JP2001329253A - Antistatic agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent composition which exhibits excellent antistatic properties in the range of from low temperature to room temperature and a molded item containing the same. SOLUTION: An antistatic agent composition containing an ionic antistatic compound and a polar organic solvent; a molded item containing the agent; safety shoes of which the soles are molded items containing the agent; and a method for producing a polyurethane foam by reacting a polyol solution containing a polyol component, a blowing agent, and a catalyst with an isocyanate prepolymer in the presence of the antistatic agent composition containing an ionic antistatic compound and a polar organic solvent are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antistatic composition and a molded article containing the same. More specifically, an antistatic composition that exhibits excellent antistatic properties even at low temperatures,
And a molded article containing the antistatic agent composition and suitable for use as, for example, shoe soles of safety shoes and work shoes.

[0002]

2. Description of the Related Art Conventionally, methods for imparting antistatic properties include the addition of carbon black and conductive fillers; the application and addition of ionic surfactants; the addition of alkali metal salts such as perchloric acid, thiocyanic acid or nitric acid. Etc. (JP-A-63-43)
951) is known. Also, a method using an alkali metal salt in which the anion of the non-volatile ionizable metal salt is trifluoromethanesulfonic acid ion, thiocyanate ion or tetraorganoboron ion (Japanese Patent Application Laid-Open No. 63-1)
No. 54763) is also known.

On the other hand, JP-A-4-298517 and JP-A-4-298518 use quaternary ammonium alkylsulfate or quaternary ammonium perchlorate, and furthermore, use of perchloric acid, thiocyanic acid and nitric acid. It describes an additive which contains at least one selected from an alkali metal salt and an alkaline earth metal salt and gives a polyurethane having excellent antistatic performance without forming problems, and a method for producing a polyurethane.

[0004] However, the use of ordinary ionic surfactants alone cannot provide sufficient performance, and the use of conductive fillers involves thickening of the raw materials themselves when polyurethane raw materials are added. There is a problem in moldability in use. In addition, perchlorate, thiocyanate, trifluoromethanesulfonate, and the like are effective alone when expressed alone, but the final conductivity is insufficient, and furthermore, perchlorate is oxidized. There is a danger of explosion, and thiocyanate has the disadvantage of having a large corrosive action on metals. Also, nitrates have the disadvantage of yellowing urethane.

[0005] Further, even if quaternary ammonium alkyl sulfate or quaternary ammonium perchlorate is used, it cannot be said that a high demand for a polyurethane exhibiting stable conductive properties immediately after molding and over time is satisfied.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antistatic composition exhibiting excellent antistatic properties in a low temperature to room temperature range, and a molded article containing the antistatic composition. And

[0007]

According to the present invention, there is provided an antistatic composition comprising (1) an ionic antistatic compound and a polar organic solvent, and (2) an ionic antistatic compound comprising:
Molding containing the antistatic composition according to the above (1), which is a nonmetallic antistatic compound and a metal antistatic compound, and (3) the antistatic composition according to the above (1) or (2). Body, (4) the molded article of (3), wherein the molded article is a shoe sole, (5) a safety shoe having the sole of (4), and (6) a polyol component, a foaming agent and a catalyst. The present invention relates to a method for producing a polyurethane foam, in which a polyol solution is reacted with an isocyanate prepolymer in the presence of an antistatic composition containing an ionic antistatic compound and a polar organic solvent.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Representative examples of ionic antistatic compounds include nonmetallic antistatic compounds and metal antistatic compounds, which may be used alone or as a mixture of two or more. Can be. In the present invention, it is preferable to use a nonmetallic antistatic compound and a metal antistatic compound in combination from the viewpoint of exhibiting excellent antistatic properties.

Typical examples of the nonmetallic antistatic compound include quaternary ammonium sulfonic acid substituted with a hydrocarbon group or an oxyhydrocarbon group (hereinafter, substituted sulfonic acid quaternary ammonium).
Grade ammonium). Among the substituted quaternary ammonium sulfonates, formula (I):

[0010]

Embedded image

(Wherein, R ¹ is an alkyl group having 6 to 24 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms or 4 to 4 carbon atoms which together form a ring. An alkylene group of 5 or an oxyalkylene group of 3 to ⁴ carbon atoms, R ⁴ is an alkyl group of 1 to ⁴ carbon atoms, and R ⁵ is 1 carbon atom of
To 24 hydrocarbon groups or oxyhydrocarbon groups).

In R ¹ , among the alkyl groups having 6 to 24 carbon atoms, a decyl group, a lauryl group, a myristyl group, a palmityl group and a stearyl group are substituted quaternary ammonium sulfonates represented by the formula (I). In the synthesis of, it is preferable because the liquidity of the amine as a raw material is good and the odor is relatively low. R ⁵ is an alkyl group such as a methyl group,
An alkoxy group such as a methoxy group and an ethoxy group, and an aryl group such as a phenyl group and a p-methylphenyl group are preferred. In the case where R ² and R ³ together form a ring, a butylene group, a pentylene group and an ethyleneoxyethylene group are preferred from the viewpoint of providing a stable ring structure.

Among the substituted quaternary ammonium sulfonates, preferred are, for example, methyl sulfate-N, N, N
-Trimethyl-N-lauryl ammonium, methyl sulfate-N, N, N-trimethyl-N-cetyl ammonium,
Ethyl sulfate-N-ethyl-N, N-dimethyl-N-stearyl ammonium, ethyl sulfate-N-ethyl-N, N
-Dimethyl-N-lauryl ammonium, ethyl sulfate-
Dialkyl sulfate derivatives such as N, N-diethylmorpholinium; methanesulfonic acid-N, N, N-trimethyl-N
-Lauryl ammonium, methanesulfonic acid -N, N,
N-trimethyl-N-cetyl ammonium, methanesulfonic acid-N-ethyl-N, N-dimethyl-N-stearyl ammonium, methanesulfonic acid-N-ethyl-N,
Methanesulfonic acid ester derivatives such as N-dimethyl-N-lauryl ammonium, methanesulfonic acid-N, N-diethylmorpholinium; p-toluenesulfonic acid-
N, N, N-trimethyl-N-lauryl ammonium,
p-Toluenesulfonic acid-N, N, N-trimethyl-N
-Cetyl ammonium, p-toluenesulfonic acid-N-
Ethyl-N, N-dimethyl-N-stearyl ammonium, p-toluenesulfonic acid-N-ethyl-N, N-dimethyl-N-lauryl ammonium, p-toluenesulfonic acid-N, N-diethylmorpholinium, p And p-toluenesulfonic acid ester derivatives such as -toluenesulfonic acid-N-ethyl-N-methylmorpholinium.

The substituted quaternary ammonium sulfonate of the formula (I) is preferably a glycol, in a suitable solvent, for example, one selected from the group consisting of ethylene glycol, 1,4-butanediol and diethylene glycol. It can be easily prepared by dropping and reacting an equivalent amount of dialkyl sulfate to the corresponding tertiary amine among the species.

Typical examples of the metal-based antistatic compound include:
Formula (II): [R ⁶ —SO ₃ ⁻ ] _n · M ^{n +} (II) (wherein, R ⁶ is substituted with an alkyl group having 1 to 7 carbon atoms, a phenyl group or an alkyl group having 1 to 7 carbon atoms) A phenyl group, M represents a metal atom, and n represents a valency of a metal atom); a metal salt of an alkylsulfonic acid represented by the formula: benzene or a metal salt of an alkylbenzenesulfonic acid; hydrochloric acid, perchloric acid, nitric acid, trifluoromethanesulfonic acid, Alkali metal salts or alkaline earth metal salts of acids such as thiocyanic acid; phosphoric acid, sulfuric acid,
Salts of boric acid or an organic derivative thereof with an alkali metal or an alkaline earth metal, and the like can be given, and these can be used alone or in combination of two or more. Among these, benzene or a metal salt of an alkylbenzene sulfonic acid represented by the formula (II) is preferable.From the viewpoint of low cost, low corrosiveness, low toxicity, and ease of incineration treatment that does not generate dioxin, etc., toluene sulfone is preferred. Acid metal salts are particularly preferred.

In the metal alkyl sulfonic acid salt, benzene or metal alkyl benzene sulfonic acid salt represented by the formula (II), M is a metal atom, and among them, lithium is preferred from the viewpoint of solubility in an organic solvent. An atom, an alkali metal atom such as a sodium atom and a potassium atom, and an alkaline earth metal atom such as a magnesium atom are preferable, and a lithium atom is particularly preferable.

Preferred specific examples of the metal alkylsulfonate, benzene or metal alkylbenzenesulfonate represented by the formula (II) include lithium p-toluenesulfonate, sodium p-toluenesulfonate and p-toluenesulfonate. Potassium acid. Among these,
Lithium p-toluenesulfonate is particularly preferred.

In the present invention, when a nonmetallic antistatic compound and a metal antistatic compound are used in combination, excellent conductivity can be imparted to, for example, a molded article. In this case, the ratio of the nonmetallic antistatic compound to the metal antistatic compound is 100 to 2000 parts by weight of the nonmetallic antistatic compound, preferably 100 to 1000 parts by weight, relative to 100 parts by weight of the metal antistatic compound. Department
It is preferable from the viewpoint of rapidly imparting excellent conductivity to a molded article or the like in a wide temperature and humidity range.

When the antistatic agent composition is contained in a resin molded article such as a polyurethane foam, the ionic antistatic compound is used as a raw material for the resin molded article from the viewpoint of uniformly dispersing the resin molded article. The compound is preferably a compound that can be dissolved in a compound having two or more hydroxyl groups in a molecule, and is preferably used after being previously dissolved in an organic solvent, particularly a compound having two or more hydroxyl groups in a molecule. .

Examples of the compound having two or more hydroxyl groups in the molecule include polyol components such as polyester polyol and polyether polyol, and ethylene glycol, diethylene glycol, propylene glycol, and dipropylene in the case of producing a polyurethane foam. Chain extenders such as glycols, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, polyhydric alcohols such as alkylene oxide adducts of bisphenol A, and the like. Can be Among them, at least one selected from the group consisting of ethylene glycol, diethylene glycol and 1,4-butanediol dissolves an ionic antistatic compound better than various organic solvents to form a concentrated solution. Therefore, regardless of whether it is a constituent or a third component, it has little adverse effect on the resin, which is preferable. Particularly preferred is ethylene glycol.

Examples of the ionic antistatic compound soluble in a compound having two or more hydroxyl groups in the molecule include methyl sulfate-N, N, N-trimethyl-N-laurylammonium, methyl sulfate-N, N, methyl sulfate. N-trimethyl-N-cetyl ammonium, ethyl sulfate-N-ethyl-N, N-
Dimethyl-N-stearyl ammonium, ethyl sulfate-
Dialkyl sulfate derivatives such as N-ethyl-N, N-dimethyl-N-laurylammonium, ethyl sulfate-N, N-diethylmorpholinium; methanesulfonic acid-N, N,
N-trimethyl-N-lauryl ammonium, methanesulfonic acid-N, N, N-trimethyl-N-cetylammonium, methanesulfonic acid-N-ethyl-N, N-dimethyl-N-stearyl ammonium, methanesulfonic acid-N Methanesulfonic acid ester derivatives such as -ethyl-N, N-dimethyl-N-laurylammonium and methanesulfonic acid-N, N-diethylmorpholinium; p-toluenesulfonic acid-N, N, N-trimethyl-N- Lauryl ammonium, p-toluenesulfonic acid-N, N, N
-Trimethyl-N-cetyl ammonium, p-toluenesulfonic acid-N-ethyl-N, N-dimethyl-N-stearyl ammonium, p-toluenesulfonic acid-N-ethyl-N, N-dimethyl-N-lauryl ammonium,
Nonmetallic ionic compounds such as p-toluenesulfonic acid ester derivatives such as p-toluenesulfonic acid-N, N-diethylmorpholinium, lithium chloride, lithium perchlorate, lithium nitrate, lithium p-toluenesulfonic acid, etc. And the like. These are preferred, especially when dissolved in ethylene glycol, as they produce a concentrated solution of 33% by weight or more.

The content of the ionic antistatic compound in the resin molded article containing the antistatic agent composition is preferably 0.5% by weight or more from the viewpoint of sufficiently exhibiting the antistatic ability. More preferably, it is 1% by weight or more. In addition, the content is preferably 10% by weight or less, more preferably 5% by weight or less, from the viewpoint of maintaining the mechanical properties of the resin molded body. In consideration of the above points, the preferred range of the content of the antistatic compound in the resin molded article containing the antistatic agent composition,
0.1 to 10% by weight, and a more preferable range is 1 to 5%.
% By weight.

The present invention has one major feature in that an ionic antistatic compound and a polar organic solvent are used in combination. As described above, by using the ionic antistatic compound and the polar organic solvent in combination, for example, even in a low temperature state of about 0 ° C., an excellent antistatic effect can be imparted to various molded articles. Can be.

Here, the “polar organic solvent” referred to in this specification
The term “organic solvent” refers to an organic solvent composed of polar molecules and having a high relative dielectric constant. The melting point of the polar organic solvent is 4
The temperature is preferably 0 ° C. or lower from the viewpoint of easy handling.

The relative permittivity of the polar organic solvent at 20 ° C. is preferably 20 or more, more preferably 30 or more, and further preferably 4 or more, from the viewpoint of imparting excellent antistatic ability.
It is 0 or more, most preferably 50 or more. The relative dielectric constant is less susceptible to temperature changes, but tends to increase as the temperature decreases.

As the polar organic solvent, ethylene carbonate (4
Relative permittivity at 0 ° C. of 86.6), propylene carbonate (2
Carbonic acid esters represented by cyclic carbonates such as a relative dielectric constant at 3 ° C. of 69.0); formamide (relative dielectric constant at 20 ° C. of 111.0) and N-methylformamide (relative dielectric constant at 25 ° C. of 182. 4), N, N-dimethylformamide (dielectric constant 36.7 at 25 ° C.)
1), N-methylacetamide (relative dielectric constant at 32 ° C. 191.3), N, N-dimethylacetamide (25
Amide compounds such as dielectric constant at 37 ° C .; nitrile compounds such as acetonitrile (relative dielectric constant at 20 ° C. 37.5); nitro compounds such as nitromethane (relative dielectric constant at 30 ° C. 35.87); dimethyl sulfoxide Sulfur compounds such as (relative permittivity at 20 ° C. of 48.9) and sulfolane (relative permittivity at 30 ° C. of 43.3);
Phosphorus compounds such as hexamethylphosphoric triamide (dielectric constant at 20 ° C. 29.6) and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, carbonates represented by cyclic carbonates such as ethylene carbonate and propylene carbonate, amide compounds,
One or more selected from the group consisting of a sulfur compound and a phosphorus compound is preferable, and from the viewpoint of safety to the human body,
N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, ethylene carbonate, propylene carbonate, and a mixture of ethylene carbonate and propylene carbonate are preferable, and among them, ethylene carbonate, propylene carbonate, and a mixture of ethylene carbonate and propylene carbonate are more preferable. And a mixture of ethylene carbonate and propylene carbonate,
It is particularly preferred because it is liquid at room temperature.

The content of the polar organic solvent in the resin molded article containing the antistatic agent composition is preferably 0.1% by weight or more, and more preferably 1% by weight, from the viewpoint of sufficiently exhibiting the antistatic ability. More preferably, it is the above. Further, the content is preferably 5% by weight or less, from the viewpoint of maintaining the mechanical properties of the resin molded body, and is preferably 3% by weight or less.
It is more preferable that the content be not more than weight%. In consideration of the above points, the preferable range of the content of the polar organic solvent in the resin molded product containing the antistatic agent composition is 0.1 to 5
%, More preferably 1 to 3% by weight.

Ratio of ionic antistatic compound to polar organic solvent (ionic antistatic compound / polar organic solvent:
Weight ratio) is 1/2 to 20 / from the viewpoint of imparting sufficient antistatic performance and maintaining the physical properties of the resin molded article.
1, preferably 2/3 to 5/1.

The antistatic composition can be suitably used for various molding materials and the like. For example, an antistatic agent composition can be contained in a molded article by mixing the antistatic agent composition with a liquid molding material and then molding the mixture into a desired shape using the molding material.

The amount of the antistatic agent composition to be contained in the molded product cannot be unconditionally determined because it varies depending on the antistatic performance required for the molded product. In general, the content of the antistatic agent composition in the molded article is preferably 0.6% by weight or more, and more preferably 2% by weight or more, from the viewpoint of sufficiently imparting antistatic properties. 15% by weight from the viewpoint of maintaining the mechanical properties of
Or less, preferably 8% by weight or less.

Typical examples of the liquid molding material include polyurethane, epoxy resin, phenol resin, polyester resin, urea resin, olefin resin such as polyethylene and polypropylene, and resin such as styrene resin; natural rubber and isoprene rubber. Rubber such as chloroprene rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, butyl rubber, and acrylic rubber.

The liquid molding material may be a material which foams during molding to give a foam molded article. Examples of the liquid molding material for providing the foamed molded body include self-foaming polyurethane and the like, an olefin-based resin, a styrene-based resin, and the like. When using an olefin-based resin, a styrene-based resin, or the like, a method of expanding the resin using pre-expanded particles obtained by pre-expanding the resin, or a method of impregnating the resin with a foaming agent and performing a foam molding in a mold. Can be adopted.

An example of a liquid molding material that can be suitably used is polyurethane. In particular, when the antistatic agent composition is contained in a polyurethane foam, the obtained molded article of the polyurethane foam is preferably used for shoe soles such as safety shoes and work shoes where low electrification is required. Can be.

The raw materials for the polyurethane foam are not particularly limited, and known materials can be used. It is preferable to use a polyol solution and an isocyanate prepolymer as raw materials for the polyurethane foam.

The polyol solution contains a polyol component, a foaming agent and a catalyst, and if necessary, a foam stabilizer, a chain extender and the like.

As the polyol component, a compound having at least two active hydrogens can be used. Examples of the compound having at least two active hydrogens include propylene glycol, glycerin, trimethylolpropane, polyether polyols such as ethylene oxide adducts such as sorbitol and propylene oxide adducts,
Examples thereof include polyester polyols obtained from adipic acid, succinic acid, maleic acid, phthalic acid and the like and ethylene glycol, propylene glycol, butylene glycol, and the like, and polybutadiene polyol. Of these, polyether polyols and polyester polyols are preferred. The compound having at least two active hydrogens preferably has a number average molecular weight of about 500 to 3000.

As the blowing agent, water is generally used. In addition to water, low boiling organic solvents such as monofluorotrichloromethane, methylene chloride and pentane can also be used as foaming aids.

Examples of foam stabilizers include commercially available silicone compounds for polyurethane foams such as polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymers; soaps, ethylene oxide and / or propylene oxide adducts of alkylphenols and fatty acids, and the like. Surfactants and the like.

As the chain extender, a compound containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32 to 400 can be used. Specific examples of the compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-
1,3-propanediol, dibromobutanediol,
Glycerol, trimethylolpropane, 1,2,6-
Hexanetriol, trimethylolethane, pentaerythritol, xylitol, mannitol, sorbitol, castor oil, diethylene glycol, triethylene glycol, tetraethylene glycol, molecular weight 400
Polyethylene glycol, dipropylene glycol, polypropylene glycol up to a molecular weight of 400, dibutylene glycol, polybutylene glycol up to a molecular weight of 400, 4,4′-dioxydiphenylpropane,
Dioxymethylhydroquinone; aliphatic diamines such as ethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine and 1,4-tetramethylenediamine; tolylenediamine, 4,4'-diaminodiphenylmethane And the like, and these can be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of ethylene glycol, 1,4-butanediol and diethylene glycol is preferable, and ethylene glycol is more preferable.

Among the chain extenders, those having excellent solubility of an ionic antistatic compound such as glycol having a short molecular chain such as ethylene glycol, diethylene glycol and 1,4-butanediol can be used. There is. Such a chain extender excellent in solubility of an ionic antistatic compound can be used alone or as a mixture as a solvent for the ionic antistatic compound. in this case,
Within the range of the amount of chain extender used as a solvent, the amount of chain extender can be reduced.

Examples of the catalyst include organotin compounds such as stannas octoate and dibutyltin dilaurate, and amines such as triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, pentamethyldiethylenetriamine, and palmityldimethylamine. No.

The isocyanate prepolymer is obtained from a polyol component such as polyether polyol and polyester polyol, and a polyisocyanate component such as methylene diphenyl diisocyanate or a modified product thereof.

The method for incorporating the antistatic agent composition into the molded article is not particularly limited. For example, when the molded body is composed of a plurality of raw material compounds such as a polyurethane foam or the like, one of the raw material compounds may contain the antistatic agent composition, or each of the raw material compounds may be charged. The ionic antistatic compound and the polar organic solvent constituting the antistatic composition are separately contained, and the resulting antistatic agent composition is contained in a molded article produced using the raw material compound. You may do so.

More specifically, for example, when the molded article is a polyurethane foam, (A) a method in which an antistatic agent composition comprising an ionic antistatic compound and a polar organic solvent is contained in a polyol component; A) a method in which an ionic antistatic compound and a polar organic solvent are separately contained in a polyol component; and (C) an ionic antistatic compound is contained in a polyol component, and the polar organic solvent is contained in an isocyanate prepolymer. And a method in which a polyurethane foam obtained by reacting both reactants eventually contains the antistatic agent composition.
Among these methods, the method (C) has an advantage that the polar organic solvent can be prevented from being decomposed due to direct contact between the polar organic solvent and the catalyst used for the polyol component. ,preferable.

Next, after the antistatic agent composition is contained in the liquid molding material, the liquid molding material is put into a mold and molded by a conventional method to obtain a molded article having a desired shape. be able to.

The material of the molding die is not particularly limited. Examples include iron, stainless steel, copper, aluminum, aluminum alloys, epoxy resins, phenolic resins, and the like. Further, there is no particular limitation on the inner surface shape of the mold, and any shape may be used as long as it has a shape corresponding to the shape of the target molded body.

When the liquid molding material is molded in a mold, the inner surface of the mold is provided with
It is preferable that the release agent is previously applied to the inner surface of the mold by applying, spraying, dipping, or the like. As a release agent,
Examples thereof include dimethyl silicone oil, mineral oil, and paraffin wax, but the present invention is not limited to such examples.

Thus, a molded article having a predetermined shape is obtained by removing the mold after molding. Since the obtained molded article contains the antistatic agent composition of the present invention, it exhibits an excellent antistatic effect at low to room temperature.

In particular, when the molded article is a polyurethane foam molded article, it can be suitably used as a shoe sole of safety shoes, work shoes, and the like in which the occurrence of sparks is desired to be suppressed by grounding to the ground. Things. In this case, the density of the polyurethane foam molded body is preferably 0.3 to 1.0 g / cm ³ from the viewpoint of maintaining the mechanical properties, and is preferably 0.4 to 1.0 g / cm ^3.
0.8 g / cm ³ is more preferable, and 0.5 to 0.7 g / cm ³
cm ³ is particularly preferred.

[0050]

EXAMPLES Production Example 1 Copolymer of adipic acid with ethylene glycol and 1,4-butanediol [ethylene glycol / 1,4-butanediol (molar ratio) = 2/1, acid value: 0.50 mg
KOH / g, hydroxyl value: 52.0 mg KOH / g] 90
Parts by weight, copolymer of adipic acid with diethylene glycol and trimethylolpropane [diethylene glycol / trimethylolpropane (molar ratio) = 15/1, acid value: 0.50 mg KOH / g, hydroxyl value: 61.0 mg
KOH / g] 10 parts by weight, ethylene glycol 6.77
Parts by weight, 1 part by weight of silicone foam stabilizer (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SRX-295), 0.40 parts by weight of water, and 0.68 parts by weight of triethylenediamine as a catalyst are premixed. The composition A was obtained.

Production Example 2 41.0 parts by weight of dimethyl laurylamine and 10 parts by weight of ethylene glycol were charged, and a heat was generated while stirring.
59.0 parts by weight of diethyl sulfuric acid was added dropwise so as not to exceed ℃.

After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour to obtain a 90% ethylene glycol solution of ethyl sulfate-N-ethyl-N, N-dilauryl ammonium (composition B).

Production Example 3 19.59 parts by weight of lithium hydroxide monohydrate and 100 of water
After adding and stirring the parts by weight, 88.82 parts by weight of p-toluenesulfonic acid monohydrate was added. After the completion of the dropwise addition, it was confirmed that the solution was neutral using a bromcresol green indicator. Thereafter, water was distilled out of the system. After adjusting the temperature in the tank to 100 ° C. and the pressure in the tank to 50 hPa to confirm that water was not distilled off, 249.5 parts by weight of ethylene glycol was added and the ethylene glycol solution (composition C) was added. Obtained.

Preparation Example 1 Polyol solution A was obtained by mixing 110.60 parts by weight of composition A and 2.692 parts by weight of ethylene glycol.

Preparation Example 2 110.60 parts by weight of the composition A, 6.318 parts by weight of the component B, and 3.091 parts by weight of the composition C were mixed to obtain a polyol solution B.

Examples In Experiment Nos. 1 and 3 to 11 shown in Table 1, 113.292 parts by weight of the polyol solution A or 120.09 parts by weight of the polyol solution B obtained in Preparation Examples 1 and 2 were used as the polyol components. And a mixture of 6.032 parts by weight of a polar or non-polar organic solvent shown in Table 1 and an organic polyisocyanate compound [organic polyisocyanate compound [manufactured by Kao Corporation, trade name: Ediform B-2009, NCO% 18.5%].

In Experiment No. 2 shown in Table 1,
As a polyol component, a polyol solution B is used, and as an organic polyisocyanate compound, an organic polyisocyanate compound [manufactured by Kao Corporation, trade name: Ediform B
-2009, NCO% 18.5%] 100 parts by weight and 5.672 parts by weight of a polar or non-polar organic solvent shown in Table 1 were used.

The polyol component (A component) and the organic polyisocyanate compound (B component) were mixed with a polyurethane injection molding machine [manufactured by Polyurethane Engineering Co., Ltd., trade name:
MU-203S], and the mixture was poured into a molding die having a straight length of 300 mm, a short length of 100 mm, and a depth of 10 mm.
A test piece was prepared at a temperature of 5 ± 1 ° C. and a demolding time of 5 minutes. In addition, the A component and the B component both adjust the liquid temperature to 40 ± 1 ° C., and the mixing ratio is 95 to 95%.
Within the range of 100, the surface hardness was selected to be the highest after 3 minutes from the injection of the free form.

Table 1 shows the composition of the antistatic agent composition contained in the obtained test pieces. In Table 1, the ionic antistatic agent is added as an ethylene glycol solution (in a form containing ethylene glycol), but the amount does not include ethylene glycol.

Using a resist meter (manufactured by YOKOGAWA ELECTRIC WORKS, trade name: insulation resistance meter (battery type) TYPE3213), the resistance of the test piece was measured to be 300 m long on the lower surface.
m, an aluminum plate having a short length of 100 mm and a thickness of 1 mm, an aluminum plate having a length of 150 mm, a short length of 70 mm and a thickness of 1 mm was brought into contact with the upper surface, and the terminals were brought into contact with upper and lower aluminum plates to measure the resistance value. The resistance value after one day was measured as a representative value immediately after molding, and the resistance value after one week was measured as a representative value after stabilization. The results are also shown in Table 1.

[0061]

[Table 1]

From the results shown in Table 1, in Examples 1 to 4, the conductivity was good because a polar organic solvent was used, and the conductivity at 0 ° C. which was the severest was 100 MΩ.
It can be seen that the following values are shown.

In Experimental Examples 5 to 8, since the ionic antistatic compound was not contained, the electric resistance was measured at the measurement limit even in the presence of a solvent having a high relative dielectric constant, in the absence of a solvent. It turns out that it exceeds.

In Experimental Example 9, since an ionic antistatic composition was used, conductivity was exhibited. However, a standard of 100 MΩ (JIS T 8103-198)
3: Performance standard as a kind of electrostatic shoes is 0.1-100M
Ω) is almost at the upper limit of that performance criterion. J
In the IS, the conductivity of the shoe was evaluated. In the present invention, a sheet-shaped thing was evaluated.

In Experimental Examples 10 to 11, decane (dielectric constant of 1.99 at 40 ° C.) and di-2-ethylhexyl phthalate (dielectric constant of 5.degree.
It can be seen that since 3) was added, the conductivity was rather lowered.

Next, as the physical properties of the polyurethane foams obtained in Experimental Examples 1 and 9, the density, C hardness, modulus, breaking strength and elongation at break, tear strength, and bending resistance were measured according to the following methods. Examined. Table 2 shows the results.

(Density) 300 mm × 100 mm × 10 m
The weight (g) of the polyurethane foam having a thickness of m (thickness) is measured and divided by a volume of 300 cm ³ .

(C hardness) Measured with an Asker C hardness meter.

(Modulus) When measuring the breaking strength and elongation according to JIS K 6301, the elongation was 100%.
%, 200% or 300% tensile stress
They are called 0% modulus, 200% modulus and 300% modulus.

(Break strength, elongation at break, and tear strength) Measured according to JIS K6301.

(Bending resistance) According to JIS K 6301, the crack growth was examined 20,000 times and evaluated according to the following criteria. (Judgment criteria) ：: No crack growth. ×: There is crack growth.

[0072]

[Table 2]

From the results shown in Table 2, the polyurethane foams obtained in Experimental Examples 1 and 9 were all
Standards of tensile test for polyurethane foam described in JIS T 8103-1983 (tensile strength of 6 MPa or more,
Elongation of 300% or more) and the criteria of the tear test (25 N /
mm or more).

[0074]

According to the present invention, it is possible to obtain an antistatic composition exhibiting excellent antistatic properties even at a low temperature, and a molded article containing the antistatic composition. In particular, the antistatic agent composition of the present invention can be suitably used for molded articles such as polyurethane foam used for safety shoe soles.

Claims (7)

[Claims] 1. An antistatic composition comprising an ionic antistatic compound and a polar organic solvent. 2. The antistatic composition according to claim 1, wherein the ionic antistatic compound is a nonmetallic antistatic compound and a metal antistatic compound. 3. A molded article comprising the antistatic agent composition according to claim 1. 4. The method according to claim 3, which is made of a polyurethane foam.
The molded article according to the above. 5. The molded article according to claim 3, wherein the molded article is a shoe sole. 6. A safety shoe having the sole according to claim 5. 7. A polyurethane foam in which a polyol solution containing a polyol component, a blowing agent and a catalyst is reacted with an isocyanate prepolymer in the presence of an antistatic composition containing an ionic antistatic compound and a polar organic solvent. Manufacturing method.