JP2002146178A - Additive for producing antistatic polyurethane, antistatic polyurethane and method for producing antistatic polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an antistatic polyurethane having thermal stability free from environment dependence while maintaining excellent antistatic properties, preventing troubles such as bleedout, etc., readily colorable and an additive for producing the antistatic polyurethane and to provide a method for producing the antistatic polyurethane. SOLUTION: This antistatic polyurethane is characterized in that lithium bis(trifluoromethanesulfonyl)imide and/or lithium tris(trifluoromethanesulfonyl) methane is added to a polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for producing an antistatic polyurethane, an antistatic polyurethane, and a method for producing the antistatic polyurethane.

[0002]

2. Description of the Related Art In recent years, it has become important to impart antistatic properties to a resin, and in order to achieve this, an antistatic agent such as a surfactant has conventionally been applied to the surface of a resin molded product. And a method of kneading an antistatic agent into a resin is known. However, the former method has a drawback that the antistatic property is dependent on humidity or the antistatic property is significantly reduced after a long period of time. Was. On the other hand, in the latter method,
There are problems such as the antistatic agent falling off the surface of the molded article, coloring from yellow to brown due to low heat resistance, and low antistatic performance.

[0003] Here, polyurethane is structurally low in electrical insulation compared to other resins, but is still insufficient for practical use. Therefore, polyurethane is used as a resin to impart antistatic performance to the polyurethane. The way to be done. Conventionally, the method includes adding carbon black, a conductive filler, and the like, applying and adding a surfactant, and adding an alkali metal salt such as perchloric acid, thiocyanic acid, or nitric acid (JP-A-63-43951). And a method of adding a special quaternary ammonium salt (see JP-A-4-298518).

However, when a normal surfactant is used, sufficient antistatic properties cannot be imparted, and after a long period of time, the antistatic properties are significantly reduced, and furthermore, there is a humidity dependency. Therefore, there are practical restrictions. In addition, when carbon black or a conductive filler is added, when added to a polyurethane raw material, it is scattered or the raw material is thickened, which causes a problem in moldability. Furthermore, when an alkali metal salt of perchloric acid is added, the solubility in the polyol is insufficient or heat is generated during the dissolution, which causes a problem in industrial production. In addition, the quaternary ammonium salt may be colored by heating, and there is a limitation in coloring to a desired color.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned conventional problems, and is thermally stable while maintaining excellent antistatic properties and has no environmental dependency. To provide an antistatic polyurethane which can prevent an obstacle such as bleed-out and can be easily colored, an additive for producing the antistatic polyurethane, and a method of producing the antistatic polyurethane. It is in.

[0006]

The present inventors have made various studies to solve the above-mentioned problems, and as a result, have found that lithium bis (trifluoromethanesulfonyl) imide and / or lithium tris (trifluoromethanesulfonyl) are contained in the polyurethane raw material. ) By adding methane, it has been found that a polyurethane having excellent antistatic performance can be obtained without impairing general physical properties at all.

Therefore, the invention according to claim 1 is as follows:
And / or lithium tris (trifluoromethanesulfonyl) methane as an essential component.

[0008]

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[0009]

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According to a second aspect of the present invention, a lithium bis (trifluoromethanesulfonyl) imide represented by Chemical Formula 3 and / or a lithium tris (trifluoromethanesulfonyl) methane represented by Chemical Formula 4 are added to polyurethane. It is characterized by having been done.

The invention according to claim 3 is the invention according to claim 2, wherein the lithium bis (trifluoromethanesulfonyl) imide represented by the formula (3) and / or the lithium tris (trifluoromethanesulfonyl) represented by the formula (4) are used. ) Methane is added to the polyurethane raw material in an amount of 0.01 to 2
It is characterized by adding 0% by weight.

The reason for this restriction is that when the amount of lithium bis (trifluoromethanesulfonyl) imide or the like is less than 0.01% by weight, sufficient antistatic performance cannot be obtained, while the amount exceeds 20% by weight. In such a case, there is a problem that the cost is increased.

According to a fourth aspect of the present invention, when a polyol having at least two active hydrogen atoms is reacted with an isocyanate to produce a polyurethane, lithium bis (trifluoromethanesulfonyl) imide represented by the above formula (3) and And / or adding lithium tris (trifluoromethanesulfonyl) methane represented by the above formula (4). By such a method, the antistatic polyurethane according to claim 2 is produced.

According to a fifth aspect of the present invention, in the fourth aspect of the present invention, there is provided lithium bis (trifluoromethanesulfonyl) imide represented by the above formula (3) and / or lithium tris (trifluoromethanesulfonyl) represented by the above formula (4). ) Methane is dissolved in and added to the polyol having at least two active hydrogen atoms.

For example, there is a method of adding a solution in which the above-mentioned additive is dissolved to a low molecular weight polyol of monoethylene glycol, diethylene glycol, 1,4-butanediol, a polyether polyol, or a polyester polyol.

There is no problem even if the other polyol component contains a compound having three or more active hydrogen atoms.

The invention according to claim 6 is the invention according to claim 4 or 5, wherein the lithium bis (trifluoromethanesulfonyl) imide represented by the formula (3) and / or the lithium tris (trifluorofluoride) represented by the formula (4) are used. Romethanesulfonyl) methane in an amount of 0.1 to 90% by weight based on the polyol having at least two active hydrogen atoms.
It is characterized by adding a dissolved solution.

The reason for this restriction is that the dissolved concentration is set at 0.1.
When the amount is less than 1% by weight, the uniformity of the performance of the antistatic polyurethane may be lacked, while when the dissolved concentration exceeds 90% by weight, there is a problem that the cost is increased.

Regarding each raw material component other than lithium bis (trifluoromethanesulfonyl) imide and / or lithium tris (trifluoromethanesulfonyl) methane used in the present invention, any known methods for obtaining polyurethane can be used. No special technique or technique is required.

The polyol having at least two active hydrogen atoms used in the present invention includes polyether polyols such as ethylene oxide adducts and propylene oxide adducts such as propylene glycol, glycerin, trimethylolpropane and sorbitol. Also,
Examples include polyester polyols and polybutadiene polyols obtained from adipic acid, succinic acid, maleic acid, phthalic acid, etc. and ethylene glycol, butylene glycol, and the like. Further, as the low molecular polyol, 1,4-
Butanediol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol. Particularly, polyether polyol, polyester polyol and polytetramethylene ether glycol are preferred.

The isocyanate used in the present invention includes, for example, tolylene diisocyanate, diphenylenemethane diisocyanate, hexamethylene diisocyanate, and prepolymers having these isocyanates at their terminals.

Further, as for each auxiliary material component other than the additive for producing the antistatic polyurethane used in the present invention, any of those conventionally known for producing polyurethane may be used. For example, as the catalyst, an amine compound,
Organometallic compounds and the like can be used. Further, a foaming agent, a foam stabilizer, a chain extender, a crosslinking agent, a flame retardant, and the like can be used.

In addition, by adding a pigment as a coloring agent, the antistatic polyurethane can be easily colored. As the pigment, pigments such as talc, titanium oxide, red iron oxide, clay, silica white, calcium carbonate,
Organic pigments such as azo pigments, phthalocyanine pigments and carbon black are exemplified.

The method for producing a highly antistatic polyurethane of the present invention comprises a polyurethane foam such as a flexible foam, a rigid foam polyurethane foam, a cross-linked polyurethane elastomer and a thermoplastic polyurethane elastomer, a reaction injection molded polyurethane, and 85% by weight. The present invention can be applied to a material requiring high antistatic properties, such as a synthetic fiber formed of a long-chain polymer having segmented polyurethane and a polyurethane resin paint.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to a number of embodiments, but the present invention is not limited to these embodiments. In addition, the part in each form means a weight part. In addition, lithium imide represents lithium bis (trifluoromethanesulfonyl) imide represented by Chemical Formula 3, and lithium methane represents lithium tris (trifluoromethanesulfonyl) methane represented by Chemical Formula 4.

[Embodiment 1] 5% by weight of lithium imide was added to 100 parts of polyethylene adipate (OHV = 56).
8 parts of dissolved ethylene glycol, 0.5 parts of water, 0.4 parts of triethylenediamine, silicone-based surfactant
After adding and mixing 0 parts, 100 parts of a mixture of diphenylmethane diisocyanate and a polyethylene adipate-based terminal isocyanate prepolymer were mixed and stirred to produce a plate-like test piece having a thickness of about 4.5 mm. did. The product thus manufactured is hereinafter referred to as Invention Example A1.

[Embodiment 2] A mixture of 90 parts of propylene glycol-based polyether polyol (OHV = 56) and 10 parts of propylene glycol-based polyether polyol (OHV = 56) in which 10% by weight of lithium imide is dissolved, After 4.5 parts of water, 0.1 part of pentamethylenetriamine and 2.0 parts of a silicone surfactant were added and mixed, 56 parts of tolylene diisocyanate was mixed with the mixture, and the mixture was stirred. 48 bubbles /
A flexible polyurethane foam having a good in was obtained. The product thus manufactured is hereinafter referred to as Invention Example A2.

Embodiment 3 A polyester polyol synthesized from adipic acid and butanediol in which 5% by weight of lithium methane is dissolved (OHV = 56, average molecular weight 20)
00) 100 parts, water 3.6 parts, pentamethylene triamine 0.1 part, silicone surfactant 2.0 parts, stannas octoate 0.3 parts, HCFC-141b 13
Then, 56 parts of tolylene diisocyanate was mixed and stirred to obtain a good flexible polyurethane foam. The product thus manufactured is hereinafter referred to as Invention Example A3.

[Embodiment 4] A room temperature-curable polyurethane prepolymer and a propylene glycol-based polyether polyol (2% by weight of lithium imide dissolved) were mixed with NCO
The mixture was prepared and mixed so that the group / OH group = 1.15.
1% of lead octylate was added to this mixture. Then, the mixture was applied on a polyester film (thickness: 50 μm), left to cure, and a film-like transparent resin having a thickness of 0.2 mm was obtained. The product thus produced is hereinafter referred to as Invention Example A4.

[Embodiment 5] 100 parts of glycerin polyoxypropylene triol (OHV = 57, average molecular weight 5000) in which 2% by weight of lithium imide is dissolved, 6.03 parts of tolylene diisocyanate, 4 parts of a silicone surfactant, 0.035 parts of dibutyltin dilaurate and 0.03 parts of tetracyanoethylene are mechanically stirred and foamed with dry air, and the mixture is poured into a cylindrical mold having an inner diameter of 16.5 mm and a length of 210 mm, and is heated at 120 ° C. for 1 hour. After curing, it was released from the mold. The product thus produced is hereinafter referred to as Invention Example A5.

[Embodiment 6] Hydrogenated 1,2-polybutadiene polyol (GI-1000, manufactured by Mitsubishi Chemical Corporation) 15
0 parts, a trimethylolpropane adduct of isophorone diisocyanate (Takenate D, manufactured by Takeda Pharmaceutical Co., Ltd.)
-140N) 65 parts, a caprolactam adduct of hexamethylene diisocyanate (E405- manufactured by Asahi Kasei Corporation)
80T) 26 parts, polytetrafluoroethylene powder 20
Parts, 10 parts of lithium imide and 65 parts of toluene,
A paint was prepared. This paint is applied on a rubber sheet having a thickness of 1 mm by a spray method to form a coating having a thickness of 30 μm.
The coating was dried and cured at 120 ° C. for 1 hour to form a coating layer. The product thus manufactured is hereinafter referred to as Invention Example A6.

Embodiment 7 A sorbitol-based polyol in which 4% by weight of lithium imide is dissolved (OHV = 45)
0) 25 parts, pentaerythritol polyol (OHV
= 450) 75 parts, pentamethyldiethylenetriamine 0.15 parts, silicone surfactant 1.5 parts, HCF
After mixing and preparing 15 parts of C-141b, tolylene diisocyanate prepolymer (NCO group 30
%) And mixing and stirring, a good rigid polyurethane foam was obtained. The product thus manufactured is hereinafter referred to as Invention Example A7.

[Embodiment 8] 4,4-diphenylmethane diisocyanate and polytetramethylene glycol (average molecular weight: 1000, 10 parts by weight of 1,4-dimethylolbenzene dissolved in 50% by weight of lithium imide) were added to an NCO group / The viscous mixture mixed and prepared so as to have an OH group of 1.05 was heated at 120 ° C. for 6 hours to obtain a thermoplastic elastomer. This was cut into pellets having a diameter of about 5 mm, and then pressed to form sheet-like test pieces having a thickness of about 5 mm. The product thus manufactured is hereinafter referred to as Invention Example A8.

[Comparative Example 1] In the first embodiment, ethylene glycol 8 in which 5% by weight of n-lauryltrimethylammonium chloride was dissolved instead of lithium imide was used.
A plate-shaped test piece was prepared in the same manner as in Embodiment 1 except that the addition was partially performed. The product thus manufactured is hereinafter referred to as Comparative Example X1.

Comparative Example 2 A film-like transparent resin was obtained in the same manner as in Example 4, except that a propylene glycol-based polyether polyol which did not dissolve lithium imide was used. After spraying 2-ethylhexylammonium nitrate diluted to 10% by weight on methanol on the surface of this film,
Let dry. The product thus manufactured is hereinafter referred to as Comparative Example X2.

Comparative Example 3 Example 1 was repeated except that 8 parts of ethylene glycol in which 5% by weight of lithium perchlorate was dissolved was added instead of lithium imide.
A plate-shaped test piece was prepared in the same manner as in Example 1. The product thus manufactured is hereinafter referred to as Comparative Example X3.

Comparative Example 4 In the seventh embodiment, an attempt was made to prepare a sorbidol-based polyol in which lithium perchlorate was dissolved, but it was not dissolved. The product thus manufactured is hereinafter referred to as Comparative Example X4.

[Experiment] The surface specific resistance (volume specific resistance in Example A5 of the present invention) was measured in Examples A1 to A8 of the present invention and Comparative Examples X1 to X3, and the results are shown in Table 1. In Examples A1 and A4 of the present invention and Comparative Example X2, the surface was left under a water stream for 30 minutes, dried, and the surface resistivity was measured again. The results are also shown in Table 1. Furthermore, in Example A1 of the present invention and Comparative Example X3, a moist heat acceleration test in which the sample was stored for 5 days under a high-temperature and high-humidity condition of a temperature of 80 ° C and a humidity of 95% was performed, and the strength retention was measured. Also shown.

[0039]

[Table 1]

The surface resistivity after the preparation of each test piece was 5 × 10 ^{6 to} 7 × 1 in Examples A1 to A8 of the present invention and Comparative Example X2.
0 ⁸ Ω / sq, and 3 × 10 ^{10 to} 5 × 10 ¹⁰ Ω / in Comparative Examples X1 and X3.
It can be seen that it has increased to sq. In addition, it is recognized that the volume resistivity value of Inventive Example A5 is as small as 4 × 10 ⁷ Ω · cm.

As described above, the surface resistivity (volume resistivity in Example A5 of the present invention) after preparation of each test piece is excellent not only in Examples A1 to A8 of the present invention but also in Comparative Example X2. However, in Comparative Example X2, the surface resistivity after the water flow test was as large as 9 × 10 ⁹ Ω / sq, whereas in Examples A1 and A4 of the present invention, the surface resistivity was 8 after the water flow test.
It is recognized that it is not so large as from × 10 ^{7 to} 7.5 × 10 ⁸ Ω / sq.

Further, it is recognized that the strength retention rate after the accelerated wet heat test is as high as 90% in Example A1 of the present invention and as low as 60% in Comparative Example X3.

[0043]

According to the production method of the present invention, a polyurethane having excellent antistatic properties without impairing the appearance and physical properties of the polyurethane can be obtained. In addition, the polyurethane produced by adding the lithium imide and / or lithium methane of the present invention has a sustained antistatic property, and
The performance is not deteriorated even by washing with water or the like, and an excellent effect such as excellent durability and high antistatic performance is exhibited.

Continued on the front page F term (reference) 4J002 CK031 CK041 CK051 EV266 FD206 GH01 GK01 4J034 CA03 CA04 CA05 CC03 DA01 DF01 DF16 DF20 DF22 DG03 DG04 DG14 HA07 HC03 HC12 HC64 HC67 HC71 MA03 MA04 MA14 MA15 RA07 RA09

Claims (6)

[Claims] 1. A lithium bis (trifluoromethanesulfonyl) imide represented by the following formula 1 and / or
An additive for producing an antistatic polyurethane, comprising lithium tris (trifluoromethanesulfonyl) methane represented by the following formula as an essential component: Embedded image Embedded image 2. A polyurethane, wherein lithium bis (trifluoromethanesulfonyl) imide represented by Chemical Formula 1 and / or lithium tris (trifluoromethanesulfonyl) methane represented by Chemical Formula 2 are added. Antistatic polyurethane. 3. The lithium bis (trifluoromethanesulfonyl) imide represented by the formula 1 and / or the formula 2
Lithium tris (trifluoromethanesulfonyl) methane represented by the formula:
The antistatic polyurethane according to claim 2, wherein 20% by weight is added. 4. A method for producing a polyurethane by reacting a polyol having at least two active hydrogen atoms with an isocyanate, wherein lithium bis (trifluoromethanesulfonyl) imide represented by the above formula 1 and / or A method for producing an antistatic polyurethane, comprising adding lithium tris (trifluoromethanesulfonyl) methane represented by the formula: 5. The lithium bis (trifluoromethanesulfonyl) imide represented by the formula 1 and / or the formula 2
5. The method for producing an antistatic polyurethane according to claim 4, wherein lithium tris (trifluoromethanesulfonyl) methane represented by the following formula is dissolved in and added to the polyol having at least two active hydrogen atoms. 6. 6. The lithium bis (trifluoromethanesulfonyl) imide represented by the formula 1 and / or the formula 2
A solution obtained by dissolving 0.1 to 90% by weight of lithium tris (trifluoromethanesulfonyl) methane represented by the formula in the polyol having at least two active hydrogen atoms is added. 6. The method for producing an antistatic polyurethane according to 4 or 5.