JPH1037072A - Penetrating agent for alkali having high concentration - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit good stability of a treating bath and penetrating property in a wide range of an alkali concentration by using a specific quaternary ammonium salt as a penetrating agent for carrying out amount-reducing treatment of polyester fiber or a penetrating agent for carrying out mercerization of cotton. SOLUTION: This penetrating agent is prepared by using at least one kind of quaternary ammonium salts represented by formula I and formula II [R1 is a 1-12C aliphatic alkyl, hydroxyethyl or benzyl; R2 and R3 are each a 1-3C aliphatic alkyl; R4 is a 1-12C aliphatic alkyl or phenyl; A is a 2-4C alkylene; (m) is an integer of 1-3; (n) is o or an integer of 1-5].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a penetrant for high concentration alkali. The present invention particularly relates to a high-performance penetrant excellent in bath stability, which is useful in high-concentration alkali processing in a dyeing step, for example, mercerizing cotton and reducing alkali in polyester fibers.

[0002]

2. Description of the Related Art As a penetrant for high-concentration alkalis, there have hitherto been used penetrants mainly composed of lower to intermediate alcohols having about 1 to 8 carbon atoms and sulfates or phosphates of alkylene oxide adducts thereof. Many are on the market. However, none of these compounds alone sufficiently satisfies both the stability in a high-concentration alkaline bath and the high permeability. In addition, in order to obtain high permeability, a middle alcohol is often used in combination, so that the stability of the treatment bath becomes insufficient, and a stable penetration effect may not be obtained in some cases.

[0003] Recently, there is also a weight-reduction process which requires a higher concentration of alkali to penetrate than conventionally used ones. A conventionally known compound-based penetrant has a high permeability. There is no high-alkaline treatment bath with excellent stability.As a result, the treatment bath lacks stability in mercerizing processing and alkali weight reduction processing, and the quality of the treated cloth is stabilized due to uneven adhesion of the alkaline agent. There is a problem with sex.

[0004]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is to provide a penetrant for high-concentration alkali having excellent stability in a high-concentration alkali bath and having high permeability. It was made for the purpose.

[0005]

Means for Solving the Problems The inventors of the present invention provide:
As a result of intensive studies to solve the above problems, they have found that certain quaternary ammonium salts are stable to high concentrations of alkali and show excellent permeability, and have completed the present invention. is there. That is, the present invention provides a penetrant for high-concentration alkali, comprising at least one quaternary ammonium salt represented by the following general formulas (1) and (2).

[0006]

Embedded image

[0007]

Embedded image

(Wherein R ₁ represents an aliphatic alkyl group having 1 to 12 carbon atoms, hydroxyethyl group or benzyl group, R ₂ and R ₃ each represent an aliphatic alkyl group having 1 to 3 carbon atoms, R ₄ represents an aliphatic alkyl group having 1 to 12 carbon atoms or a phenyl group which is unsubstituted or substituted by an alkyl group having 1 to 6 carbon atoms;
Represents an alkylene group having 2 to 4 carbon atoms, and m represents 1
And n is an integer of 0 or 1 to 5)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds represented by the above general formulas (1) and (2) useful in the present invention are obtained by neutralizing a tertiary amine with a phosphoric acid ester and converting an alkylene oxide to 9
It can be easily synthesized by introducing at 0 to 120 ° C. and performing an addition reaction. 3rd used here
Examples of the secondary amine include trimethylamine, triethylamine, dimethylbutylamine, dimethyloctylamine, dimethylbenzylamine, dimethylethanolamine and the like. Preferred tertiary amines are trimethylamine and triethylamine.

[0010] Phosphate esters of counter salts include lower to middle alcohols such as methanol, ethanol, propanol, butanol and octanol, ethyl carbitol, butyl carbitol, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and the like. Obtained by reacting ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monomethyl phenyl ether, ethylene glycol dimethyl phenyl ether, ethylene glycol monotertiary butyl phenyl ether, etc. with a phosphorylating agent such as phosphoric anhydride, phosphorus oxychloride, etc. Phosphoric acid monoesters and phosphoric diesters. These can be obtained individually or as a mixture of both, but are generally obtained as a mixture of a monoester and a diester. Various tertiary amine phosphate ester salts can be obtained by arbitrarily adjusting the neutralization amount with a tertiary amine according to the acid value of these phosphate esters. Preferred examples of the phosphate ester include a reaction product of butanol or butyl carbitol with a phosphorylating agent.

Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, and preferably ethylene oxide and propylene oxide. In the compounds of the general formulas (1) and (2), when the total number of carbon atoms of R ₁ , R ₂ and R ₃ is 14 or more, the stability of the alkali bath may be deteriorated. The total of these carbon numbers is preferably 4 to 10. Also, R ₁ , R ₂ , R
_If the total number of carbon atoms of ₃ and R ₄ is 20 or more, the stability of the alkaline bath may be poor, and R ₁ , R ₂ , R ₃ and R
_When the sum of 4 is 4 or less, high permeability may not be obtained. Further, n is preferably 0-4. In particular, when the sum of n in the compound of the general formula (2) is 10 or more, the bath stability becomes poor.

The penetrant of the present invention includes a conventionally used anionic surfactant such as a sulfate ester salt or a phosphate ester salt, and a nonionic interface such as an alkylene oxide adduct of an alcohol or an alkylene oxide adduct of an alkylphenol. Activators, chelating agents such as sodium tripolyphosphate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methanol, ethanol, propanol, butanol,
-A solvent such as ethylhexanol, butyl cellosolve, or butyl carbitol may be used in combination.

The penetrating agent of the present invention having the above-described structure can satisfy both the stability in an alkaline bath and the permeability. Further, the penetrant has good compatibility with the anionic activator, and therefore hardly remains on the treated cloth, and does not cause problems such as dye specifications and spots due to cation remaining in a later step.

[0014]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 A reaction vessel was charged with 222 g of n-butanol, and at 30 ° C, 142 g of phosphoric anhydride was added while taking heat generation into consideration.
Add slowly. After the addition, the temperature was gradually raised after the exotherm had subsided, and the mixture was reacted at 70 to 90 ° C. for 3 hours to obtain a mixture of n-butanol monophosphate and diphosphate. The acid value of this product was 455.

Next, 101 g of triethylamine, 100 g of water and 123 g of the above-obtained phosphoric acid ester mixture are added to another high-pressure reactor for neutralization. After replacing the inside of the apparatus with nitrogen gas, the temperature was raised, and 66 g of ethylene oxide was introduced at 90 to 110 ° C. After the internal pressure was reduced by the reaction, a quaternization reaction for aging was performed for 2 hours. Cooled and added water to give a 50% aqueous solution of the product.

EXAMPLE 2 59 g of trimethylamine and 10 parts of water were placed in a high-pressure reactor.
After charging 0 g, 123 g of the phosphoric ester mixture obtained in the first stage of Example 1 is added and neutralized. After replacing the inside of the apparatus with nitrogen gas, the temperature was raised, and 66 g of ethylene oxide was introduced at 90 to 110 ° C. After the internal pressure was reduced by the reaction, a quaternization reaction for aging was performed for 2 hours. ,
Cool and add water to give a 50% aqueous solution of the product.

Example 3 135 g of dimethylbenzylamine and 150 g of water are charged into a high-pressure reactor, and 123 g of the phosphoric ester mixture obtained in the first stage of Example 1 is added to neutralize the mixture. Then, after replacing the inside of the apparatus with nitrogen gas, the temperature is raised to 90 to 110
After introducing 66 g of ethylene oxide at ℃ and lowering the internal pressure by the reaction, a quaternization reaction for aging was performed for 2 hours, followed by cooling and adding water to obtain a 50% aqueous solution of the product. .

Example 4 A high-pressure reactor was charged with 59 g of trimethylamine and 10 g of water.
After charging 0 g, 123 g of the phosphoric ester mixture obtained in the first stage of Example 1 is added and neutralized. After replacing the inside of the apparatus with nitrogen gas, the temperature was raised, and 87 g of propylene oxide was introduced at 90 to 110 ° C., and after the internal pressure was reduced by the reaction, a quaternization reaction for aging was performed for 2 hours. Cooled and added water to give a 50% aqueous solution of the product.

Example 5 A high-pressure reactor was charged with 157 g of dimethyloctylamine and 150 g of water, and 123 g of the phosphoric ester mixture obtained in the first stage of Example 1 was added to neutralize the mixture. Then, after replacing the inside of the apparatus with nitrogen gas, the temperature is raised to 90 to 110
After introducing 66 g of ethylene oxide at ℃ and lowering the internal pressure by the reaction, a quaternization reaction for aging was performed for 2 hours, followed by cooling and adding water to obtain a 50% aqueous solution of the product. .

Example 6 A reaction vessel is charged with 138 g of ethanol, and at 30 ° C., 142 g of phosphoric anhydride is gradually added in consideration of heat generation. After the addition, the temperature was gradually increased after the exotherm had subsided, and the mixture was reacted at 70 to 90 ° C. for 3 hours to obtain a mixture of monophosphate and diphosphate of ethanol. The acid value of this product was 590.

Next, 101 g of triethylamine, 100 g of water and 95 g of the above-obtained phosphoric acid ester mixture are added to another high-pressure reactor for neutralization. After replacing the inside of the apparatus with nitrogen gas, the temperature was raised, and 66 g of ethylene oxide was introduced at 90 to 110 ° C. After the internal pressure was reduced by the reaction, a quaternization reaction for aging was performed for 2 hours. ,
Cool and add water to give a 50% aqueous solution of the product.

Example 7 486 g of butyl carbitol was charged into a reaction vessel, and 30
At ° C., 142 g of phosphoric anhydride are slowly added, taking into account the exotherm. After the addition, the temperature was gradually raised after the exotherm had subsided, and the mixture was reacted at 70 to 90 ° C. for 3 hours to obtain a mixture of monophosphate and diphosphate of butyl carbitol. The acid value of this product was 270.

Next, 101 g of triethylamine, 100 g of water and 207 g of the above-obtained phosphoric ester mixture are added to another high-pressure reactor for neutralization. After replacing the inside of the apparatus with nitrogen gas, the temperature was raised, and 66 g of ethylene oxide was introduced at 90 to 110 ° C. After the internal pressure was reduced by the reaction, a quaternization reaction for aging was performed for 2 hours. Cooled and added water to give a 50% aqueous solution of the product.

Comparative Example 1 50% aqueous solution of butyl phosphate Comparative Example 2 5-ethyl hexanol sulfate sodium salt 5
0% aqueous solution Comparative Example 3 Neolate NA-30 (Nika Chemical Co., Ltd., phosphate ester salt of lower alcohol) Comparative Example 4 50 of tetramethylammonium butyl phosphate salt
% Aqueous solution Comparative Example 5 50% of dodecyldimethylbenzylammonium chloride
% Aqueous solution performance evaluation The following performance evaluation was performed using the obtained penetrants of Examples 1 to 7 and Comparative Examples 1 to 5. Table 1 shows the results.

1) Alkali compatibility First grade caustic soda is dissolved in water, and
A solution having a concentration of 30 and 35% by weight is prepared, and the above-mentioned penetrant (having a nonvolatile content of 50%) is added thereto in an amount of 10 g / liter to prepare a test solution. Evaluation method Each test solution is left at 25 ° C., and the state of the test solution is visually determined based on the following criteria.

○ Uniform and transparent as in the case of no addition, no change even when left for a long time △ Translucent and separated when left for a long time (24 hours) × Oily and separated in a short time 2) Permeability A test solution prepared in the same manner as in 1) is used.

Test Method A test piece (cotton knitted greige) is cut into 2.5 cm × 2.5 cm, and the test piece is floated on a test solution at 25 ° C., and the time until the surface is completely wetted is measured. The smaller the value, the better the permeability. 3) Pickup rate Among test liquids prepared in the same manner as in the liquid preparation method of 1) above, 30% by weight of reagent-grade caustic soda is used as the test liquid.

Test Method A scoured polyester fabric (satin) is passed through the test solution, squeezed with a mangle at a nip pressure of 1 kg / cm ² (1 dip-1 nip), and the pickup rate is determined from the weight change of the fabric before and after the test. Pickup ratio (%) = [(weight after test−weight before test) / weight before test] × 100 It is judged that the larger the value, the better the permeability.

4) Weight Loss Effect (Pad-Steam Method) Of the test liquids prepared in the same manner as in the liquid preparation method of 1) above, a reagent-grade caustic soda of 30% by weight is used as the test liquid. Test Method A scoured polyester fabric (satin) is passed through the above test solution, squeezed with a mangle at a nip pressure of 1 kg / cm ² (1 dip-1 nip), and stretched on a tenter. 1 at 105 ° C by steamer
After steaming for 0 minutes, perform hot water washing, water washing and drying,
The weight loss rate (%) is determined by the following equation.

Weight loss rate (%) = [(weight of raw cloth−weight of treated cloth) / weight of raw cloth] × 100 It is judged that the larger the value, the better the weight loss effect. 5) Persistence (qualify the cationic surfactant remaining on the treated cloth) A dye (CI Di) was added to the treated cloth treated in the same manner as in 4) above.
Rect Black 22) 0.5% by weight (to treated cloth)
The degree of coloring after the dyeing treatment at 30 ° C. for 20 minutes is compared with that of the untreated cloth and evaluated based on the following criteria. The stronger the coloring, the higher the residual property.

○ Same level as untreated cloth, almost no dyeing △ Fairly dyed × Fairly dyed

[0032]

[Table 1]

[0033]

EFFECTS OF THE INVENTION The penetrant for high-concentration alkalis of the present invention has better treatment bath stability over a wide range of alkali concentrations than conventional penetrants comprising sulfate esters and phosphate esters. It has permeability and can be advantageously used as a penetrating agent for reducing the alkali of polyester and a penetrating agent for mercerizing cotton.

Claims (1)

[Claims] 1. A penetrant for high concentration alkali, comprising at least one quaternary ammonium salt represented by the following general formulas (1) and (2). Embedded image Embedded image (Wherein, R ₁ represents an aliphatic alkyl group having 1 to 12 carbon atoms, a hydroxyethyl group or a benzyl group, R ₂ and R ₃ each represent an aliphatic alkyl group having 1 to 3 carbon atoms, and R ₄ represents Represents an aliphatic alkyl group having 1 to 12 carbon atoms or a phenyl group which is unsubstituted or substituted by an alkyl group having 1 to 6 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, Is an integer of 1 to 3, and n is 0 or an integer of 1 to 5)