JP5350020B2 - Antistatic agent for polyurethane resin, antistatic polyurethane resin molding using the same, method for producing polyurethane resin molding, and use of dicyanamide organic salt as antistatic agent in polyurethane resin - Google Patents

Abstract

There is provided an antistatic agent for a polyurethane resin which exhibits sufficient antistatic properties with a smaller addition amount and in which an effective component has no halogen atom. As the effective component of an antistatic agent for a polyurethane resin, there is used an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cationic component represented by the following general formula (2): wherein R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.

Description

  The present invention relates to an antistatic agent comprising, as an active ingredient, an organic salt in which the anion component is a dicyanamide anion and the cation component is a cation containing no halogen atom. Specifically, the present invention relates to an antistatic agent used for polyurethane resin moldings such as polyurethane fibers and polyurethane foams, an antistatic polyurethane resin molding using the same, and a method for producing an antistatic polyurethane resin molding About. The present invention further relates to a method of using the organic salt as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molded product, and a method of using the organic salt as an antistatic agent in a polyurethane resin or a polyurethane resin molded product. .

In a polymer material typified by polyurethane resin having a volume resistivity exceeding 10 ¹³ Ωcm, a large positive or negative electrostatic charge is easily generated on the contact surface with other objects due to friction. As a result, electrostatic charges do not leak in such polymer materials, and various static electricity failures occur, or products using such polymer materials adsorb dust in the air by electrostatic attraction, reducing the product value. To do. In some cases, such polymer materials may cause a fire such as dust explosion caused by discharge spark or ignition to a flammable solvent depending on the intended use or place of use, such as when processing at a processing factory. Therefore, it is necessary to impart antistatic properties to such a polymer material from the time of molding.

  Conventionally, addition of a conductive filler or a quaternary ammonium salt type antistatic agent is known as a method for imparting antistatic properties to a polyurethane resin. As quaternary ammonium salt type antistatic agents, quaternary ammonium alkyl sulfates (JP-A-4-298517) and quaternary ammonium perchlorates (JP-A-4-298518) are known. ing. However, when a conductive filler is added to a polyurethane resin raw material and used, a large amount of addition is required in order to obtain the desired antistatic property. When a large amount of the conductive filler is added, the viscosity of the raw material is increased, so that this method has a drawback that it is difficult to use in terms of the raw material handling surface. In addition, the use of a quaternary ammonium salt type antistatic agent has a problem in obtaining antistatic properties such that a sufficient effect cannot be obtained or a high addition concentration is required. Furthermore, since quaternary ammonium perchlorate contains halogen, there is a problem from the viewpoint of environmental load.

  In recent years, so-called “ionic liquids” composed of organic compounds and having a melting point of room temperature or lower have been found to be applied as antistatic agents for polymers due to their conductivity and low volatility (Japanese Patent Publication No. 2003-511505). Issue gazette). However, most of the anions contain halogens such as fluorine atoms, which has a problem in terms of environmental load.

  International Publication No. 2007/090755 pamphlet describes 1-ethyl-3-methylimidazolium dicyanamide and 1-butyl-3-methylimidazolium dicyanamide as antistatic agents used in polyurethane resins.

JP-A-4-298517 JP-A-4-298518 Special table 2003-511505 gazette International Publication No. 2007/090755 Pamphlet

  The present invention has been made in view of the above-mentioned problems of the prior art, and exhibits sufficient antistatic properties with a small amount of addition, and an antistatic agent for polyurethane resins containing an organic salt containing no halogen atom as an active ingredient. The purpose is to provide. A further object of the present invention is to provide an antistatic polyurethane resin molded article and a method for producing the polyurethane resin molded article using this antistatic agent. A further object of the present invention is to use the organic salt as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molded product, and as an antistatic agent in a polyurethane resin or a polyurethane resin molded product of the organic salt. It is to provide a method of use.

  The antistatic agent of the present invention is characterized in that an anionic component is a dicyanamide anion, an organic salt whose cation component is a cation containing no halogen atom as a main component, and an antistatic property can be imparted to a polyurethane resin with a small addition amount. And Furthermore, since the antistatic agent of the present invention uses an organic salt containing no halogen atom as an active ingredient, the antistatic agent as a whole can be in a form containing no halogen element.

  That is, the antistatic agent for polyurethane resins of the present invention comprises an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2) as an active ingredient. Including.

(Where
R ¹ is a linear or branched alkyl group, aryl group or benzyl group having 1 to 8 carbon atoms, R ² and R ³ are the same or different, and H or a linear chain having 1 to 8 carbon atoms. Alternatively, it represents a branched alkyl group. )

  A first aspect of the antistatic polyurethane resin molded product according to the present invention is characterized by including the above-described antistatic agent. A second aspect of the antistatic polyurethane resin molded product according to the present invention is characterized in that the antistatic agent is attached to at least the surface of the polyurethane resin molded product.

  The polyurethane resin composition according to the present invention comprises a polyurethane resin and the above-described antistatic agent.

The first aspect of the method for producing an antistatic polyurethane resin molded product of the present invention includes a step of obtaining a polyurethane resin from a mixture containing a polyol and a polyisocyanate, and a step of obtaining the molded product of the polyurethane resin,
In the step of obtaining the polyurethane resin, an antistatic property is imparted to the polyurethane resin molding by adding the antistatic agent described above. In the method according to the first aspect, an antistatic polyurethane resin molded article can be obtained by adding an antistatic agent during preparation of a polyurethane resin from a mixture containing a polyol and a polyisocyanate. As a preferable production method according to the first aspect, there is the following method.
(1) A method of imparting antistatic properties to a polyurethane resin molded article by curing a mixture containing a polyol, a polyisocyanate and the above antistatic agent under molding conditions.
(2) A method in which a polyurethane resin is obtained from a mixture containing a polyol, a polyisocyanate, and the above-described antistatic agent, and then the obtained polyurethane resin is molded to impart antistatic properties to the polyurethane resin molded product.

  A second aspect of the method for producing an antistatic polyurethane resin molding of the present invention is characterized in that the mixture obtained after the above-mentioned antistatic agent is mixed with a polyurethane resin composition containing a polyurethane resin is molded. To do.

  A third aspect of the method for producing an antistatic polyurethane resin molding of the present invention is characterized in that the antistatic agent is applied to the surface of the polyurethane resin molding or impregnated in the polyurethane resin molding.

  In the present invention, an organic salt in which the anion component is a dicyanamide anion represented by the general formula (1) and the cation component is a cation represented by the general formula (2) is used as a polyurethane resin or a polyurethane resin molded product. For use as an antistatic agent in the manufacture of

The antistatic agent for polyurethane resins according to the present invention has the following advantages derived from an organic salt which is an active ingredient.
・ The active ingredient of antistatic agent does not volatilize even at room temperature and high temperature.
-The active ingredient of the antistatic agent has good compatibility with polyols and polyisocyanates.
-Since the active ingredient of the antistatic agent is a compound having a charge, it is excellent in antistatic properties even in a low humidity environment.

  In addition, the organic salt in the present invention does not contain an anion containing a halogen atom such as a tetrafluoroborate anion or a bistrifluoromethylsulfonylimide anion, and the cation contains no halogen atom. There is an advantage that it is not corrosive and has a low environmental load.

  According to the present invention, an excellent antistatic property can be imparted to a polyurethane resin molded article using an organic salt composed of a dicyanamide anion of the general formula (1) and a cation of the general formula (2). Therefore, according to the present invention, an antistatic agent for polyurethane resin, an antistatic polyurethane resin molding using the same, and a method for producing a polyurethane resin molding can be provided. Furthermore, according to the present invention, the organic salt is used as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molded article, and the organic salt is used as an antistatic agent in a polyurethane resin or a polyurethane resin molded article. A method can be provided.

  Hereinafter, the present invention will be described with reference to preferred embodiments thereof.

  First, the antistatic agent for polyurethane resins of the present invention will be described.

  The antistatic agent for polyurethane resins of the present invention contains an organic salt in which the anion component is a dicyanamide anion represented by the following general formula (1) and the cation component is a cation represented by the general formula (2) as an active ingredient. .

(Where
R ¹ is a linear or branched alkyl group, aryl group or benzyl group having 1 to 8 carbon atoms, R ² and R ³ are the same or different, and H or a linear chain having 1 to 8 carbon atoms. Alternatively, it represents a branched alkyl group. )

In the general formula (2), R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, ^one of R ² and R ³ is H, and the other is a methyl group A salt is more preferable because of its excellent compatibility with polyisocyanates and polyols. Furthermore, R ¹ is a linear or branched alkyl group having 2 to 4 carbon atoms, ^one of R ² and R ³ is H, and the other is a methyl group. Is more preferable because it is more excellent. In these cases, the position of the methyl group is preferably the 3rd or 4th position.

  A phenyl group can be mentioned as an aryl group in each substituent in the quaternary ammonium represented by the general formula (2).

  The present inventors infer the reason why the organic salt which is an active ingredient of the antistatic agent of the present invention exhibits an excellent effect as an antistatic agent as follows.

  The dicyanamide anion has a molecular weight of about 66 and is one of the anions having the lowest molecular weight as an anion constituting an organic salt that usually has a melting point of room temperature or lower. Therefore, the electrical conductivity of the organic salt alone is high and contributes to the reduction of the leakage resistance value of the polyurethane resin. The polyurethane resin is a resin having a urethane bond, and this urethane bond has a very high polarity. The dicyanamide anion is an anion composed only of C and N among C, N, and O, which are constituent elements of a urethane bond, and has a high affinity for the urethane bond. Therefore, the antistatic agent of the present invention can be easily mixed into a polyurethane resin. Regarding the mixed state, the dicyanamide anion is easily compatible with the hard segment region containing a urethane bond from the viewpoint of its constituent elements. That is, the organic salt used in the present invention is not uniformly distributed in the polyurethane resin microscopically, but is unevenly distributed in the hard segment region. In such a mixed state, the organic salt forms a continuous contact structure (percolation structure), and as a result, a conductive path having high conductivity is efficiently formed. Therefore, the leakage resistance value can be specifically reduced, and as a result, high antistatic properties can be expressed. The present inventors infer that the same applies when the antistatic agent of the present invention is applied to the surface of a polyurethane resin molded product. In other words, since the affinity between the dicyanamide anion and the urethane bond is high, the organic salt has high wettability to the surface of the molded product, and it is easy to form a continuous contact structure (percolation structure). Is estimated to form efficiently.

Furthermore, the affinity with a polyurethane resin is further improved by combining the pyridinium cation represented by General formula (2) as a cation with a dicyanamide anion. In particular, the pyridinium cation has better affinity for polyurethane than the imidazolium cation.
As described above, the organic salt used in the present invention can effectively exhibit an antistatic effect in a polyurethane resin having a urethane bond, and the type of the target polyurethane resin is not limited.

  The antistatic agent of the present invention can be prepared with the above-described organic salt alone or with a solvent. Examples of the solvent for preparing the antistatic agent include alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, and water. One of these or a mixture of two or more can be used according to the intended use.

  An antistatic polyurethane resin molded article can be obtained by adding the antistatic agent of the present invention to the polyurethane resin molded article. Alternatively, the antistatic polyurethane resin molding can be obtained by applying the antistatic agent of the present invention to the surface of the polyurethane resin molding or impregnating the polyurethane resin molding. Any of these methods can impart excellent antistatic properties to the polyurethane resin molded product. Two or more of these methods can be used in combination.

In the case of a polyurethane resin molded article containing or impregnated with the antistatic agent of the present invention, the content of the organic salt is preferably 0.01 to 5% by mass relative to the mass of the polyurethane resin. It is preferable that it is -3.5 mass%. Moreover, in the case of a polyurethane resin molded product having the antistatic agent of the present invention attached to the surface, the amount of organic salt attached is preferably 0.02 to 1 g / m ² . In any case, when the amount of the organic salt is less than the above range, the antistatic property becomes insufficient. On the other hand, when the amount exceeds the above range, not only the improvement of the antistatic property commensurate with the amount of the organic salt can be obtained, but the physical properties of the polyurethane resin and the quality of the molded product may be deteriorated. Examples of such molded products include various molded articles such as polyurethane fibers, films, elastomers, polyurethane foams (hard, soft or semi-rigid polyurethane foams, cushioning materials, etc.), artificial leather skins and various paint surfaces. Examples include coatings.

Specifically, the antistatic polyurethane resin molded product can be produced by the following method.
(I) having a step of obtaining a polyurethane resin from a mixture containing a polyol and a polyisocyanate and a step of obtaining a molded product of the polyurethane resin, and adding the antistatic agent according to the present invention in the step of obtaining the polyurethane resin. A production method by imparting antistatic properties to the molded product of the polyurethane resin.
(Ii) A production method by molding a mixture obtained after mixing the antistatic agent according to the present invention with a polyurethane resin composition containing a polyurethane resin.
(Iii) A production method by applying the antistatic agent according to the present invention to the surface of a polyurethane resin molded article or impregnating the polyurethane resin molded article.
These methods can be used in combination as necessary.

  In the production method (i), polyurethane is produced from a mixture for producing a polyurethane resin obtained by adding additives such as a catalyst, a chain extender, a foaming agent, and a foam stabilizer to polyol and polyisocyanate as necessary. By adding the antistatic agent of the present invention at any stage in the preparation of the resin, an antistatic polyurethane resin molded product is obtained. In this case, the addition amount of the antistatic agent is within the above-mentioned range with respect to the mass of the polyurethane resin to be produced (that is, the amount of the organic salt is preferably 0.01 to 5% by mass, 0.5% by mass) is preferred.

In the production method (i), the step of obtaining the polyurethane resin and the step of obtaining the molded product of the polyurethane resin can be carried out simultaneously, partially overlapping or separately. Therefore, as a preferred embodiment of the production method (i), there is the following method.
(Ia) A method of imparting antistatic properties to a polyurethane resin molded article by curing a mixture containing a polyol, a polyisocyanate and the above-mentioned antistatic agent under molding conditions.
(Ib) A method in which a polyurethane resin is obtained from a mixture containing a polyol, a polyisocyanate, and the above-described antistatic agent, and then the obtained polyurethane resin is molded to impart antistatic properties to the polyurethane resin molded product.

  In the production method of (ia), when the polyol and the polyisocyanate are reacted in a mixture to which additives such as a catalyst, a chain extender, a foaming agent, and a foam stabilizer are added as necessary, the present invention. The antistatic agent is added, and these are reacted and molded. The mixture can be prepared and immediately placed under molding conditions, or the mixture can be prepared and allowed to proceed to some extent before being subjected to molding conditions. In the production method (ib), a polyurethane resin for molding is prepared from a mixture containing a polyol, a polyisocyanate and the antistatic agent of the present invention, and the resulting polyurethane resin is molded. The addition amount of the antistatic agent in these cases is the above-mentioned range with respect to the mass of the polyurethane resin to be produced (that is, the amount of the organic salt is preferably 0.01 to 5% by mass, An amount of 3.5% by mass) is preferred. The addition of the antistatic agent to the reaction system is performed at a stage where the effect as the antistatic agent is effectively obtained in consideration of curing conditions such as the curing rate of the reaction mixture. An antistatic agent can be added in advance to at least one of the component containing a polyol and the component containing a polyisocyanate. Alternatively, an antistatic agent can be added to a reaction system in which a component containing a polyol and a component containing a polyisocyanate are mixed. Since the organic salt which is an active ingredient of the antistatic agent has good compatibility with the polyol and polyisocyanate, it is preferable to previously mix the antistatic agent of the present invention with the polyol or polyisocyanate, particularly with the polyol. . In this case, the content of the organic salt is preferably about 0.05 to 5.0% by mass with respect to the polyol.

  The molding conditions in the production method (i) can be imparted by various molding methods. This molding method is not particularly limited, and a conventionally known method can be applied. For example, when molding a polyurethane foam, a catalyst, water, a foam stabilizer, and the antistatic agent according to the present invention are added to the polyol in advance, and the mixture is stirred well to prepare a mixture. This mixture and a slight excess of polyisocyanate are mixed well with a polyurethane preparation stirrer, and the resulting mixture is foamed on a belt conveyor or in a molding die. The molding conditions can also be given by a flat surface comprising a belt of a belt conveyor, the surface of a molding substrate, an extruder, a film molding roller, or the like. The timing of molding and curing of the mixture can be set according to curing conditions such as the curing temperature of the mixture.

  In the production method (i), when the antistatic agent of the present invention is added to the reaction system, the above-mentioned antistatic agent comprising an organic salt can be added as it is. Alternatively, an antistatic agent as a solution obtained by dissolving the above-described organic salt in a solvent can be added. As the solvent to be used, in addition to the above-mentioned solvent for preparing the antistatic agent, a known solvent or liquid medium used for dissolving or dispersing the polyurethane resin can be used.

  In the production method (ii), the antistatic agent of the present invention is mixed with a polyurethane resin composition containing a polyurethane resin and then molded. The polyurethane resin composition is not particularly limited as long as it is a resin composition containing a polyurethane resin and obtaining a molded product. Examples of the polyurethane resin composition include liquid polyurethane resin compositions such as an aqueous dispersion system and a solvent dissolution system. In this case, the addition amount of the antistatic agent is also in the above-mentioned range (that is, the amount of the organic salt is preferably 0.01 to 5% by mass, and 0.03 to 3.5% by mass with respect to the mass of the polyurethane resin). %) Is preferred. In this production method, when the antistatic agent of the present invention is added to the polyurethane resin composition, the above-described antistatic agent comprising an organic salt can be added as it is. Alternatively, an antistatic agent as a solution obtained by dissolving the above-described organic salt in a solvent can be added. As the solvent to be used, the above-mentioned solvent for preparing the antistatic agent can be used, and in particular, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol can be preferably used.

  In addition to the polyurethane resin and the antistatic agent, resins other than the polyurethane resin and various additives can be blended in the polyurethane resin composition.

  In the production method (iii), the antistatic agent of the present invention is applied to the surface of the polyurethane resin molded article or impregnated in the polyurethane resin molded article. Also in this production method, the above-described antistatic agent comprising an organic salt can be used as it is. Alternatively, an antistatic agent as a solution in which the above-described organic salt is dissolved in a solvent can be used. As the solvent to be used, the above-mentioned solvent for preparing the antistatic agent can be mentioned. The method of application and impregnation is not particularly limited, and methods such as coating, spraying, and dipping can be used. When the polyurethane resin molded product is impregnated with the antistatic agent of the present invention, it is preferable that the antistatic agent is applied to at least the surface of the polyurethane resin molded product. The amount of adhesion in this case can be selected from the above-mentioned range in application. After applying or impregnating the antistatic agent of the present invention, the molded product can be appropriately air-dried or heat-dried.

  The polyurethane resin to which the antistatic agent of the present invention can be applied contains at least polyurethane obtained by the reaction of polyisocyanate and polyol, and can further contain various additives. Furthermore, polyurethane resins incorporating other polymer structures such as polyester and polycarbonate are also included in the polyurethane resins according to the present invention.

  As the raw material of the polyurethane resin, a polyol and a polyisocyanate and components selected as desired from a catalyst, a chain extender, a crosslinking agent, water, a foam stabilizer, and the like can be used. There is no restriction | limiting in particular in a polyol, The polyester polyol, polyether polyol, polycarbonate polyol, etc. which have a hydroxyl group at a molecular terminal are used. Polyester polyols include, for example, those produced by an ester reaction between a dibasic acid such as adipic acid and a divalent or trivalent alcohol, and those obtained by ring-opening polymerization of a lactone. Polyether polyol, for example, the above-mentioned ethylene oxide, propylene oxide, or butylene oxide is polymerized to a diol that is a homopolymer or copolymer of ethylene oxide, propylene oxide, and butylene oxide, or a polyhydric alcohol such as glycerin or trimetrolepropane. The polyol etc. which were made to be mentioned. There is no restriction | limiting in particular also about polyisocyanate, and aromatic, aliphatic, and alicyclic polyisocyanate can be used. For example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like can be mentioned. Conventionally known catalysts, chain extenders, crosslinking agents, foam stabilizers and the like can be used without particular limitation.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. The evaluation of “antistatic property”, the measurement of “foaming ratio” and the measurement of “breaking strength” of the polyurethane resin molded products obtained in Examples and Comparative Examples were performed by the following methods.
(Evaluation of antistatic properties)
The polyurethane resin molded product was allowed to stand for 3 hours under constant temperature and humidity conditions of a temperature of 20 ° C. and a humidity of 40%, and then the leakage resistance value on the surface of the molded product was measured at a voltage of 1000V. The smaller the value, the better the antistatic property. For the measurement, a leakage resistance value measuring device: TOA super megohm meter SM-5E (manufactured by Toa Denpa Kogyo Co., Ltd.) was used.
(Measurement of expansion ratio)
In the process (3) of Production Example 1 of polyurethane foam molded article, the volume (a) of the mixture immediately after pouring the molding mixture into the frame and the volume (b) of the polyurethane foam molded article after aging for 1 day And measured. When the volume (a) is “1”, the ratio of the volume (b) is calculated and set as the expansion ratio.
(Measurement of breaking strength)
The polyurethane film was allowed to stand for 3 hours under constant temperature and humidity conditions of a temperature of 20 ° C. and a humidity of 65%, and then cut out with a dumbbell-shaped test piece punching blade according to JIS K 6251 (2004). The breaking strength of was measured. For the measurement, an autograph (AG-1S) manufactured by Shimadzu Corporation was used, and the tensile strength was 300 mm / min.

(1) Polyurethane foam molded product production example 1
The components for producing polyurethane foam molded products in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.

  In the table, “Adeka Polyether P-3000” (manufactured by ADEKA) was used as polypropylene glycol, and “SH-190” (manufactured by DOW CORNING) was used as the foam stabilizer.

The polyurethane foam molded product was produced by the following steps.
(1) No. Components 1 to 6 were mixed and stirred with a disper (2000 rpm × 2 minutes) to obtain a mixture.
(2) Next, No. 2 was added to the mixture obtained in the step (1). 7 component was added and stirred with a disper (2000 rpm × 10 seconds) to obtain a molding mixture.
(3) The molding mixture thus obtained was immediately poured into a frame and aged at room temperature (about 25 ° C.) for 1 day to obtain a polyurethane foam molded product.

Example 1
As an antistatic agent, 0.1 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 ° C. is added to polypropylene glycol (the component of No. 1 in Table 1), and polyurethane foam molding is performed according to Production Example 1. I got a thing.
(Example 2)
As an antistatic agent, 0.3 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 ° C. is added to polypropylene glycol (the component of No. 1 in Table 1), and polyurethane foam molding is performed according to Production Example 1. I got a thing.
(Example 3)
1 mass% isopropanol of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 ° C. as an antistatic agent on the surface of a polyurethane foam produced in the same manner as in Production Example 1 except that no antistatic agent is added. the solution was sprayed at a spray volume of 10 g / m ^2. Then, it was left to stand at room temperature (about 25 ° C.) for 24 hours to obtain a polyurethane foam molded product.

(Comparative Example 1)
A polyurethane foam molded article was obtained in the same manner as in Production Example 1 except that no antistatic agent was added.
(Comparative Example 2)
As an antistatic agent, 0.3 part by mass of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of −21 ° C. is added to polypropylene glycol (the component of No. 1 in Table 1), and polyurethane foam is produced according to Production Example 1. A body molding was obtained.
(Comparative Example 3)
Except for adding 0.1 parts by mass of (2-hydroxyethyl) dimethyl [3- (lauroylamino) propyl] ammonium perchlorate as an antistatic agent to polypropylene glycol (the component of No. 1 in Table 1). A polyurethane foam molded product was obtained in the same manner as in Production Example 1.

  Table 2 shows the measurement results of the leakage resistance value and the expansion ratio of the polyurethane resin molded products obtained in Examples 1 to 3 and Comparative Examples 1 to 3.

(2) Polyurethane film (spray treatment)
Example 4
Evaphanol HA-107C (aqueous dispersion of polycarbonate-based polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 39.2 g was poured into a stainless steel box (vertical 10 cm × width 12 cm × height 1 cm), This was dried at room temperature (about 25 ° C.) for 3 days to obtain a polyurethane film (length 10 cm × width 12 cm × thickness 1 mm). This film was sprayed with a 1% by mass isopropanol solution of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 ° C. as an antistatic agent at a spray amount of 10 g / m ² , and room temperature (about 25 ° C.). For 24 hours to obtain an antistatic polyurethane film.

(Comparative Example 4)
Evaphanol HA-107C (aqueous dispersion of polycarbonate-based polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 39.2 g was poured into a stainless steel box (vertical 10 cm × width 12 cm × height 1 cm), This was dried at room temperature (about 25 ° C.) for 3 days to obtain a polyurethane film (length 10 cm × width 12 cm × thickness 1 mm). This film was evaluated as a blank.
(Comparative Example 5)
Evaphanol HA-107C (aqueous dispersion of polycarbonate-based polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 39.2 g was poured into a stainless steel box (vertical 10 cm × width 12 cm × height 1 cm), This was dried at room temperature (about 25 ° C.) for 3 days to obtain a polyurethane film (length 10 cm × width 12 cm × thickness 1 mm). This film was sprayed with a 1% by weight isopropanol solution of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of −21 ° C. as an antistatic agent at a spray amount of 10 g / m ² , and room temperature (about 25 At 24 ° C. for 24 hours to obtain an antistatic polyurethane film.
(Comparative Example 6)
Evaphanol HA-107C (aqueous dispersion of polycarbonate-based polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 39.2 g was poured into a stainless steel box (vertical 10 cm × width 12 cm × height 1 cm), This was dried at room temperature (about 25 ° C.) for 3 days to obtain a polyurethane film (length 10 cm × width 12 cm × thickness 1 mm). This film was sprayed with a 5% by mass isopropanol solution of (2-hydroxyethyl) dimethyl [3- (lauroylamino) propyl] ammonium perchlorate as an antistatic agent at a spray amount of 10 g / m ² , at room temperature. It was allowed to stand at (about 25 ° C.) for 24 hours to obtain an antistatic polyurethane film.

  Table 3 shows the results of measuring the leakage resistance value and the expansion ratio of the polyurethane films obtained in Example 4 and Comparative Examples 4 to 6.

(3) Polyurethane film (kneading)
(Example 5)
1-butyl-3-methyl having a melting point of 16 ° C. as an antistatic agent in 100 parts by mass of Evaphanol HA-107C (aqueous dispersion of polycarbonate polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 0.15 parts by mass of pyridinium dicyanamide was added and mixed well. 12 g of this mixture was poured into a stainless steel box (length 10 cm × width 12 cm × height 1 cm), dried at room temperature (about 25 ° C.) for 3 days, and polyurethane film (length 10 cm × width 12 cm × thickness 0.4 mm). )

(Comparative Example 7)
Evaphanol HA-107C (Aqueous dispersion of polycarbonate polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 12 g was poured into a stainless steel box (length 10 cm x width 12 cm x height 1 cm). It was dried at room temperature (about 25 ° C.) for 3 days to obtain a polyurethane film (length 10 cm × width 12 cm × thickness 0.4 mm).
(Comparative Example 8)
Evaphanol HA-107C (aqueous dispersion of polycarbonate polyurethane resin, nonvolatile content 40% by mass, manufactured by Nikka Chemical Co., Ltd.) 100 parts by mass, 1-butyl-3-is a melting point of -21 ° C. as an antistatic agent 0.15 parts by mass of methylimidazolium dicyanamide was added and mixed well. 12 g of this mixture was poured into a stainless steel box (length 10 cm × width 12 cm × height 1 cm), dried at room temperature (about 25 ° C.) for 3 days, and polyurethane film (length 10 cm × width 12 cm × thickness 0.4 mm). )

  Table 4 shows the results of measuring the leakage resistance value and the expansion ratio of the polyurethane films obtained in Example 5 and Comparative Examples 7 to 8.

  As described above, according to the antistatic agent according to the present invention containing as an active ingredient an organic salt in which the anion component is a dicyanamide anion and the cation component is a pyridinium cation that does not contain a halogen atom, polyurethane resin molding is possible even with a small amount of use. Excellent antistatic properties can be imparted to the product. Moreover, according to the antistatic agent of this invention, the fall of the intensity | strength of a polyurethane resin molding can be suppressed compared with the conventional antistatic agent. Furthermore, when the polyurethane resin molded product is a polyurethane foam, the use of the antistatic agent of the present invention does not inhibit foaming during production, and provides a good foaming ratio and excellent antistatic properties. An effect is obtained.

Claims (10)

An antistatic agent for polyurethane resin comprising an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2) as active ingredients.

(Where
R ¹ is a linear or branched alkyl group, aryl group or benzyl group having 1 to 8 carbon atoms, R ² and R ³ are the same or different, and H or a linear chain having 1 to 8 carbon atoms. Alternatively, it represents a branched alkyl group. )   An antistatic polyurethane resin molded article comprising the antistatic agent according to claim 1. A step of obtaining a polyurethane resin from a mixture containing a polyol and a polyisocyanate; and a step of obtaining a molded product of the polyurethane resin,
A method for producing an antistatic polyurethane resin molded product, wherein in the step of obtaining the polyurethane resin, an antistatic property is imparted to the molded product of the polyurethane resin by adding the antistatic agent according to claim 1.   The manufacturing method of the antistatic polyurethane resin molding of Claim 3 which provides an antistatic agent to the said polyurethane resin molding by hardening the mixture containing a polyol, polyisocyanate, and the said antistatic agent on molding conditions.   The antistatic agent according to claim 3, wherein a polyurethane resin is obtained from a mixture containing a polyol, a polyisocyanate, and the antistatic agent, and then the antistatic agent is imparted to the polyurethane resin molding by molding the obtained polyurethane resin. For producing a porous polyurethane resin molded product.   A method for producing an antistatic polyurethane resin molding, comprising molding the mixture obtained after mixing the antistatic agent according to claim 1 with a polyurethane resin composition containing a polyurethane resin.   An antistatic polyurethane resin composition comprising the antistatic agent according to claim 1 and a polyurethane resin.   An antistatic polyurethane resin molded article, wherein the antistatic agent according to claim 1 is attached to at least the surface of the polyurethane resin molded article.   A method for producing an antistatic polyurethane resin molded article, wherein the antistatic agent according to claim 1 is applied to the surface of a polyurethane resin molded article or impregnated in the polyurethane resin molded article. A method of using an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2) as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molded product .

(Where
R ¹ is a linear or branched alkyl group, aryl group or benzyl group having 1 to 8 carbon atoms, R ² and R ³ are the same or different, and H or a linear chain having 1 to 8 carbon atoms. Alternatively, it represents a branched alkyl group. )