JPH0892476A - Permanently antistatic composite resin composition - Google Patents

Abstract

PURPOSE: To obtain a permanently antistatic agent with which a thermoplastic synthetic resin composition satisfactory in permanently antistatic properties and mechanical properties can be obtained, by using a specific polyurethane and a polyacetal in combination. CONSTITUTION: The subject permanent antistatic agent comprises a polyurethane (A) having a surface resistivity of 10<14> Ω or lower and a polyacetal (B) in a weight ratio of 1:10 to 40:1. This " agent is mixed with a thermoplastic resin (C) to give a composition in which the contents of the ingredients (A), (B), and (C) are 2-40wt.%, 1-20wt.%, and 60-97wt.%, respectively. The ingredient (C) is preferably a (co)polymer of a vinyl compound, in particular, a thermoplastic polyolefin or styrene resin. This composition may contain a dispersant, preferably a polyolefin containing hydroxyl, epoxy, or acid anhydride groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent antistatic composite composition, a permanent antistatic resin molding and an antistatic method for resin molded articles.

[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]

Means for Solving the Problems The present inventors arrived at the present invention as a result of extensive studies to obtain a composite composition and a composite resin molded product having good permanent antistatic properties and mechanical properties. .

That is, the present invention is characterized in that the polyurethane (A) having a surface resistivity of 10 ¹⁴ Ω or less and the polyacetal (B) are used together in a weight ratio of 1:10 to 40: 1. Permanent antistatic agent for blending plastic synthetic resin; 2-40% by weight of 10 ¹⁴ based on the weight of the composition.
Polyurethane (A) having a surface resistivity of Ω or less, 2
-20% by weight of polyacetal (B), and 60-9
A permanent antistatic composite composition comprising 7% by weight of a thermoplastic resin (C); and molding using the composition, (A)
Permanent antistatic composite resin molded product in which at least a part of the phases are dispersed in a streak form on the surface layer of the molded product; and further, in the molten (B) and (C), the active hydrogen-containing polyfunctional compound is reacted with polyisocyanate complexes by forming a (a) Te, or (a), (B), and (C) to the composite body formed by melt-kneading, giving shear of at least 10 ² sec ^-1 (a) phase Is a permanent antistatic method for a molded product in which at least a part of the above is dispersed in a streak form at the surface layer of the composite resin.

In the present invention, the surface resistivity of the polyurethane (A) alone must be 10 ¹⁴ Ω or less, preferably 10 ¹³ Ω or less. Even if polyurethane having a surface resistivity of more than 10 ¹⁴ Ω is used, the composite composition having permanent antistatic property, which is the object of the present invention, cannot be obtained.

Polyurethanes having a surface resistivity of 10 ¹⁴ Ω or less include sulfonic acid groups as hydrophilic functional groups,
Examples thereof include polyurethane having a sulfonate group, a hydroxyl group, a carboxylic acid group, a carboxylate group, a quaternary cation, and betaine in the main chain or side chain, and a polyurethane mainly composed of polyethylene glycol.

As such a polyurethane, one having an active hydrogen-containing compound (A-1) and / or a polyisocyanate (A-2) having a hydrophilic group and / or a precursor thereof as at least a part thereof is used. A-1)
It can be produced by reacting (A-2) with (A-2), and then performing neutralization and the like if necessary.

Among (A-1) and (A-2), those having a sulfonic acid group and a sulfonate group include, for example, di (carboxy) benzenesulfonic acid [3,5-di (carboxy) benzenesulfonic acid, 2,5-di (carboxy) benzenesulfonic acid and the like], di (carboxy) benzenesulfonic acid metal salt [3,5-di (carboxy) benzenesulfonic acid sodium salt, 2,5-di (carboxy)
Sodium benzenesulfonate, lithium 3,5-di (carboxy) benzenesulfonate, calcium 3,5-di (carboxy) benzenesulfonate, etc.], bis (hydroxyethoxy) benzenesulfonic acid metal salt [2,5
-Potassium bis (hydroxyethoxy) benzenesulfonate, etc.], carbo- (β-hydroxyethoxy) -hydroxyethoxy-benzenesulfonic acid metal salt [2-carbo- (β-hydroxyethoxy) -hydroxyethoxy-benzenesulfonate, etc. ] In addition, these and polyols [ethylene glycol, polyethylene glycol (hereinafter abbreviated as PEG), diethanolamine, dihydroxymethylpropionic acid, etc.], polyamines (ethylenediamine, hexamethylenediamine, monoethanolamine, diethylenetriamine, etc.), polycarboxylic acids (succinic acid, adipine) Acid, terephthalic acid, etc.) [sodium 3,5-bis (carbo-β hydroxyethoxy) -benzenesulfonate, sodium 3,5-di (carboxy) benzenesulfonate and polyethylene glycol Condensate,
A polycondensate of sodium 3,5-di (carboxy) benzenesulfonate and ethylenediamine, a polycondensate of sodium 3,5-bis (carbo-βhydroxyethoxy) -benzenesulfonate and adipic acid, and the like]. 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.

Among (A-1) and (A-2), those having a hydroxyl group, a carboxylic acid group, and a carboxylic acid group include, for example, ω-hydroxyamines (monoethanolamine, etc.) and monocarboxydiols (dicarboxylic acid). Methylol propionic acid, dimethylol sodium propionate, etc.) and the like. Examples of the compound used for neutralization as necessary include compounds described in JP-B-43-9076, preferably amines (trimethylamine, triethylaminepyridine, ammonia, etc.), inorganic bases (sodium hydroxide, Potassium hydroxide, potassium carbonate, sodium bicarbonate, etc.) and phosphorus compounds (triphenylphosphine, trimethylphosphine, etc.).

Among (A-1) and (A-2), those having a quaternary cation, betaine and / or a precursor thereof include, for example, the compounds described in JP-B-43-9076. Preferably amines (N-methyl-
Diethanolamine, N-butyl-diethanolamine, N, N-dimethyl-ethylenediamine, monoethanolamine and the like). Examples of the neutralizing compound used as necessary include, for example, JP-B-43-9076.
Examples of the compounds described in JP-A No. 1989-242, preferably alkyl halides (methyl chloride, butyl chloride,
Benzyl chloride, ethylene chlorohydrin, sodium monochloroacetate, etc.) and inorganic acids (hydrochloric acid, nitric acid, acetic acid, sulfuric acid, etc.).

Examples of the polyurethane mainly containing polyethylene glycol include polyurethane having a polyoxyethylene chain described in Japanese Patent Application No. 6-137893, and preferably polyethylene glycol (number average molecular weight 300 to 20,000). Is a polyurethane using.

In the present invention, an active hydrogen-containing polyfunctional compound can be optionally used in the production of (A).
For example, low molecular weight diols [ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.]; polyether diol [alkylene oxides of the low molecular weight diols exemplified above (ethylene oxide, propylene oxide, butylene oxide, etc. ) Addition products, ring-opening polymerization products of alkylene oxides (polytetramethylene glycol, etc.)]; Polyester diols [Aliphatic dicarboxylic acids (adipic acid, maleic acid,
Dimerized linoleic acid, etc.) or aromatic dicarboxylic acid (phthalic acid, terephthalic acid, etc.) with the above-exemplified low molecular weight diols, polyester diol, polylactone diol by ring-opening polymerization of ε-caprolactone, etc.]; 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 alcohols (triethanolamine, etc.); Examples thereof include an active hydrogen-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound with the following polyisocyanate.

In the present invention, the polyisocyanate optionally used for the production of (A) is, for example, an aromatic diisocyanate (tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate,
Diphenylmethane diisocyanate), alicyclic diisocyanate (isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, diisocyanate methylcyclohexane, etc.), aliphatic diisocyanate (hexamethylene diisocyanate, etc.), trifunctional or higher polyisocyanate [triphenylmethane triisocyanate, Tris (isocyanate phenyl) thiophosphate, a cyclic trimer of hexamethylene diisocyanate, and the like, and an isocyanate group-containing urethane prepolymer obtained by the reaction of these 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 isocyanate group to active hydrogen is 1: 2 to 2: 1, the terminal group may be either an isocyanate group or active hydrogen, and the terminal isocyanate group is a compound having one active hydrogen. May be blocked.

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

These will be described in more detail by way of examples. Polyurethanes described in Japanese Patent Application No. 6-137893, such as polyethylene glycol (molecular weight = 300).
To 20000) and a polyisocyanate polyurethane; Patent application dated September 14, 1994 (reference number P362
7) Polyurethane containing sulfonate group described in the specification, for example, polyurethane of polyester and polyisocyanate derived from sodium 3,5- (dicarboxy) benzenesulfonate and alkylene glycol; dimethylolpropionic acid as urethane extender or Examples thereof include polyurethanes using monoethanolamine and the like; polyurethanes obtained by reacting N-methyldiethanolamine-containing polyurethane with methyl chloride, and the like.

The content of (A) is usually 2 to 40% by weight, preferably 2 to 20% by weight. If it is less than 2% by weight, the antistatic property becomes insufficient, and if it exceeds 40% by weight, the mechanical properties become insufficient, which is not preferable.

The content of the hydrophilic portion in (A) can be changed within the range where the surface resistivity is 10 ¹⁴ Ω or less (preferably 10 ¹³ Ω or less). When the hydrophilic portion is a polyoxyethylene chain, the total amount thereof is 5 to 60% by weight, preferably 5 to 40% by weight in (A). If it is less than 5% by weight (A)
When the surface resistivity of the above exceeds 10 ¹⁴ Ω and exceeds 60% by weight, the mechanical properties become insufficient. When the hydrophilic portion is a sulfonate group, a sulfonate group, a hydroxyl group, a carboxylic acid group, a carboxylate group or a quaternary cation, the total amount thereof is 0.02 equivalent / 1,000 g to 40 equivalent / in (A). 1,000
g, preferably 0.02 equivalent / 1,000 g to 20 equivalent / 1,000 g. When it is less than 0.02 equivalent / 1,000 g, the surface resistivity of (A) exceeds 10 ¹⁴ Ω, and when it exceeds 40 equivalent / 1,000 g, the mechanical properties become insufficient.

The polyacetal (B) used in the present invention is not particularly limited and may be a homopolymer type or a copolymer type. For example, US Pat. No. 3,0
No. 27,352, and can be prepared by polymerizing anhydrous formaldehyde or trioxane, such as homopolymers of trioxane, and trioxane with ethylene oxide, dioxolane, substituted dioxolane, 1,4-dioxane, and the like. Examples thereof include copolymers.

The MFR (melt flow rate) of (B) in the permanent antistatic agent and the permanent antistatic resin molding obtained in the present invention is usually 0.1 to 100 g under the measurement conditions of 190 ° C. and 2.16 kg load. / 10 minutes, preferably 1-50
g / 10 minutes. Less than 0.1g / 10 minutes or 10
If it exceeds 0 g / 10 minutes, the moldability is poor. Again 130
Those having a melting point of ℃ or more are preferable, and the melting point is 130 ℃
If less than the above, the antistatic ability of the composite using the same is poor.

The content of polyacetal (B) is (A):
It is usually 1:10 to 40: 1, preferably 1: 1 to 10: 1 based on the weight ratio of (B), and if it is out of this range, the desired permanent antistatic property may not be sufficiently exhibited, or resin molding may be performed. Poor body mechanical properties and appearance. (B) in the resin composition
The content of is usually 1 to 20% by weight, preferably 1 to
15% by weight. If it is less than 1% by weight, the effect of adding polyacetal is not sufficient, and if it exceeds 20% by weight, the mechanical properties and appearance of the resin molded product are deteriorated, which is not preferable.

As (C) in the resin composition of the present invention,
Thermoplastic resins other than (A) and (B) include thermoplastic resins such as (co) polymers of vinyl compounds, polyesters, polyamides, polyimides, hydrophobic 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 the polymers or copolymers of these vinyl compounds include thermoplastic polyolefin resins [polyethylene, polypropylene, ethylene-α-olefin copolymers (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.]; Aliphatic polyesters [Polymers of aliphatic dicarboxylic acid esters (polybutylene adipate, polyethylene adipate, etc.)] Etc.]; polycarbonate; and a co-polycondensation product of an alkylene oxide (polyethylene glycol, polypropylene glycol, etc.) with a compound constituting two or more kinds of these, or a compound constituting these polymers.

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 thereof include a co-amidated compound of at least one kind, and a copolycondensate of a compound forming the polymer with a compound forming the polyester or an alkylene oxide (polyethylene glycol, polypropylene glycol, etc.).

Examples of the hydrophobic polyurethane include polyfunctional compounds containing active hydrogen (polytetramethylene glycol, polylactone diol, polyester diol, polycarbonate diol, etc.) and polyisocyanates (MDI, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene). Examples thereof include polyester polyurethanes and polyether polyurethanes having a surface specific resistance of more than 10 ¹⁴ Ω obtained from diisocyanate).

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.

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.

Among these thermoplastic resins (C), preferred are (co) polymers of vinyl compounds, particularly polyolefin type thermoplastic resins and styrene type thermoplastic resins.

Two or more of the above examples of the thermoplastic resin (C) can be used in combination.

The molecular weight of this thermoplastic resin (C) is usually 1
10,000 to 7,000,000, preferably 10.0
It is 00 to 3,000,000. Molecular weight is 10,000
If it is less than 0 or exceeds 7,000,000, molding becomes difficult and it is not practical.

The amount of this thermoplastic resin (C) 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 (C) is 80 ° C. or higher, preferably 100 ° C. or higher. 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 constituents.

The preferred dispersant (D) is
When the thermoplastic resin (C) 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 (C) is polystyrene, preferred (D) 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 mechanical properties of the molded product containing these dispersants (D) are improved. (C)
Is an aromatic polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene oxide, polyether ether ketone, polyphenylene sulfide, and polysulfone, styrene maleic anhydride copolymer, SBS resin, SEBS resin,
A terminal amino type and / or carboxylic acid type polyamide oligomer and a terminal carboxylic acid type and / or hydroxyl group type polyester oligomer are mainly used.

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

When the dispersant (D) is used, the proportion of (D) is usually 0. 0 relative to the total weight of (A) and (C).
05 to 50%, preferably 0.1 to 20%.

The composite resin composition of the present invention is obtained by polymerizing a compound having at least two active hydrogens in the molten (B) and (C) with a polyisocyanate. It can also be obtained by melt-kneading (B) and (C) with a compound having at least two active hydrogens in advance and (A) produced from polyisocyanate. 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 compound (A) is prepared by subjecting a compound having at least two active hydrogens and a polyisocyanate to a urethanization reaction in advance, the reaction temperature is usually 30 to 2
Within the range of 30 ° C, preferably 40 to 200 ° C.
The reaction pressure at that time is not particularly limited, but is usually reduced pressure (0.1 mmHg) to 50 atm, preferably reduced pressure (0.1 mmHg) to 30 atm in view of industrial production.

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 (A) phase is dispersed in a stripe shape in the surface layer of the composite resin. 10 ² sec to disperse in stripes
^-It is necessary to give a shear of ^-1 or more. Shear is 10 ² s
When it is less than ec ^-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 includes containers, cases,
It is suitable for bumpers, hoses, films and various housing materials.

[0048]

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 value. (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.

Production Example 1 36.1 parts of sodium 3,5-bis (carbo-βhydroxyethoxy) -benzenesulfonate (hereinafter referred to as SIPE)
Abbreviated), 67.1 parts of ethylene glycol, 930.
8 parts of PEG1540 (polyethylene glycol having a molecular weight of 1540; the same applies below) and 456.9 parts of diphenylmethane diisocyanate (hereinafter abbreviated as MDI) are twin-screw extruders (TEM35B manufactured by Toshiba Machine Co., Ltd., 37 mm).
φ, L / D = 41), cylinder temperature 190 ℃
The mixture was melt-kneaded for 5 minutes to obtain polyurethane (hereinafter abbreviated as PU-1). The surface resistivity of the obtained PU-1 alone is
It was 1.9 × 10 ⁹ Ω.

Example 1 850 parts of polypropylene [UBE-manufactured by Ube Industries, Ltd.]
Polypro J609H, hereinafter abbreviated as PP], 150 parts of P
U-1, 50 parts of polyacetal [DURACON M90 manufactured by Polyplastics Co., Ltd., hereinafter abbreviated as POM], 15
Parts of maleic anhydride modified polypropylene [bound maleic acid content 5%, number average molecular weight 5,000, abbreviated as PP-MA hereinafter; which corresponds to dispersant (D)] were added in the twin-screw extruder used in Production Example-1. It was melt extruded at 220 ° C. Cylinder temperature 200 ℃, mold temperature 50 ℃
Injection molding was carried out to prepare a test piece of the molded product of the present invention (shear at this time was 10 ³ sec ⁻¹ ) and the surface resistivity and mechanical property evaluation results of this test piece are shown in Table 1. .

Example 2 The same material as in Example 1 except that PP-MA was not added,
It was melt-kneaded under the conditions. The obtained composite resin was injection molded under the same conditions as in Example 1, and the test pieces were evaluated. The results are shown in Table 1.

Production Example 2 984 parts of PEG 2000, 90.7 parts of ethylene glycol, and 493.8 parts of MDI were melt-kneaded under the same conditions as in Production Example 1 to prepare polyurethane (hereinafter abbreviated as PU-2). Obtained. The surface resistivity of the obtained PU-2 alone was 1.2 × 10 ¹² Ω.

Example 3 850 parts PP, 150 parts PU-2, 50 parts PO
M and 15 parts of PP-MA were melt-kneaded under the same conditions as in Example 1. The obtained composite resin was injection molded under the same conditions as in Example 1, and the test pieces were evaluated. The results are shown in Table 1.
Shown in.

Production Example 3 927.1 parts of PEG1540, 23.1 parts of ethylene glycol, 38.3 parts of SIPE, 49.4 parts of dimethylolpropionic acid, and 463.6 parts of MDI were added to a Kneader Ruder [( Kasamatsu Chemical Research Institute KR-3
5] was melt-kneaded at a heating medium temperature of the kneader of 175 ° C. and a rudder temperature of 170 ° C. for 10 minutes to obtain polyurethane (hereinafter abbreviated as PU-3). The surface resistivity of the obtained PU-3 alone was 3.4 × 10 ¹⁰ Ω.

Example 4 850 parts PP, 150 parts PU-3, 50 parts PO
M and 15 parts of PP-MA were melt-kneaded under the same conditions as in Example 1. The obtained composite resin was injection molded under the same conditions as in Example 1, and the test pieces were evaluated. The results are shown in Table 1.
Shown in.

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 composition obtained was injection molded under the same conditions as in Example 1 and the test pieces were evaluated. The results are shown in Table 1.

[0057]

[Table 1]

Example 5 800 parts of polystyrene (Asahi Kasei Polystyrene 600 manufactured by Asahi Kasei Corporation, hereinafter abbreviated as PS), 200 parts of PU-
2, 50 parts of POM and 20 parts of Admast 3000 [styrene-maleic anhydride copolymer manufactured by Idemitsu Petrochemical Co., Ltd .; corresponding to dispersant (D)] were melt-kneaded under the same conditions as in Example 1. Cylinder temperature of the obtained composite resin 2
Injection molding was performed at 10 ° C and a mold temperature of 50 ° C to prepare a test piece of the molded product of the present invention (shear at this time was 10 ³ sec ^-1 ).
Table 2 shows the surface resistivity and mechanical property evaluation results of this test piece.

Example 6 850 parts of high impact polystyrene (Dialex HT-60 manufactured by Mitsubishi Kasei Co., Ltd.), 150 parts of PU-2, 50
Parts of POM and 15 parts of Admast 3000 were melt-kneaded under the same conditions as in Example 1. The obtained composite resin was injection molded at a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C. to prepare a test piece of the molded article of the present invention (shear at this time was 10 ³ sec ⁻¹ ). Table 2 shows the surface resistivity and mechanical property evaluation results of the test pieces.

Comparative Example 2 990 parts of PS, 10 parts of polyhydric alcohol fatty acid ester-based antistatic agent (Chemistat 1 manufactured by Sanyo Kasei Co., Ltd.)
100) was melt-kneaded under the same conditions as in Example 4. The obtained composition was injection molded under the same conditions using the same injection molding machine as in Example 4 to prepare test pieces. The characteristics of this test piece were evaluated in the same manner as in Example 4. The results of the characteristic evaluation are shown in Table 2.

[0061]

[Table 2]

[0062]

The molded product of the present invention has a permanent antistatic property which cannot be achieved by the conventional techniques and has excellent mechanical properties. The permanent antistatic method of using the polyurethane (A) and the polyacetal (B) in combination according to the present invention expands the molding temperature to a lower temperature range as compared with the conventionally known method of using a permanent antistatic polymer. It is excellent in molding processability. Also, the appearance of the molded product is excellent. From the fact that the above-mentioned effect is exhibited, the molded article of the present invention,
It is useful as a molding material for various applications requiring antistatic properties such as containers, cases, automobile parts, hoses, films and various housing materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 59:00)

Claims (10)

[Claims] 1. A polyurethane (A) having a surface resistivity of 10 ¹⁴ Ω or less and a polyacetal (B) are mixed in a ratio of 1:10.
A permanent antistatic agent for blending a thermoplastic synthetic resin, characterized by being used together in a weight ratio of -40: 1. 2. The molecular weight of (A) is from 6,000 to 20.
The composition of claim 1 which is 10,000. 3. Polyurethane (A) having a surface resistivity of 10 ¹⁴ Ω or less of 2 to 40% by weight, 1 to 20% by weight of polyacetal (B), and 60 to 97% by weight, based on the weight of the composition. % Of the thermoplastic resin (C), a permanent antistatic composite composition. 4. The composition according to claim 3, wherein (C) is a polyolefin-based thermoplastic resin. 5. The composition according to claim 4, comprising a complex of (A), (B), (C) and the following dispersant (D). Dispersant (D): a modified polyolefin dispersant having active hydrogen, a (anhydrous) carboxylic acid group, or a carboxylic acid halide group, or a polyolefin-polyurethane copolymer dispersant. 6. The composition according to claim 3, wherein (C) is a styrene-based thermoplastic resin. 7. The composition according to claim 6, comprising a complex of (A), (B), (C) and the following dispersant (D). Dispersant (D): Styrene-based dispersant having active hydrogen, (anhydrous) carboxylic acid group, or carboxylic acid halide group, or [styrene-based (co) polymer] -polyurethane copolymer-based dispersant. 8. (C) is a thermoplastic resin selected from the group consisting of aromatic polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene oxide, polyether ether ketone, polyphenylene sulfide, hydrophobic polyurethane, and polysulfone. 4. The composition of claim 3, which is certain. 9. A permanent antistatic composite resin molding obtained by molding using the composition according to any one of claims 3 to 8, in which at least a part of the (A) phase is dispersed in stripes at the surface layer portion of the molded product. body. 10. A composite formed by reacting an active hydrogen-containing polyfunctional compound with a polyisocyanate in molten (B) and (C) to form (A), or (A),
A composite obtained by melt-kneading (B) and (C) is subjected to shearing of at least 10 ² sec ^-1 to disperse at least a part of the (A) phase in a streak form at the surface layer of the composite resin. Item 10. A permanent antistatic method for a molded article according to any one of Items 3 to 9.