JPH08113703A - Additive for producing polyurethane and production of polyurethane - Google Patents

Abstract

PURPOSE: To obtain an additive for producing a polyurethane having excellent immediate effect and stability of performance, providing a polyurethane having excellent antistatic performances and hydrolytic resistance without impairing general properties such as moldability and physical properties, comprising an amide group-containing compound of a specific formula as an essential component. CONSTITUTION: This additive comprises an amide group-containing quaternary ammonium compound of formula I (X is CO-NR<5> or NR<5> -CO; Y is ClO4 or R<6> -SO4 ; R<1> is a 6-18C alkylene; R<2> is a 1-6C alkylene; R<3> , R<3> ', R<5> and R<6> are each H or a 1-3C alkyl; R<4> is a 1-3C alkyl) as essential component, preferably further (B) one or more selected from an alkali (alkaline earth) metal salt of perchloric acid, thiocyanic acid and nitric acid and (C) a quaternary ammonium compound of formula II (Y' is ClO4 or a R<10> -SO4 ; R<7> and R<10> are each H or a 1-3C alkyl; R<8> is a 1-3C alkyl; R<9> is a 8-18C alkyl).

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 an antistatic polyurethane excellent in conductivity and hydrolysis resistance.

[0002]

2. Description of the Related Art Generally, plastics have a high electric insulation property, so they are very liable to be charged with static electricity, causing dirt on the surface due to the adhesion of dust or dust, and depending on the place of use, they may be flammable solvents due to static electricity sparks charged. Ignited,
May cause fire or explosion. In the electronic industry, static electricity generated during integrated circuit (IC) manufacture and assembly causes damage to internal circuits, resulting in defective products. Therefore, excellent antistatic performance is imparted to clothes, floors, soles, and the like. There is a need.

By the way, although polyurethane has a lower electric insulation property than other plastics due to its structure, it is still insufficient and the above-mentioned inconvenience may occur. Conventionally, as a method of imparting antistatic performance, addition of carbon black, conductive filler, etc., coating or addition of a surfactant, addition of alkali metal salts such as perchloric acid, thiocyanic acid, nitric acid, etc. are known ( JP-A-63-43951).

[0004]

However, it is difficult to impart sufficient antistatic performance by using a general surfactant, and in using a conductive filler, the raw material itself is added when the polyurethane raw material is added. Since it is accompanied by thickening, there are problems in use and moldability. Further, addition of perchloric acid, thiocyanic acid, an alkali metal salt of nitric acid is excellent in the final conductive performance, but the effect of antistatic performance is slow, and physical properties deteriorate when the amount used is large, especially It has a drawback that it causes hydrolysis.

An object of the present invention is to provide an additive capable of obtaining a polyurethane having excellent antistatic performance and a method for producing the polyurethane without impairing general performance such as moldability and various physical properties.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted earnest studies for the purpose of obtaining a polyurethane having no problem in molding and having excellent antistatic performance. As a result, the following general formula ( 1)

[0007]

Embedded image

(In the formula, X is --CO--NR ⁵ --or-
NR ⁵ —CO—, Y is ClO ₄ or R ⁶ —SO ₄
R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ³ ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ Has 1 to 1 carbon atoms
In the alkyl group of 3, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. By using a quaternary ammonium compound having an amide group represented by the formula (4), a polyurethane having an antistatic property that is extremely good without any deterioration in general performance such as moldability and various physical properties and has a rapid onset of effect. It was determined that Also,
Surprisingly, while the use of general quaternary ammonium salts is mainly aimed at reducing the surface resistance due to bleeding,
The amide-containing quaternary ammonium compound represented by the general formula (1) used in the present invention has a particularly large effect of lowering the volume resistance value and is also effective in the production of a foam such as polyurethane foam. I understood.

That is, the gist of the present invention is (1) the following general formula (1)

[0010]

[Chemical 6]

(In the formula, X is --CO--NR ⁵ --or-
NR ⁵ —CO—, Y is ClO ₄ or R ⁶ —SO ₄
R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ³ ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ Has 1 to 1 carbon atoms
In the alkyl group of 3, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. (2) An additive for producing polyurethane, which contains a quaternary ammonium compound having an amide group represented by the formula (2) as an essential component, (2) Y is R ⁶ -SO ₄ , and R ⁴ and R ⁶ are the same. 1) The additive for polyurethane production described in (3) R ² has ² to 4 carbon atoms
The alkylene group, R ³ , R ³ ′ is an alkyl group having 1 or 2 carbon atoms, and R ⁴ and R ⁵ are alkyl groups having 1 or 2 carbon atoms; )
(2) wherein R ¹ is an alkyl group having 6 to 12 carbon atoms
Or (5) the additive for producing polyurethane described in (3),
(1) The additive for producing polyurethane according to the above (1), wherein Y is ClO ₄ , (6) R ² is an alkylene group having 2 to 4 carbon atoms, R ³ , R ³ ′ is an alkyl group having 1 or 2 carbon atoms,
The additive for producing polyurethane according to the above (5), wherein R ⁴ and R ⁵ are alkyl groups having 1 or 2 carbon atoms, (7) R ¹
Is an alkyl group having 6 to 12 carbon atoms, (5) or (6) the additive for producing polyurethane, (8) further selected from perchloric acid, thiocyanic acid and alkali or alkaline earth metal salts of nitric acid. An additive for polyurethane production according to any one of the above (1) to (7), containing one or more of (9), and further the following general formula (2)

[0012]

[Chemical 7]

(Wherein Y'is ClO ₄ or R ¹⁰ -S
O ₄ , R ⁷ and R ⁷ ′ are hydrogen atoms or 1 to 3 carbon atoms.
The alkyl group, R ⁸ is an alkyl group having 1 to 3 carbon atoms,
R ⁹ represents an alkyl group having 8 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. (1) containing a quaternary ammonium compound represented by
(8) The additive for producing polyurethane according to any one of (1)
0) In the method for producing a polyurethane in which a compound having at least two active hydrogen atoms is reacted with an organic isocyanate, the following general formula (1)

[0014]

Embedded image

(In the formula, X is --CO--NR ⁵ --or-
NR ⁵ —CO—, Y is ClO ₄ or R ⁶ —SO ₄
R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ³ ′ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ Has 1 to 1 carbon atoms
In the alkyl group of 3, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) A quaternary ammonium compound having an amide group represented by the formula (4) is added, wherein (11) Y is R ⁶
(SO) ₄ , wherein the quaternary ammonium compound having an amide group in which R ⁴ and R ⁶ are the same is added, (12) R ²
Is an alkylene group having 2 to 4 carbon atoms, R ³ and R ³ ′ are alkyl groups having 1 or 2 carbon atoms, and R ⁴ and R ⁵ are alkyl groups having 1 or 2 carbon atoms. , (1
3) The production method according to the above (11) or (12), wherein R ¹ is an alkyl group having 6 to 12 carbon atoms, and (14) adding a quaternary ammonium compound having an amide group in which Y is ClO _4. the method of manufacturing the (10), wherein, (15) R ² is an alkylene group having 2 to 4 carbon atoms, R ^3, R ³ 'is an alkyl group having 1 or 2 carbon atoms,
(14) The production method according to (14) above, wherein R ⁴ and R ⁵ are alkyl groups having 1 or 2 carbon atoms, and (16) R ¹ has 6 to 6 carbon atoms.
(14) The production method according to the above (14) or (15), wherein the alkyl group is 12; and (17) one or more selected from alkali or alkaline earth metal salts of perchloric acid, thiocyanic acid and nitric acid. (10) to (1) to be added
6) Any one of the production methods, (18) Further, the following general formula (2)

[0016]

[Chemical 9]

(Wherein Y'is ClO ₄ or R ¹⁰ -S
O ₄ , R ⁷ and R ⁷ ′ are hydrogen atoms or 1 to 3 carbon atoms.
The alkyl group, R ⁸ is an alkyl group having 1 to 3 carbon atoms,
R ⁹ represents an alkyl group having 8 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) In addition to the quaternary ammonium compound represented by the above (10)
To (17), the production method according to any one of (10) to (18), wherein the compound having at least two active hydrogen atoms is a polyester polyol or a polyether polyol, and (19) 20) The production method according to the above (19), wherein the polyester polyol is a cocondensate obtained from a diol having a linear and / or branched alkyl group and a dicarboxylic acid.

First, the additive for producing polyurethane of the present invention will be described. The additive for producing polyurethane according to the present invention has the amide group-containing fourth group represented by the following general formula (1).
The primary ammonium compound is an essential component.

[0019]

[Chemical 10]

In the general formula (1), X is --CO--NR.
⁵ - or represents a -NR ⁵ -CO-. Where R ⁵
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

Y represents ClO ₄ or R ⁶ --SO ₄ . Here, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms.
Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ¹ represents an alkyl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 7 to 12 carbon atoms. If it is smaller than this range or larger than this range, the physical properties of urethane tend to be significantly deteriorated. Specifically, a hexyl group, a heptyl group,
Examples thereof include an octyl group, a nonyl group, a decyl group, a lauryl group, a myristyl group, a cetyl group, a stearyl group, and a methylpentyl group.

R ² represents an alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. If it is larger than this range, the conductive performance tends to be significantly lowered. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group and the like.

R ³ and R ³ 'are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ⁴ represents an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

As the quaternary ammonium compound having an amide group, a quaternary ammonium sulfate having an amide group, that is, Y is R ^6- , is used because of its ease of synthesis, stability and excellent performance. SO ₄ is preferred, and R ⁴ and R ⁶ in the general formula (1) are particularly preferred.

As the quaternary ammonium compound having an amide group represented by the general formula (1) according to the present invention,
In addition to those used in the examples described below, for example, the compounds shown in Table 1 below may be mentioned.

[0027]

[Table 1]

The quaternary ammonium compound having an amide group represented by the general formula (1) according to the present invention can be produced by a generally known method. For example, it can be obtained by reacting the corresponding amidoamine with an equimolar amount of dialkyl sulfuric acid dropwise in a suitable solvent.
This method does not require a technical method which is different from the known method for the production technology of amidoamine and quaternization.

In addition to the above-mentioned quaternary ammonium compound having an amide group, the additive for producing polyurethane of the present invention is optionally selected from alkali or alkaline earth metal salts of perchloric acid, thiocyanic acid and nitric acid. One or two or more of the above are contained. For example, lithium perchlorate, sodium perchlorate, lithium thiocyanate, sodium thiocyanate, lithium nitrate and the like are preferably used. In the present invention, by using such an inorganic acid metal salt in combination, it is possible to obtain a conductive polyurethane that exhibits an antistatic effect more quickly and has excellent final physical properties and performance. It should be noted that when the inorganic acid metal salt is used alone, the antistatic performance is exhibited quickly, but the conductivity is low and the stability is not stable.

Here, the compounding ratio (weight ratio) of the quaternary ammonium compound having an amide group represented by the above general formula (1) and the inorganic acid metal salt in the additive for producing polyurethane of the present invention is the amide group. The quaternary ammonium compound having the formula: inorganic acid metal salt = 20: 0.1 to 1: 1 is preferable, and 10: 0.1 to 2: 1 is more preferable. The mixing ratio of the quaternary ammonium compound having an amide group is
If it is smaller or larger than this range, moldability and various physical properties tend to deteriorate.

In addition to the amide group-containing quaternary ammonium compound represented by the general formula (1), the additive for producing polyurethane of the present invention further comprises the following general formula (2), if necessary.

[0032]

[Chemical 11]

(In the formula, Y'is ClO ₄ or R ¹⁰ -S
O ₄ , R ⁷ and R ⁷ ′ are hydrogen atoms or 1 to 3 carbon atoms.
The alkyl group, R ⁸ is an alkyl group having 1 to 3 carbon atoms,
R ⁹ represents an alkyl group having 8 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) A quaternary ammonium compound represented by In the present invention, by further containing such a compound, it is possible to obtain a conductive polyurethane that exhibits an antistatic property more rapidly and has excellent final physical properties and performance.

In the general formula (2), Y'represents ClO ₄ or R ¹⁰ -SO ₄ . Here, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ⁷ and R ⁷ 'are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ⁸ represents an alkyl group having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ⁹ represents an alkyl group having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms. If it is smaller than this range or larger than this range, the physical properties of urethane tend to be significantly deteriorated. Specific examples thereof include hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, stearyl group, myristyl group, cetyl group and the like.

In the present invention, R ⁸ and R ^{10 in the} general formula (2) are particularly preferred because of their excellent stability and performance.
Are preferably the same.

Examples of the quaternary ammonium compound represented by the general formula (2) according to the present invention include, but are not limited to, those used in Examples described later.

The quaternary ammonium compound represented by the general formula (2) according to the present invention can be produced by a generally known method. For example, an equimolar amount of dialkyl sulfuric acid is added dropwise to the corresponding alkylamine in a suitable solvent,
It can be produced by reacting.

Here, in the case of using the quaternary ammonium compound of the general formula (2), the amide group-containing quaternary ammonium compound represented by the general formula (1) in the additive for producing polyurethane of the present invention is used. Blending ratio (weight ratio)
Is a quaternary ammonium compound having an amide group of the general formula (1): a quaternary ammonium compound of the general formula (2) =
It is preferably 10: 0.1 to 1: 1 and more preferably 1
It is 0: 1 to 2: 1. If the compounding ratio of the quaternary ammonium compound of the general formula (2) is smaller or larger than this range, the desired high antistatic performance tends not to be easily exhibited.

Next, the method for producing the polyurethane of the present invention will be described.

The method for producing a polyurethane of the present invention is the method for producing a polyurethane in which a compound having at least two active hydrogen atoms is reacted with an organic isocyanate, and the method for producing a polyurethane having the amide group represented by the above general formula (1) is used. It is characterized by adding a quaternary ammonium compound.

Examples of the compound having at least two active hydrogen atoms used in the present invention include polyether polyols such as ethylene oxide adducts and propylene oxide adducts such as propylene glycol, glycerin, trimethylolpropane and sorbitol, and adipine. Examples thereof include polyester polyols obtained from acids, succinic acid, maleic acid, phthalic acid and the like and ethylene glycol, propylene glycol, butylene glycol and the like, and polybutadiene polyols. In addition, low molecular weight glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol are also included therein. It is particularly preferable to use polyether polyol and polyester polyol. Further, there is no problem even if the polyol component contains a compound having 3 or more active hydrogen atoms. The average molecular weight of the compound having at least two active hydrogen atoms is preferably about 500 to 3000.

Examples of the organic isocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and / or prepolymers having such isocyanate at the terminal.

The molar ratio of the amount of the compound having at least two active hydrogen atoms to the amount of the organic isocyanate used is usually 0.8 to 1.2, as in the known urethane production.
It is preferably 0.9 to 1.1.

The amide group-containing quaternary ammonium compound represented by the above general formula (1) is preferably used in an amount of 0.05 to 15% by weight, particularly 1 to 1% by weight, based on the raw material for producing polyurethane. A range of 10% by weight is preferable. If the amount used is less than this range, sufficient antistatic performance tends not to be obtained, and if it exceeds this range, the physical properties of polyurethane tend to be significantly reduced.

As a method for adding the additive of the present invention, any general method can be applied. For example, a method of producing a polyurethane by adding the additive of the present invention to a polyol component or the like to perform premixing, mixing organic isocyanate or the like with this, and stirring the mixture is exemplified. At this time, regarding each raw material component other than the quaternary ammonium compound used,
Any of these may be conventionally known ones for obtaining polyurethane. Further, regarding the manufacturing technique, a technical method that is different from a known method is not required.

In addition to the above-mentioned quaternary ammonium compound having an amide group, the method for producing a polyurethane of the present invention comprises:
If necessary, one or more selected from perchloric acid, thiocyanic acid and alkali or alkaline earth metal salts of nitric acid may be added. For example, lithium perchlorate, sodium perchlorate, lithium thiocyanate, sodium thiocyanate, lithium nitrate and the like are preferably used. In the present invention, by further adding such an inorganic acid metal salt, it is possible to obtain a conductive polyurethane which exhibits an antistatic effect more quickly and has excellent final performance. If the inorganic acid metal salt is used alone, the above-mentioned problems occur.

For the same reason as described above, these inorganic acid metal salts are used in an amount of 0.05 to 1 with respect to the raw material for producing polyurethane.
It is preferably used in the range of 0% by weight, and more preferably in the range of 0.1 to 5% by weight.

The addition ratio (weight ratio) of the quaternary ammonium compound having an amide group represented by the above general formula (1) to the inorganic acid metal salt has an amide group for the same reason as described above. Quaternary ammonium compound: inorganic acid metal salt = 20: 0.1 to 1: 1 is preferable, and 10: 0.1 to 2: 1 is more preferable.

Further, in the method for producing a polyurethane of the present invention, a quaternary ammonium compound represented by the general formula (2) can be further added. In this case, the quaternary ammonium compound of the general formula (2) is preferably used in the range of 0.05 to 10% by weight, more preferably 1 to 5% by weight, based on the raw material for producing polyurethane. To be

The mixing ratio (weight ratio) with the quaternary ammonium compound having an amide group represented by the general formula (1) is the same as that of the amide group of the general formula (1). Quaternary Ammonium Compound Having: General Formula (2)
The quaternary ammonium compound is preferably 10: 0.1 to 1: 1 and more preferably 10: 1 to 2: 1.

In the present invention, in addition to the above raw materials, a foaming agent, a catalyst, a foam stabilizer, an anti-yellowing agent and the like can be used, if necessary. These raw materials may be used together with the additive of the present invention, or may be contained in the additive in advance. In the latter case, these raw materials are contained in the additive of the present invention, and it goes without saying that in that case as well, it is included in the technical scope of the additive of the present invention. Absent.

Water is generally used as the foaming agent. In addition to water, a low boiling organic solvent such as monofluorotrichloromethane or methylene chloride can be used as a foaming aid.

As the catalyst, for example, stannous octoate, organotin compounds such as dibutyltin dilaurate, amines such as triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, pentamethyldiethylenetriamine and palmityldimethylamine. Compounds can be used.

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

In the present invention, a quaternary ammonium salt other than the quaternary ammonium compound represented by the above general formula (1) or (2), for example, n-alkyl-trimethylammonium chloride, n- Alkyl-pyridinium bromide or the like can be used. When such a quaternary ammonium salt is used alone, sufficient antistatic performance cannot be obtained and bleeding on the urethane surface becomes severe.

According to the production method of the present invention, it is possible to produce a polyurethane exhibiting an excellent antistatic effect without impairing the appearance and physical properties of the polyurethane.

The polyurethane prepared by adding the amide group-containing monium sulfate of the present invention has a semi-permanent antistatic effect, and its performance hardly deteriorates even by washing with water, and is excellent in durability. Exhibits antistatic effect. Further, in the case of using other metal salt instead of the inorganic acid metal salt used in the present invention, for example, sodium sulfate, potassium sulfate, sodium phosphate, sodium carbonate, etc.,
Solubility in urethane raw materials is also low and almost no antistatic effect is observed. Also, in the case of alkali metal halides and alkaline earth metal salts, potassium iodide, potassium bromide, etc., which are dissolved to some extent in the polyurethane manufacturing raw material, have an antistatic effect, but iodine and bromine are deposited on the polyurethane surface and discolor There is a drawback that

[0061]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" means "part by weight" unless otherwise specified.

Examples 1-1 and 1-2 100 parts of polyethylene adipate (OHV = 56), 8 parts of ethylene glycol, 0.5 part of water, 0.4 part of triethylenediamine, silicone surfactant (manufactured by Toray Silicone Co., Ltd.) , SH-193), and quaternary ammonium salts having an amide group shown in Table 2 are premixed in the amounts shown in Table 2, respectively, and 100 parts of a mixture of diphenylmethane diisocyanate and polyethylene adipate-terminated isocyanate prepolymer is added thereto. After mixing and stirring, a test piece on a plate having a thickness of about 5 mm was prepared. Table 3 shows the results of daily measurement of the resistance value of this test piece using a resist meter. In the evaluation of the antistatic performance, the applied voltage when the resist meter was used was 500 V, and the test piece was measured at a temperature of 25 ° C. and a humidity of 50% (RH).

[0063]

[Table 2]

[0064]

[Table 3]

Examples 2-1 to 2-2 Glycerin polyoxypropylene triol (OHV =
571) 100 parts of water 4.5 parts of pentamethyldiethylenetriamine 0.1 part of silicone surfactant (U.S.A.
C. C silicone oil, L-520) 1.0 part,
0.3 parts stanna octoate, 10 freons
Part, the quaternary ammonium salt having an amide group shown in Table 2 was premixed in the amounts shown in Table 2, and tolylene diisocyanate (commercially available 2,4- and 2,6-tolylene diisocyanate 80:20 56 parts of the mixture) were mixed and stirred to prepare a test piece similar to that in Example 1. Table 3 shows the results of evaluation of antistatic performance (resistance value) performed using this test piece in the same manner as in Example 1.

Examples 3-1 to 3-2 Sorbitol polyoxypropylene hexol (OHV
= 480) 100 parts of water 4.5 parts, pentamethyldiethylenetriamine 0.1 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, Freon 11 30 parts, shown in Table 2. The quaternary ammonium salt having an amide group was premixed in the amounts shown in Table 2, and 125 parts of Sumidule 44V (Crude MDI manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed to prepare a test piece.
Table 3 shows the results of evaluation of antistatic performance (resistance value) performed using this test piece in the same manner as in Example 1.

Examples 4-1 to 4-2 80 parts of poly-3-methyl-1,5-pentanediol adipate (OHV = 86), polybutylene adipate (O
HV = 86) 10 parts, ethylene glycol 6 parts, triethylenediamine 0.3 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, quaternary having amide group shown in Table 2. The ammonium salts were premixed in the amounts shown in Table 2, and 45 parts of diphenylmethane diisocyanate was mixed with this and stirred to prepare similar test pieces. Table 3 shows the results of evaluation of antistatic performance (resistance value) performed using this test piece in the same manner as in Example 1.

Examples 5-1 to 5-2 80 parts of polybutylene adipate (OHV = 86), 6 parts of ethylene glycol and 0.3 part of triethylenediamine,
Silicone-based surfactant (SH-, manufactured by Toray Silicone Co., Ltd.
193) 0.5 parts of quaternary ammonium salt having an amide group shown in Table 2 was premixed in the amounts shown in Table 2, and 45 parts of diphenylmethane diisocyanate was mixed and stirred to prepare a test piece. Table 3 shows the results of evaluation of antistatic performance (resistance value) performed using this test piece in the same manner as in Example 1.

Examples 6-1 to 6-2 A cocondensate (OHV = 57) obtained by reacting an equimolar mixture of 3-methyl-1,5-pentanediol and ethylene glycol with adipic acid in a weight ratio of 3: 1. ) 100 parts of water 4.
5 parts, pentamethyldiethylenetriamine 0.1 part, silicone type surfactant (U.S.C.C., USA, silicone oil L-520) 2.0 parts, stannas octoate 0.3 part, Freon 11 10 parts Parts, quaternary ammonium salts having an amide group shown in Table 2 are premixed in the amounts shown in Table 2, and tolylene diisocyanate (commercially available 2,4- and 2,6-tolylene diisocyanate 8
56 parts of a mixture of 0:20) were mixed and stirred to prepare a similar test piece. Table 3 shows the results of evaluation of antistatic performance (resistance value) performed using this test piece in the same manner as in Example 1.

Comparative Examples 1-1 to 1-3 In Example 1, as shown in Table 2, a quaternary ammonium salt having no amide group was added instead of the quaternary ammonium salt having an amide group. Alternatively, a test piece was prepared in the same manner as in Example 1 except that it was not used at all. Table 3 shows the evaluation results of antistatic performance (resistance value) by the same method.

Examples 7-1 to 7-2 100 parts of polyethylene adipate (OHV = 56), 8 parts of ethylene glycol, 0.5 part of water, 0.4 part of triethylenediamine, silicone surfactant (Toray Silicone Co., Ltd.). , SH-193) 1.0 part, and the quaternary ammonium salt having an amide group shown in Table 4 and the quaternary ammonium salt are premixed in the amounts shown in Table 4, respectively, and diphenylmethane diisocyanate and polyethylene adipate substrate-terminated isocyanate are added thereto. 10 prepolymer mixture
0 parts were mixed and stirred to prepare a test piece on a plate having a thickness of about 5 mm. Using this test piece, the resistance value was measured daily using a resist meter, and a wet heat acceleration test was carried out under a high temperature and high humidity condition of 80 ° C. × 95%. In addition, hydrolysis resistance is 0, 1, under the condition of 80 ° C × 95% in a constant temperature and humidity chamber.
Strength measurement after 3 and 5 days, strength retention rate (%)
(Strength after standing in wet heat / urethane strength × 100).
Table 5 shows the results of these evaluations.

[0072]

[Table 4]

[0073]

[Table 5]

Examples 8-1 to 8-2 Glycerin polyoxypropylene triol (OHV =
571) 4.5 parts to 100 parts water, 0.1 part pentamethyldiethylenetriamine 0.1 part Silicone surfactant (U.S.A.
C. C silicone oil, L-520) 1.0 part,
0.3 parts stanna octoate, 10 freons
Part, the quaternary ammonium salt having an amide group shown in Table 4 and the quaternary ammonium salt are premixed in the amounts shown in Table 4, and tolylene diisocyanate (commercially available 2,4- and 2,6-triethyl Range Isocyanate 80:
56 parts of (20 mixture) were mixed and stirred to prepare a test piece similar to that in Example 7. Table 5 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 7.

Examples 9-1 to 9-2 Sorbitol polyoxypropylene hexol (OHV
= 480) 100 parts of water 4.5 parts, pentamethyldiethylenetriamine 0.1 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, Freon 11 30 parts, shown in Table 4. An amide-containing quaternary ammonium salt and a quaternary ammonium salt were premixed in the amounts shown in Table 4, and 125 parts of Sumidule 44V (Crude MDI manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed to prepare a test piece. did. Example 7 using this test piece
Table 5 shows the evaluation results of the antistatic performance (resistance value) and hydrolysis resistance, which were performed in the same manner as in.

Examples 10-1 to 10-2 80 parts of poly-3-methyl-1,5-pentanediol adipate (OHV = 86), polybutylene adipate (O
HV = 86) 10 parts, ethylene glycol 6 parts, triethylenediamine 0.3 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, quaternary having amide group shown in Table 4. Premixed ammonium salt and quaternary ammonium salt in the amounts shown in Table 4, respectively,
45 parts of diphenylmethane diisocyanate is mixed with this,
A similar test piece was prepared by stirring. Table 5 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 7.

Examples 11-1 to 11-2 80 parts of polybutylene adipate (OHV = 86), 6 parts of ethylene glycol and 0.3 part of triethylenediamine,
Silicone-based surfactant (SH-, manufactured by Toray Silicone Co., Ltd.
193) 0.5 part, quaternary ammonium salt having an amide group shown in Table 4 and quaternary ammonium salt were premixed in the amounts shown in Table 4, and 45 parts of diphenylmethane diisocyanate was mixed and stirred to test. Pieces were made. Table 5 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 7.
Shown in

Examples 12-1 to 12-2 A cocondensate (OHV = 57) obtained by reacting an equimolar mixture of 3-methyl-1,5-pentanediol and ethylene glycol with adipic acid in a weight ratio of 3: 1. ) 100 parts of water 4.
5 parts, pentamethyldiethylenetriamine 0.1 part, silicone-based surfactant (U.S.C.C. company made, silicone oil L-520) 2.0 parts, stance octoate 0.3 part, Freon 11 10 parts , A quaternary ammonium salt having an amide group shown in Table 4 and a quaternary ammonium salt are premixed in the amounts shown in Table 4, and tolylene diisocyanate (commercially available 2,4- and 2,6-tolylene diamine 56 parts of 80:20 isocyanate) were mixed and stirred to prepare a similar test piece. Table 5 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 7.

Comparative Examples 2-1 to 2-3 In Example 7, as shown in Table 4, a quaternary ammonium salt having an amide group and a quaternary ammonium salt having no amide group instead of the quaternary ammonium salt. A test piece was prepared in the same manner as in Example 7 except that the ammonium salt was added alone or not used at all. Table 5 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance performance by the same method.

Examples 13-1 to 13-2 100 parts of polyethylene adipate (OHV = 56), 8 parts of ethylene glycol, 0.5 part of water, 0.4 part of triethylenediamine, a silicone type surfactant (manufactured by Toray Silicone Co., Ltd.) , SH-193), quaternary ammonium salts having an amide group shown in Table 6 and inorganic acid metal salts shown in Table 6, respectively, were premixed therein, and diphenylmethane diisocyanate and polyethylene adipate substrate-terminated isocyanate premix were added thereto. 100 parts of the polymer mixture was mixed and stirred to prepare a plate-shaped test piece having a thickness of about 5 mm.
The resistance value of this test piece was measured daily using a resist meter, and a wet heat acceleration test was carried out under a high temperature and high humidity condition of 80 ° C. × 95%. As for the hydrolysis resistance, the strength was measured after 0, 1, 3, and 5 days in a thermo-hygrostat at 80 ° C x 95%, and the strength retention rate (%) (strength after standing in wet heat /
Urethane strength × 100). The results of these evaluations are shown in Table 7.

[0081]

[Table 6]

[0082]

[Table 7]

Examples 14-1 to 14-2 Glycerin polyoxypropylene triol (OHV =
571) 100 parts of water 4.5 parts, pentamethyldiethylenetriamine 0.1 part, silicone type surfactant (U.S.C.C., USA, silicone oil L-520) 1.0
Part, Stance Octoate 0.3 parts, Freon 11
0 parts of the quaternary ammonium salt having an amide group shown in Table 6 and the inorganic acid metal salt are premixed in the amounts shown in Table 6, and tolylene diisocyanate (commercially available 2,4
56 parts of a mixture of -and 2,6-tolylene diisocyanate 80:20) were mixed and stirred to prepare a similar test piece. Table 7 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 13.

Examples 15-1 to 15-2 Sorbitol polyoxypropylene hexol (OHV)
= 480) 100 parts of water 4.5 parts, pentamethyldiethylenetriamine 0.1 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, Freon 11 30 parts, shown in Table 6. The quaternary ammonium salt having an amide group and the inorganic metal salt were premixed in the amounts shown in Table 6, and 125 parts of Sumidule 44V (Crude MDI manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed to prepare a test piece. Table 7 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were obtained by using this test piece in the same manner as in Example 13.

Examples 16-1 to 16-2 80 parts of poly-3-methyl-1,5-pentanediol adipate (OHV = 86), polybutylene adipate (O
HV = 86) 10 parts, ethylene glycol 6 parts, triethylenediamine 0.3 part, silicone surfactant (Toray Silicone Co., Ltd., SH-193) 0.5 part, quaternary having amide group shown in Table 6. An ammonium salt and an inorganic acid metal salt were premixed in the amounts shown in Table 6, and 45 parts of diphenylmethane diisocyanate was mixed and stirred therein,
A similar test piece was prepared. Example 1 using this test piece
Table 7 shows the evaluation results of antistatic performance (resistance value) and hydrolysis resistance, which were performed in the same manner as in No. 3.

Examples 17-1 to 17-2 Polybutylene adipate (OHV = 86) 80 parts, ethylene glycol 6 parts, triethylenediamine 0.3 part,
Silicone-based surfactant (SH-, manufactured by Toray Silicone Co., Ltd.
193) 0.5 part of the quaternary ammonium salt having an amide group shown in Table 6 and the inorganic acid metal salt are premixed in the amounts shown in Table 6, and 45 parts of diphenylmethane diisocyanate is mixed and stirred to obtain a test piece. Was produced. Table 7 shows the evaluation results of the antistatic performance (resistance value) and the hydrolysis resistance performance, which were performed in the same manner as in Example 13 using this test piece.

Examples 18-1 to 18-2 A cocondensate (OHV = 57) obtained by reacting an equimolar mixture of 3-methyl-1,5-pentanediol and ethylene glycol with adipic acid in a weight ratio of 3: 1. ) 100 parts, 4.5 parts water, 0.1 parts pentamethyldiethylenetriamine
Parts, silicone-based surfactant (U.S.C.C., USA, silicone oil L-520) 2.0 parts, stance octoate 0.3 parts, Freon 11 10 parts, and amide groups shown in Table 6. A quaternary ammonium salt and an inorganic acid metal salt were premixed in the amounts shown in Table 6, and 56 parts of tolylene diisocyanate (commercial mixture of 2,4- and 2,6-tolylene diisocyanate 80:20) was added thereto. A similar test piece was prepared by mixing and stirring. Table 7 shows the evaluation results of the antistatic performance (resistance value) and the hydrolysis resistance performance, which were performed in the same manner as in Example 13 using this test piece.

Comparative Examples 3-1 to 3-3 In the same manner as in Example 13, except that, as shown in Table 6, an inorganic acid metal salt is added instead of the quaternary ammonium salt having an amide group. To prepare a test piece.
Table 7 shows evaluation results of antistatic performance (resistance value) and hydrolysis resistance performance by the same method.

As is clear from the above results, in each of the examples using the additive for producing polyurethane of the present invention, the resistance value is low and the antistatic property is excellent, and the fast-acting property and the performance stability are also excellent. It was also found that it has excellent hydrolysis resistance. On the other hand, Comparative Example 1 using a quaternary ammonium salt having no amide group
1,1-2,2-1,2-2, Comparative Examples 1-3, 2-3 which did not use quaternary ammonium salt, and Comparative Examples 3-1-3-3 which used only inorganic acid metal salt. In No. 3, the resistance value was high and the antistatic performance was inferior, the resistance value did not decrease so much over time, and the hydrolysis resistance was also inferior.

[0090]

Industrial Applicability When a polyurethane is produced using the additive for producing polyurethane of the present invention, a polyurethane having excellent antistatic performance and hydrolysis resistance can be obtained without impairing general performance such as moldability and physical properties. it can. The additive is also excellent in fast-acting property and performance stability.

Claims (20)

[Claims] 1. The following general formula (1): (In the formula, X is —CO—NR ⁵ — or —NR ⁵ —CO
- a, Y is a ClO ₄ or R ⁶ -SO _4, the R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ^3, R ³ 'is a hydrogen atom Alternatively, R ⁴ represents an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group having 1 to 3 carbon atoms, and R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4) having an amide group represented by
Additives for polyurethane production containing a quaternary ammonium compound as an essential component. 2. Y is R ⁶ —SO ₄ , and R ⁴ and R
^The additive for producing polyurethane according to claim 1, wherein ⁶ are the same. 3. R ² is an alkylene group having 2 to 4 carbon atoms, R ^2
3 , R ³ 'is an alkyl group having 1 or 2 carbon atoms, R ⁴ , R ⁵
The additive for producing polyurethane according to claim 2, wherein is an alkyl group having 1 or 2 carbon atoms. 4. The additive for producing polyurethane according to claim 2, wherein R ¹ is an alkyl group having 6 to 12 carbon atoms. 5. The additive for producing polyurethane according to claim 1, wherein Y is ClO ₄ . 6. R ² is an alkylene group having 2 to 4 carbon atoms, R ^2
3 , R ³ 'is an alkyl group having 1 or 2 carbon atoms, R ⁴ , R ⁵
The additive for producing polyurethane according to claim 5, wherein is an alkyl group having 1 or 2 carbon atoms. 7. The additive for producing polyurethane according to claim 5, wherein R ¹ is an alkyl group having 6 to 12 carbon atoms. 8. The additive for producing polyurethane according to claim 1, further comprising one or more selected from alkali or alkaline earth metal salts of perchloric acid, thiocyanic acid and nitric acid. 9. The following general formula (2): (In the formula, Y ′ is ClO ₄ or R ¹⁰ —SO ₄ ,
R ⁷ and R ⁷ ′ are hydrogen atoms or an alkyl group having 1 to 3 carbon atoms, R ⁸ is an alkyl group having 1 to 3 carbon atoms, R ⁹ is an alkyl group having 8 to 18 carbon atoms, and R ¹⁰ is hydrogen. Represents an atom or an alkyl group having 1 to 3 carbon atoms. ) Represented by
The additive for polyurethane production according to any one of claims 1 to 8, which contains a secondary ammonium compound. 10. A method for producing a polyurethane by reacting a compound having at least two active hydrogen atoms with an organic isocyanate, wherein the following general formula (1): (In the formula, X is —CO—NR ⁵ — or —NR ⁵ —CO
- a, Y is a ClO ₄ or R ⁶ -SO _4, the R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ^3, R ³ 'is a hydrogen atom Alternatively, R ⁴ represents an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group having 1 to 3 carbon atoms, and R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4) having an amide group represented by
A method for producing a polyurethane, which comprises adding a quaternary ammonium compound. 11. The process according to claim 10, wherein Y is R ⁶ —SO ₄ and a quaternary ammonium compound having an amide group in which R ⁴ and R ⁶ are the same is added. 12. R ² is an alkylene group having 2 to 4 carbon atoms,
R ³ and R ³ 'are alkyl groups having 1 or 2 carbon atoms, R ⁴ and R
The production method according to claim 11, wherein ⁵ is an alkyl group having 1 or 2 carbon atoms. 13. The production method according to claim 11, wherein R ¹ is an alkyl group having 6 to 12 carbon atoms. 14. The method according to claim 10, wherein a quaternary ammonium compound having an amide group in which Y is ClO ₄ is added. 15. R ² is an alkylene group having 2 to 4 carbon atoms,
R ³ and R ³ 'are alkyl groups having 1 or 2 carbon atoms, R ⁴ and R
The production method according to claim 14, wherein ⁵ is an alkyl group having 1 or 2 carbon atoms. 16. The method according to claim 14 or 15, wherein R ¹ is an alkyl group having 6 to 12 carbon atoms. 17. The method according to claim 10, further comprising one or more selected from alkali or alkaline earth metal salts of perchloric acid, thiocyanic acid and nitric acid. 18. A compound represented by the following general formula (2): (In the formula, Y ′ is ClO ₄ or R ¹⁰ —SO ₄ ,
R ⁷ and R ⁷ ′ are hydrogen atoms or an alkyl group having 1 to 3 carbon atoms, R ⁸ is an alkyl group having 1 to 3 carbon atoms, R ⁹ is an alkyl group having 8 to 18 carbon atoms, and R ¹⁰ is hydrogen. Represents an atom or an alkyl group having 1 to 3 carbon atoms. ) Represented by
The production method according to claim 10, wherein a secondary ammonium compound is added. 19. The method according to claim 10, wherein the compound having at least two active hydrogen atoms is a polyester polyol or a polyether polyol. 20. The polyester polyol is linear and / or
20. The production method according to claim 19, which is a cocondensate obtained from a diol having a branched alkyl group and a dicarboxylic acid.