JP3167137B2 - Method for producing polyurethane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of manufacturing a superior antistatic polyurethane hydrolysis resistance.

[0002]

2. Description of the Related Art In general, plastics have a high electrical insulation property and are therefore very susceptible to static electricity, causing dirt and dust to adhere to the surface, and depending on the place of use, flammable solvents due to sparks caused by charged static electricity. May ignite, causing a fire or explosion. Also, in the electronics industry, static electricity destroys internal circuits during the manufacture and assembly of integrated circuits (ICs), resulting in defective products. Therefore, clothing, floors, shoe soles (safety shoes, men's shoes, etc.), etc. It is necessary to impart excellent antistatic performance to the above.

[0003] Polyurethane is structurally less electrically insulating than other plastics, but is still inadequate, and polyurethane foams are particularly foamed and have a low density, thus causing the above disadvantages. Conventionally, methods for imparting antistatic performance include the addition of carbon black, conductive fillers, etc., the application and addition of surfactants, and the addition of alkali metal salts such as perchloric acid, thiocyanic acid or nitric acid.
No. 63-43951) is known.

[0004]

However, the use of ordinary surfactants cannot provide sufficient performance, and the use of conductive fillers increases the viscosity of the raw materials themselves when polyurethane materials are added. Accordingly, there is a problem in moldability in use. Further, although alkali metal salts of perchloric acid, thiocyanic acid or nitric acid are excellent in the final conductive performance, they have a drawback that the effect is slow to be exhibited.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of obtaining a polyurethane having no problem in molding and having excellent antistatic performance. As a result, a small amount of the following general formula ( I)

[0006]

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Wherein R ₁ is an alkyl group having 6 to 24 carbon atoms
R ₂ : H or an alkyl group, allyl group or benzyl group having 1 to 12 carbon atoms R ₃ : an alkyl group, allyl group or benzyl group having 1 to 12 carbon atoms. A quaternary ammonium compound represented by the formula: and at least two active hydrogens
3-methyl-1,5 pentanedioate
Condensate Obtained from Diol Containing Diol and Dicarboxylic Acid
It was clarified that the use of a polyurethane having extremely good antistatic performance with a fast onset of the effect can be obtained without impairing general physical properties at all. Also, surprisingly, the general purpose of the quaternary ammonium salt is to reduce the surface resistance due to bleeding, while the quaternary ammonium compound represented by the above general formula (I) used in the present invention is used. Has a particularly large effect of lowering the volume resistance value, and has been found to be particularly effective in foams such as polyurethane foam.

That is, the present invention provides a method for producing a polyurethane by reacting a compound having at least two active hydrogens with an organic isocyanate.

[0009]

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Wherein R ₁ is an alkyl group having 6 to 24 carbon atoms
R ₂ : H or an alkyl group, allyl group or benzyl group having 1 to 12 carbon atoms R ₃ : an alkyl group, allyl group or benzyl group having 1 to 12 carbon atoms. The quaternary ammonium compound was added represented by], it has at least two active hydrogen
3-methyl-1,5 pentanediol
Using co-condensate obtained from diol and dicarboxylic acid
It is intended to provide a method for producing a polyurethane having excellent hydrolysis resistance.

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

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

[0013]

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The quaternary ammonium compound represented by the above general formula (I) according to the present invention is obtained by quaternizing a tertiary amine with an alkyl chloride in a suitable solvent, and further adding sodium perchlorate dropwise to form a salt. Obtained by having them exchanged.

The above general formula is used for a raw material for producing polyurethane.
The quaternary ammonium compound represented by (I) is preferably used in the range of 0.05 to 10% by weight. If the amount is less than 0.05% by weight, sufficient antistatic performance cannot be obtained, and
If it exceeds 10% by weight, the physical properties of the polyurethane are greatly reduced. Any general method can be applied to the method of adding the additive of the present invention. For example, a method in which an additive is dissolved in a solvent such as ethylene glycol, diethylene glycol, butanediol, and the like and added to a compound having an active hydrogen atom, and the like can be mentioned.

The inorganic acid metal salt used as required in the present invention is an alkali metal salt or an alkaline earth metal salt of perchloric acid, thiocyanic acid or nitric acid. Calcium acid, lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, lithium nitrate and the like are preferably used, and two or more of them can be used in combination. The inorganic acid metal salt is preferably used in a range of 0.05 to 10% by weight based on the raw material for producing polyurethane. The ratio of the quaternary ammonium compound represented by the general formula (I) and the inorganic acid metal salt according to the present invention is preferably 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 having a fast effect and excellent final performance can be obtained. In addition, when the inorganic acid metal salt is used alone, it takes time until the antistatic performance is developed and stabilized.

In the present invention, at least two active hydrogens are
As a compound having 3-methyl-1,5 pentanediol
And if necessary, other polyols and dicarboxylic acids.
Cocondensate obtained, for example, 3-methyl-1,5 pentane
Co-condensation product of diol and adipic acid (average molecular weight 1500)
Methyl-1,5 pentanediol, ethylene glycol
Co-condensate of sebacic acid (average molecular weight 2000) 3-methyl-1,
5 Pentanediol, glycerin and adipic acid (average molecule
A cocondensate having an amount of 2000) is used. Such a co-condensate
By using this, it is possible to use poly
Urethane can be manufactured. Of these co-condensates
The average molecular weight is preferably from 500 to 3,000.

In addition to the co-condensate, compounds having at least two active hydrogens include polyether polyols such as ethylene oxide adducts such as propylene glycol, glycerin, trimethylolpropane and sorbitol, and propylene oxide adducts. Also, a polyester polyol obtained from adipic acid, succinic acid, maleic acid, phthalic acid and the like with ethylene glycol, propylene glycol, butylene glycol and the like, and a polybutadiene polyol and the like may be used in combination. In addition, low molecular weight glycol, ethylene glycol, propylene glycol, butylene glycol, and diethylene glycol are also included therein. Further, there is no problem even if a compound having three or more active hydrogen atoms is contained in other polyol components. The average molecular weight of the compound having at least two active hydrogens is preferably about 500 to 3000.

The raw materials 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 are all conventionally known for obtaining polyurethane. You may. Also, the manufacturing technique does not require a technical method that is significantly different from a known method.

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

In practicing the present invention, ordinary additives can be used in combination. That is, water is generally used as the foaming agent. In addition to water, a low boiling organic solvent such as monofluorotrichloromethane or methylene chloride can also be used as a foaming aid.

Examples of the catalyst include organic tin compounds such as stannasoctoate and dibutyltin dilaurate, and amines such as triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, pentamethyldiethylenetriamine, and palmityldimethylamine. Can be used.

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

If a quaternary ammonium salt such as n-alkyl-trimethylammonium chloride or n-alkyl-pyridinium bromide is used in place of the quaternary ammonium compound used in the present invention, sufficient antistatic performance can be obtained. In addition, bleeding becomes severe as the amount of addition increases.

When other metal salts such as sodium sulfate, potassium sulfate, sodium phosphate and sodium carbonate 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 is observed. In the case of an alkali metal halide, potassium iodide, potassium bromide, and the like, which are dissolved to some extent in the raw material for producing polyurethane, have an antistatic effect, but I ₂ and Br ₂ are deposited on the polyurethane surface to cause discoloration.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The middle part in the examples is part by weight.

Example 1 Poly-3-methyl-1,5 pentanediol adipate (OHV = 5
6) 100 parts of ethylene glycol 8 parts, water 0.5 part, triethylenediamine 0.4 part, silicone surfactant (SH-193 manufactured by Toray Silicone Co., Ltd.) 1.0 part, quaternary ammonium perchlorate shown below

[0028]

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5.0 parts were premixed, and 100 parts of a mixture of diphenylmethane diisocyanate and a polyisocyanate-terminated isocyanate prepolymer was mixed and stirred to prepare a test piece on a plate having a thickness of about 5 mm. Table 1 shows the result of the resistance value of this test piece measured over time using a resist meter and the result of accelerated wet heat test under high temperature and high humidity conditions of 80 ° C. × 95%. In addition, antistatic performance
In the evaluation of, the applied voltage when using a resist meter was
7 days after 1 day at 500V, 25 ° C x 50%
It was measured later. The hydrolysis resistance is 80% in a thermo-hygrostat.
Under the condition of 90 ° C. × 90%, the strength was measured after 0, 1, 3, and 5 days, and the strength retention rate (strength after standing in wet heat / urethane strength ×
100).

Example 2 4.5 parts of water was added to 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. Pentamethyldiethylenetriamine 0.1 part silicone surfactant (US
2.0 parts of UCC silicone oil L-520) 2.0 parts, stannas octoate 0.3 parts, Freon 11 10 parts, sodium thiocyanate 1.0 part, quaternary ammonium perchlorate shown below

[0031]

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[0032] 2.0 parts of the premix, to which a 56 parts mixture (a mixture of commercially available 2,4- and 2,6-tolylene diisocyanate 80:20) tolylene diisocyanate, stirred and the same manner as in Example 1 Test pieces were prepared. Table 1 shows the evaluation results of the antistatic performance (resistance value) and the hydrolysis resistance performance.

Example 3 Poly-3-methyl-1,5 pentanediol adipate (OHV = 8
6) 80 parts, polybutylene adipate (OHV = 86) 20 parts, ethylene glycol 6 parts, triethylenediamine 0.3 part, lithium perchlorate 1.0 part, quaternary ammonium perchlorate shown below

[0034]

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2.0 parts were premixed, and 45 parts of diphenylmethane diisocyanate was mixed and stirred.
A test piece similar to that of No. 1 was prepared. Table 1 shows the evaluation results of the antistatic performance and the hydrolysis resistance performance.

[0036] was prepared in the same manner as the test piece and Comparative Example 1 Example Example 1 by adding n- lauryl trimethyl ammonium chloride in place of the quaternary ammonium perchlorate similar to formulation 1. Also in this case, the antistatic performance and the hydrolysis resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A test was made in the same manner as in Example 3 except that no quaternary ammonium perchlorate was added. Also in this case, the antistatic performance and the hydrolysis resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 In place of sodium thiocyanate and quaternary ammonium perchlorate in Example 2 , sodium sulfate and lauryltrimethylammonium chloride were used instead of poly-3-methyl-1,5 pentanediol and ethylene glycol adipate. A test piece similar to that of Example 1 was prepared using polydiethylene adipate (OHV = 56), and its antistatic performance and hydrolysis resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1. Was.

[0039]

[Table 1]

As shown in Table 1, those according to the examples of the present invention are significantly superior to those of the comparative examples in terms of effectiveness in antistatic performance, quick action and performance stability, and hydrolysis resistance. You can see that.

[0041]

According to the production method of the present invention, a polyurethane which exerts an excellent antistatic effect without impairing the appearance and physical properties of the polyurethane, especially the polyurethane foam, can be obtained. The polyurethane prepared by adding the quaternary ammonium perchlorate of the present invention has a semi-permanent antistatic effect, and its performance is hardly deteriorated even by washing with water. Has an effect.

Continuation of the front page (72) Inventor Hiroshi Kitagawa 338-1 Enohara, Wakayama City, Wakayama Prefecture (56) References JP-A-50-35293 (JP, A) JP-A-63-43951 (JP, A) JP-A 50 −41993 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C08K 5/19 C08L 75/04-75/12

Claims (2)

(57) [Claims] In producing a polyurethane by reacting a compound having at least two active hydrogens with an organic isocyanate, a compound represented by the following general formula (I): [Wherein, R ₁ : an alkyl group having 6 to 24 carbon atoms R ₂ : H or 1 carbon atom
12 alkyl group, an allyl group or a benzyl group R _3: means an alkyl group, an allyl group or a benzyl group having 1 to 12 carbon atoms. The quaternary ammonium compound was added represented by]
As a compound having at least two active hydrogens,
Diols and dicarboxy containing chill-1,5-pentanediol
A process for producing a polyurethane having excellent hydrolysis resistance , comprising using a cocondensate obtained from an acid . 2. An alkali metal salt or an alkaline earth metal salt of perchloric acid, thiocyanic acid and nitric acid.
The method for producing a polyurethane according to claim 1, wherein one or more kinds are added.