually 800 to
3,000,000, preferably 1,000-200,
It is 000. If it is less than 800, the physical properties of the resin of the molded product are poor, and if it is 300,000 or more, the effect of adding (C) cannot be obtained.

When the dispersant (C) is used, the proportion of (C) is usually 0.0 with respect to the total weight of (B) and (A).
It is 5 to 50%, preferably 0.1 to 20%.

The composite resin composition of the present invention is obtained by polymerizing (A-1) and (A-2) in molten (B). It can also be obtained by melt-kneading (B) and (A) produced in advance from (A-1) and (A-2).
In these cases, polymerization or melt kneading can be carried out in the presence of (C).

The reaction temperature for producing the composite resin composition is usually in the range of 100 to 350 ° C., preferably 120.
~ 230 ° C. The reaction pressure is not particularly limited, but when industrial production is taken into consideration, it is usually reduced pressure (0.1 mmHg) to 50 atm, preferably reduced pressure (0.1 mmHg) to 30 atm.

When the urethanization reaction is carried out in advance from (A-1) and (A-2) to produce (A), the reaction temperature is usually in the range of 30 to 230 ° C., preferably 40 to 2
It is 00 ° C. The reaction pressure at that time is not particularly limited, but when considering industrial production, it is usually reduced pressure (0.1 mmHg) to
The pressure is 50 atm, preferably reduced pressure (0.1 mmHg) to 30 atm.

During these reactions, if necessary, a solvent,
A catalyst can also be used. The solvent to be used may be a known solvent for urethanization reaction having no active hydrogen, and examples thereof include dimethylformamide, methyl ethyl ketone and toluene. The catalyst to be used may be one known as a catalyst for urethanization reaction, and examples thereof include organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate, and amines such as triethylamine and diazabicycloundecene. .

Examples of the reaction vessel include various known mixers such as an extruder, a kneader, a Banbury mixer, and a reaction tank equipped with a stirring blade.

In the present invention, it is preferable from the viewpoint of antistatic property that at least a part of the phase (A) is dispersed in the surface layer of the composite resin in a stripe shape. 10 ² s to disperse in stripes
It is necessary to apply a shear of ec ^-1 or more. Shear 10
If it is less than ² sec ^-1 , sufficient streaky dispersion cannot be obtained in the surface layer portion, and the antistatic property is poor. For imparting shear, various known molding machines such as an injection molding machine, an inflation molding machine, an extrusion molding machine, a blow molding machine, and a spinning machine can be used.

The molded product of the present invention comprises a container, cases,
It is suitable for bumpers, hoses, films and various housing materials.

[0043]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight. The evaluation of the molded articles described in Examples and Comparative Examples was performed by the following methods. (1) Impact strength: ASTM D256 (notched, 3.2 mm thickness) (2) Bending elastic modulus: ASTM D790 (3) Surface specific resistance value: A super insulation tester (Advantest 20)
The measurement was carried out in an atmosphere of RH and 65% RH. The surface resistivity was evaluated by subjecting the test piece to the treatment and conditioning described below and measuring the surface resistivity. (A) Unwashed with water: after molding, the test piece is kept at 20 ° C.
Leave for 24 hours in an atmosphere of 65% humidity RH. (B) Washing with water: After molding, the test piece was washed with a detergent (Mama Lemon;
After washing with an aqueous solution of Lion Co., Ltd., followed by thorough washing with ion-exchanged water, the surface moisture is removed by drying, and the product is left standing at 20 ° C. and a humidity of 65% RH for 24 hours. The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, part means part by weight.

Example 1 850 parts of polypropylene [UBE-manufactured by Ube Industries, Ltd.]
Polypro J609H, hereinafter abbreviated as PP], 1.4 parts of sodium 3,5-bis (carbo-βhydroxyethoxy) -benzenesulfonate (hereinafter abbreviated as SIPE),
7.2 parts ethylene glycol, 94.8 parts PEG1
540 (PEG having a molecular weight of 1540; the same shall apply hereinafter), and 46.5 parts of MDI are twin-screw extruders (Toshiba Machinery Co., Ltd.
Using EM35B, 37 mmφ, L / D = 41), the mixture was melt-kneaded at a cylinder temperature of 190 ° C. for 5 minutes. Cylinder temperature 200 ℃, mold temperature 50 ℃
Was injection-molded to prepare a test piece of the molded article of the present invention (shear at this time was 10 ³ sec ⁻¹ ) and the surface resistivity and the resin property evaluation result of this test piece are shown in Table 1.

Example 2 15 parts of maleic anhydride modified polypropylene [bound maleic acid content 5%, number average molecular weight 5,000, hereinafter PP-M
Abbreviated as A; corresponding to dispersant (C)] was added and melt-kneaded under the same materials and conditions as in Example 1. The obtained composite resin was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a molded body test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.
Shown in

Example 3 25 parts SIPE, 47 parts ethylene glycol, 65
Example 1 with 0 parts PEG 2000, 288 parts MDI
Polyurethane (hereinafter abbreviated as PU-1) was obtained by melt-kneading for 5 minutes at a cylinder temperature of 190 ° C. using the same twin-screw extruder. 800 parts of PP, 200 parts of PU-1 and 1.50 parts of PP-MA were melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. The obtained composite resin was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a molded body test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

Example 4 70 parts of sodium 3,5-di (carboxy) benzene sulfonate, 605 parts of PEG 2000, 45 parts of ethylene glycol, 322 parts of MDI, 0.1 part of dibutyltin dilaurate were prepared as in Example 1. Polyurethane (hereinafter abbreviated as PU-2) was obtained by melt-kneading for 5 minutes at a cylinder temperature of 190 ° C. using the same twin-screw extruder. 800 copies of P
P, 200 parts of PU-2, and 15 parts of PP-MA were melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. The obtained composite resin was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a molded body test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

Comparative Example 1 990 parts of PP, 10 parts of polyhydric alcohol fatty acid ester antistatic agent (Chemistat 1 manufactured by Sanyo Kasei Co., Ltd.)
100) was melt-kneaded using the same twin-screw extruder as in Example 1. The obtained composition was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a test piece.
The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

[0049]

[Table 1]

Example 5 800 parts of polystyrene (Asahi Kasei Polystyrene 600 manufactured by Asahi Kasei Corporation, hereinafter abbreviated as PS), 3.6 parts of SIP
E, 9.6 parts ethylene glycol, 126 parts PEG
2000, 57 parts of MDI, 0.02 part of dibutyltin dilaurate, and 3 parts of one-end hydroxypolystyrene (Mw = 3300; dispersant) were added to the same twin-screw extruder as in Example 1 at a cylinder temperature of 200 ° C. And melt-kneaded for 5 minutes. The obtained composite resin is heated to a cylinder temperature of 200.
Injection molding at a mold temperature of 50 ° C. and a mold temperature of 50 ° C. to prepare a test piece of the molded article of the present invention, and the surface resistivity of this test piece was evaluated. The results of the characteristic evaluation are shown in Table 2.

Example 6 800 parts of high impact polystyrene (Dialex HT-60 manufactured by Mitsubishi Kasei Co., Ltd.), 3.6 parts of SIPE, 9.
6 parts ethylene glycol, 126 parts PEG200
Using 0, 57 parts of MDI, 0.02 part of dibutyltin dilaurate, and 30 parts of Idemitsu Petrochemical Co., Ltd. Admast 3000 (dispersant), a cylinder temperature of 200 was obtained using the same twin-screw extruder as in Example 1. Melt kneading was carried out at 0 ° C for 5 minutes. The obtained composition was injection molded under the same conditions using the same injection molding machine as in Example 5 to prepare test pieces. The characteristics of this test piece were evaluated in the same manner as in Example 5. The results of the characteristic evaluation are shown in Table 2.

Comparative Example 2 990 parts of PS, 10 parts of polyhydric alcohol fatty acid ester antistatic agent (Chemistat 1 manufactured by Sanyo Kasei Co., Ltd.)
100) was melt-kneaded under the same conditions as in Example 5. The obtained composition was injection molded under the same conditions using the same injection molding machine as in Example 5 to prepare test pieces. The characteristics of this test piece were evaluated in the same manner as in Example 5. The characteristics evaluation results are shown in Table 2.
Shown in

[0053]

[Table 2]

[0054]

EFFECTS OF THE INVENTION The molded article of the present invention has a permanent antistatic property which cannot be achieved by the conventional techniques and has excellent resin properties. The permanent antistatic method using the polyurethane (A) according to the present invention has a molding processability such that the molding temperature can be extended to a lower temperature range as compared with the conventionally known method using a permanent antistatic polymer. Are better. Also, the appearance of the molded product is excellent. Because of the above effects, the molded product of the present invention is useful as a molding material for various applications requiring antistatic properties such as containers, cases, automobile parts, hoses, films, and various housing materials.

Claims (12)

[Claims] 1. A permanent antistatic agent for blending a thermoplastic resin, comprising a polyurethane (A) having a unit of the formula (1). Embedded image (In the formula, Ar is a trivalent aromatic hydrocarbon group; -X- is -O.
-CO-, -NH-CO- or -O-; -Z- is -C
OO-, -CO-NH-, -O- or -H; M represents a monovalent or divalent metal ion. ) 2. (A) is a polyfunctional compound containing active hydrogen (A
-1) and / or polyisocyanate (A-2) is a polymerization product of (A-1) and (A-2) obtained by using a compound having a unit of the formula (1) as at least a part thereof. Item 1. The antistatic agent according to item 1. 3. The molecular weight of (A) is 6,000 to 200,
The antistatic agent according to claim 1 or 2, which is 000. 4. A permanent antistatic composite resin molded product comprising a thermoplastic resin (B) containing the antistatic agent according to any one of claims 1 to 3. 5. (A) 3 to 40% by weight, (B) 60
The molded product according to claim 4, wherein the total amount of the units of the formula (1) contained in (A) is 0.5 to 40% by weight based on (A). 6. The molded product according to claim 4, wherein (B) is a thermoplastic polyolefin resin. 7. The molded article according to claim 6, comprising a composite of (A), (B) and the following dispersant (C). Dispersant (C): a modified polyolefin-based dispersant having active hydrogen, a (anhydrous) carboxylic acid group or a carboxylic acid halide group, or a polyolefin-polyurethane copolymer-based dispersant. 8. The molded product according to claim 4, wherein (B) is a styrene-based thermoplastic resin. 9. (B), (A) and the following dispersant (C)
9. The molded body according to claim 8, which is composed of a composite body of Dispersant (C): A styrene-based dispersant having active hydrogen, a (anhydrous) carboxylic acid group or a carboxylic acid halide group, or a [styrene-based (co) polymer] -polyurethane copolymer-based dispersant. 10. The thermoplastic resin (B) is a thermoplastic resin selected from the group consisting of aromatic polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene oxide, polyetheretherketone, polyphenylene sulfide, and polysulfone.
Alternatively, the molded article according to item 5. 11. A permanent antistatic composite resin molded product comprising the composite resin composition according to any one of claims 4 to 10, in which at least a part of the (A) phase is dispersed in a stripe shape in the composite resin surface layer portion. 12. In the molten (B), (A-1) and (A)
-2) polymerized complex, or (A) and (B)
Add at least 10 ² sec ^-1 to the composite obtained by melting and kneading
The permanent antistatic method for a molded article according to any one of claims 4 to 11, wherein at least a part of the (A) phase is dispersed in the form of stripes in the surface layer of the composite resin by applying the shearing.