JPH04298518A - Additive for production of polyurethane and production of polyurethane - Google Patents

Abstract

PURPOSE:To obtain an additive which can give a polyurethane improved in hydrolysis resistance and antistatic properties by using a specified quat. ammonium compound as an essential component. CONSTITUTION:A tert. amine is quaternized with an alkyl chloride in a solvent, and the product is subjected to salt exchange by adding dropwise sodium perchlorate to obtain a quat. ammonium compound (A) of the formula (wherein R1 is 1-12 C alkyl, aryl or benzyl). Component A as an essential component is optionally mixed with a metal salt of an inorganic acid, selected from among alkali (alkaline earth) metal salts of perchloric acid, thiocyanic acid and nitric acid, in a ratio of (5-1):1 to obtain the title additive. A mixture of a compound having at least two active hydrogen groups with an organic isocyanate is reacted in the presence of 0.05-10wt.% (in terms of component A), based on the mixture, above additive to obtain 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 polyurethane and a method for producing antistatic polyurethane having excellent hydrolysis resistance.

0002

[Prior Art] Generally, plastics have high electrical insulating properties, so they are easily charged with static electricity, and dirt and dust may adhere to the surface, causing stains on the surface, and depending on where it is used, sparks caused by charged static electricity may cause flammable solvents. may ignite, causing a fire or explosion. In addition, in the electronics industry, there are problems such as internal circuits being destroyed by static electricity during integrated circuit (IC) manufacturing and assembly, resulting in defective products. It is necessary to provide excellent antistatic performance to

[0003] Due to its structure, polyurethane has lower electrical insulation properties than other plastics, but this is still insufficient, and polyurethane foam, in particular, is a foam and has a low density, resulting in the above-mentioned disadvantages. Conventionally, methods for imparting antistatic properties include the addition of carbon black, conductive fillers, etc., the coating and addition of surfactants, and the addition of alkali metal salts such as perchloric acid, thiocyanic acid, or nitric acid (Japanese Unexamined Patent Publication No. 63-43951). Publication No.) is known.

0004

[Problems to be solved by the invention] However, the use of ordinary surfactants does not provide sufficient performance, and when using conductive fillers, it is necessary to increase the viscosity of the raw materials themselves when adding polyurethane raw materials. Accordingly, there are problems with moldability during use. Furthermore, although alkali metal salts of perchloric acid, thiocyanic acid, or nitric acid are excellent in final conductive performance, they have the disadvantage that they are slow to develop their effects.

[0005]

[Means for Solving the Problems] As a result of extensive research aimed at obtaining a polyurethane that has excellent antistatic properties and is free from molding problems, the present inventors have found that a small amount of the following general formula ( I)

[0006]

[Chemical formula 3]

[In the formula, R1: an alkyl group having 6 to 24 carbon atoms R2: H or an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group R3: an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group means base. It has been found that by using a quaternary ammonium compound represented by the following formula, it is possible to obtain a polyurethane having extremely good antistatic properties with rapid onset of effects without any loss in general physical properties. Surprisingly, while the main purpose of general quaternary ammonium salts is to lower the surface resistance value through bleeding, the quaternary ammonium compound represented by the above general formula (I) used in the present invention was found to have a particularly large effect of lowering the volume resistivity, and is particularly effective in foams such as polyurethane foam.

That is, the present invention provides the following general formula (I)

0
009]

[C4]

[In the formula, R1: an alkyl group having 6 to 24 carbon atoms R2: H or an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group R3: an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group means base. ] An additive for producing polyurethane containing a quaternary ammonium compound represented by the above general formula (I) as an essential component, and a compound having at least two active hydrogens when producing polyurethane by reacting with an organic isocyanate. The present invention provides a method for producing polyurethane characterized by adding a quaternary ammonium compound represented by:

The alkyl group having 6 to 24 carbon atoms in general formula (I) includes hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, myristyl group,
Examples of the alkyl group having 1 to 12 carbon atoms include a palmityl group, stearyl group, eicosyl group, cetyl group, etc. In addition to the above alkyl group having 6 to 24 carbon atoms, methyl group, ethyl group, propyl group, butyl group, Examples include pentyl group.

As the quaternary ammonium compound represented by the above general formula (I), quaternary ammonium perchlorate is preferred because of its ease of synthesis and excellent stability. Examples of the quaternary ammonium perchlorate according to the present invention include the compounds shown below.

[0013]

[C5]

The quaternary ammonium compound represented by the above general formula (I) according to the present invention can be obtained by quaternizing a tertiary amine with an alkyl chloride in a suitable solvent, and adding sodium perchlorate dropwise to form a salt. Obtained by making an exchange. The quaternary ammonium compound represented by the above general formula (I) is preferably used in an amount of 0.05 to 10% by weight based on the raw material for producing polyurethane. Usage amount is 0.05
When the amount is less than 10% by weight, sufficient antistatic performance cannot be obtained, and when it exceeds 10% by weight, the physical properties of the polyurethane are greatly reduced. Any general method can be applied to the addition method of the additive of the present invention. For example, ethylene glycol
Examples include a method in which the additive is dissolved in a solvent such as diethylene glycol or butanediol and added to a compound having an active hydrogen atom.

[0015] The inorganic acid metal salts used as necessary in the present invention are alkali metal salts or alkaline earth metal salts of perchloric acid, thiocyanic acid, and nitric acid, such as lithium peroxygenate, perchloric acid, etc. Calcium acid, lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, lithium nitrate, etc. are preferably used, and two or more types can also be used in combination. The inorganic acid metal salt is preferably used in an amount of 0.05 to 10% by weight based on the raw material for producing polyurethane. Furthermore, the above general formula (I) according to the present invention
The ratio of the quaternary ammonium compound and the inorganic acid metal salt is expressed as: quaternary ammonium compound: inorganic acid metal salt = 5:
1 to 1:1 is preferred. When an inorganic acid metal salt is used in combination, a conductive polyurethane with quick onset of effects and excellent final performance can be obtained. Furthermore, when an inorganic acid metal salt is used alone, it takes time for antistatic performance to develop and stabilize.

[0016] Compounds having at least two active hydrogens used in the present invention include propylene glycol,
Polyether polyols such as ethylene oxide adducts and propylene oxide adducts such as glycerin, trimethylolpropane, and sorbitol; also adipic acid,
Examples include polyester polyols obtained from succinic acid, maleic acid, phthalic acid, etc. and ethylene glycol, propylene glycol, butylene glycol, etc., and polybutadiene polyols. Also included are low molecular weight glycols, ethylene glycol, propylene glycol, butylene glycol, and diethylene glycol. In particular, it is preferable to use polyether polyols and polyester polyols. Further, there is no problem even if the other polyol components contain a compound having three or more active hydrogen atoms. The average molecular weight of the compound having at least two active hydrogen atoms is preferably about 500 to 3,000.

Polyurethane produced from a polyester polyol using a quaternary ammonium compound represented by the above general formula (I) may undergo hydrolysis due to its structure, but in such a case, the polyester A cocondensate obtained from a diol having a branched alkyl group as a polyol and, if necessary, another polyol and a dicarboxylic acid, such as 3-methyl-1,5 pentanediol and adipic acid (
3-methyl-1,5-pentanediol, co-condensate of ethylene glycol and sebacic acid (average molecular weight 2,000), 3-methyl-1,5-pentanediol, glycerin and adipic acid (average molecular weight 2,000) ) can be used to produce polyurethane without impairing hydrolysis performance. The average molecular weight of these cocondensates is preferably 500 to 3,000.

[0018] Regarding each raw material component other than the quaternary ammonium compound, the inorganic acid metal salt, and the compound having at least two active hydrogens used in the present invention, all of them are conventionally known for obtaining polyurethane. It's okay. Further, regarding the manufacturing technology, there is no need for a technical method that is particularly different from known methods.

Examples of the organic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and prepolymers having these isocyanates at terminal ends.

[0020] When carrying out the present invention, conventional additives may also be used. That is, water is generally used as the blowing agent. In addition to water, low-boiling organic solvents such as monofluorotrichloromethane or methylene chloride can also be used as blowing aids.

Examples of catalysts include organotin compounds such as stannath octoate and dibutyltin dilaurate, amines such as triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, pentamethyldiethylenetriamine, and palmityldimethylamine. You can use types.

[0022] As the foam stabilizer, silicone surfactant,
For example, polydialkylsiloxane or a polysiloxane-polyalkylene oxide block copolymer is used. All commercially available silicone oils for polyurethane foam belong to this type and can be used.

If other quaternary ammonium salts such as n-alkyl-trimethylammonium chloride and n-alkyl-pyridinium bromide are used in place of the quaternary ammonium compound used in the present invention, sufficient antistatic performance can be obtained. Moreover, as the amount added increases, bleeding becomes more severe.

Furthermore, when other metal salts such as sodium sulfate, potassium sulfate, sodium phosphate, sodium carbonate, etc. are used in place of the inorganic acid metal salt used in the present invention, the solubility in the urethane raw material is low; Almost no antistatic effect was observed. In addition, in the case of alkali metal halides, potassium iodide, potassium bromide, etc., which dissolve to some extent in polyurethane manufacturing raw materials, have an antistatic effect, but
I2 and Br2 precipitate on the polyurethane surface, resulting in discoloration.

[0025]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Note that the numbers in the middle part of the example are parts by weight.

Example 1 100 parts of polyethylene adipate (OHV=56), 8 parts of ethylene glycol, 0.5 parts of water, 0.4 parts of triethylene diamine, and a silicone surfactant (SH-193 manufactured by Toray Silicone Co., Ltd.) 1. 0 parts, quaternary ammonium perchlorate shown below

[0027]

[C6]

Premix 5.0 parts of 10 parts of diphenylmethane diisocyanate and polyethylene adipate-based isocyanate prepolymer mixture.
0 parts were mixed and stirred to prepare a test piece on a plate with a thickness of about 5 mm. The resistance value of this test piece was measured over time using a resist meter, and the results are shown in Table 1. In the evaluation of antistatic performance, the voltage applied when using a resist meter was 500 V, and the test piece was measured at 25° C. x 50% after 1 day and 7 days.

Example 2 Glycerin polyoxypropylene triol (OHV=
57) 100 parts, 4.5 parts of water, 0.1 part of pentamethyldiethylenetriamine, silicone surfactant (Silicone oil L-520 manufactured by U.C.C., USA)2.
0 parts, Stanus octoate 0.3 parts, Freon 1
10 parts of 1, quaternary ammonium perchlorate shown below

[0030]

[C7]

Tolylene diisocyanate (commercially available 2,4- and 2,6-
- Tolylene diisocyanate 80:20 mixture) was mixed and stirred to prepare a test piece similar to Example 1. The evaluation results of antistatic performance (resistance value) are shown in Table 1.

Example 3 Sorbitol polyoxypropylene hexol (OHV
= 480) 100 parts, 1.0 part of silicone surfactant (SH-193 manufactured by Toray Silicone Co., Ltd.), 1 part of Freon
30 parts of lithium nitrate, 2.0 parts of lithium nitrate,
grade ammonium perchlorate

[0033]

[Chemical formula 8]

[0034] Premix 2.0 parts and add Sumidur 44V (Crude M manufactured by Sumitomo Bayer Urethane) to this.
A test piece similar to Example 1 was prepared by mixing 125 parts of DI). The evaluation results of antistatic performance are shown in Table 1.

Example 4 100 parts of polybutylene adipate (OHV=86), 6 parts of ethylene glycol, 0.3 parts of triethylene diamine
part, 1.0 part of lithium perchlorate, quaternary ammonium perchlorate shown below

[0036]

[Chemical formula 9]

[0037] Premix 2.0 parts, mix 45 parts of diphenylmethane diisocyanate, and stir.
A test piece similar to Example 1 was prepared. The evaluation results of antistatic performance are shown in Table 1.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that n-uralyltrimethylammonium chloride was added instead of quaternary ammonium perchlorate. In this case as well, the antistatic performance was evaluated in the same manner as in the examples, and the results are shown in Table 1.

Comparative Example 2 A test piece was prepared in the same manner as in Example 3 except that n-uralylpyridinium chloride was added instead of quaternary ammonium perchlorate. In this case as well, the antistatic performance was evaluated in the same manner as in the examples, and the results are shown in Table 1.

Comparative Example 3 A test piece was prepared in the same manner as in Example 3 without adding quaternary ammonium perchlorate. In this case as well, the antistatic performance was evaluated in the same manner as in the examples, and the results are shown in Table 1.

Comparative Example 4 A test piece was prepared using the same formulation and manufacturing method as in Example 1, using sodium sulfate and lauryl trimethylammonium chloride in place of lithium perchlorate and quaternary ammonium perchlorate in Example 4. Created. In this case as well, the antistatic performance was evaluated using the same method as in the example, and the results are shown in Table 1.
It was shown to.

[0042]

[Table 1]

[0043] As shown in Table 1, it can be seen that the products according to the examples of the present invention are significantly superior in antistatic performance, effectiveness, quick-acting properties, and performance stability compared to the comparative examples.

Example 5 8 parts of ethylene glycol was added to 100 parts of poly3-methyl-1,5 pentanediol adipate (OHV=56).
0.5 part of water, 0.4 part of triethylenediamine, silicone surfactant (SH-193 manufactured by Toray Silicone Co., Ltd.)
) 1.0 part, quaternary ammonium perchlorate shown below

[0045]

[Chemical formula 10]

Premix 5.0 parts of diphenylmethane diisocyanate and polyethylene adipate-based isocyanate prepolymer mixture to 10 parts.
0 parts were mixed and stirred to prepare a test piece on a plate with a thickness of about 5 mm. Table 2 shows the results of measuring the resistance value of this test piece over time using a resist meter and the results of a moist heat acceleration test under high temperature and high humidity conditions of 80° C. and 95%.

The antistatic performance was evaluated in the same manner as in Example 1.

[0048] In addition, the hydrolysis resistance is 80% in a constant temperature and humidity chamber.
The strength was measured after 0, 1, 3, and 5 days under the conditions of 90% °C and expressed as the strength retention rate (strength after being left in wet heat/urethane strength x 100).

Example 6 100 parts of a cocondensate (OHV=57) obtained by reacting an equimolar mixture of 3-methyl-1,5 pentanediol and ethylene glycol with adipic acid at a weight ratio of 3:1, and 4 parts of water were added.
．． 5 parts, pentamethyldiethylenetriamine 0.1 part, silicone surfactant (Silicone oil L-520 manufactured by U.C.C., USA) 2.0 parts, stannath octoate 0.3 parts, Freon 11 10 parts, thiocyanine 1.0 part of sodium acid, quaternary ammonium perchlorate shown below

[0050]

[Chemical formula 11]

Tolylene diisocyanate (commercially available 2,4- and 2,6-
- Tolylene diisocyanate 80:20 mixture) was mixed and stirred to prepare a test piece similar to Example 5. Table 2 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance performance.

Example 7 80 parts of poly3-methyl-1,5 pentanediol adipate (OHV=86), polybutylene adipate (
OHV=86) 20 parts, 6 parts of ethylene glycol, 0.3 parts of triethylenediamine, 1.0 parts of lithium perchlorate.
0 parts, quaternary ammonium perchlorate shown below

[0053]

[Chemical formula 12]

[0054] 2.0 parts was premixed, 45 parts of diphenylmethane diisocyanate was mixed therewith, and the mixture was stirred.
A test piece similar to Example 5 was prepared. The evaluation results of antistatic performance and hydrolysis resistance performance are shown in Table 2.

Comparative Example 5 A test piece similar to Example 5 was prepared using the same formulation as in Example 5 except that n-lauryltrimethylammonium chloride was added instead of quaternary ammonium perchlorate. In this case as well, the antistatic performance and hydrolysis resistance performance were evaluated in the same manner as in Example 5, and the results are shown in Table 2.

Comparative Example 6 A test was prepared using the same formulation as in Example 7 without adding quaternary ammonium perchlorate. In this case as well, the antistatic performance and hydrolysis resistance performance were evaluated in the same manner as in Example 5, and the results are shown in Table 2.

Comparative Example 7 Sodium sulfate and lauryltrimethylammonium chloride were used in place of sodium thiocyanate and quaternary ammonium perchlorate in Example 6, and in place of poly3-methyl-1,5 pentanediol and ethylene glycol adipate. Polydiethylene adipate (OHV
=56) A test piece similar to that in Example 5 was created using
The antistatic performance and hydrolysis resistance performance were evaluated in the same manner as in Example 5, and the results are shown in Table 2.

[0058]

[Table 2]

As shown in Table 2, the products according to the examples of the present invention are significantly superior to the comparative examples in terms of antistatic performance, fast-acting properties, performance stability, and hydrolysis resistance. I understand that.

[0060]

According to the production method of the present invention, a polyurethane, particularly a polyurethane that exhibits an excellent antistatic effect without impairing the appearance and physical properties of polyurethane foam, can be obtained.

The polyurethane made by adding the quaternary ammonium perchlorate of the present invention has a semi-permanent antistatic effect, and its performance hardly deteriorates even when washed with water, making it an excellent and durable material. It also has an antistatic effect.

Claims (6)

[Claims] Claim 1: The following general formula (I) [Formula, R1: an alkyl group having 6 to 24 carbon atoms R2: H, or an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group R3: carbon It means an alkyl group, an allyl group, or a benzyl group having numbers 1 to 12. ] An additive for producing polyurethane containing a quaternary ammonium compound represented by the following as an essential component. 2. The additive for producing polyurethane according to claim 1, further comprising one or more selected from alkali metal salts or alkaline earth metal salts of perchloric acid, thiocyanic acid, and nitric acid. 3. When producing polyurethane by reacting a compound having at least two active hydrogens with an organic isocyanate, the following general formula (I) [Chemical formula 2] [wherein R1: carbon number 6 to 24] Alkyl group R2: H or an alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group R3: An alkyl group having 1 to 12 carbon atoms, an allyl group, or a benzyl group. ] A method for producing polyurethane with excellent hydrolysis resistance, which comprises adding a quaternary ammonium compound represented by the following. 4. Claim 3, characterized in that one or more selected from alkali metal salts or alkaline earth metal salts of perchloric acid, thiocyanic acid, and nitric acid are further added.
The method for producing the polyurethane described. 5. The method for producing polyurethane according to claim 3 or 4, wherein the compound having at least two active hydrogens is a polyether polyol or a polyester polyol. 6. The method for producing polyurethane according to claim 5, wherein the polyester polyol is a cocondensate obtained from a diol having a branched alkyl group and a dicarboxylic acid.