KR20050108189A - An amido compound as a bleach activator and preparation thereof - Google Patents

Abstract

The present invention relates to an amido-based compound and a method for preparing the same, wherein the amido-based compound represented by the following Chemical Formula 1 emits peroxycarboxylic acid activating an inorganic peroxide only in water at room temperature or low temperature so that bleaching power for hydrophilic and hydrophobic stains Because of its excellent storage stability, it can be usefully used as an activator of bleach.

[Formula 1]

Wherein R ₁ , R ₂ , n, R ₃ , L are the same as defined in the specification.

Description

Amido compound as a bleach activator and preparation according to the present invention

The present invention relates to an amido-based compound and a method for preparing the same, and more particularly, to release peroxycarboxylic acid activating an inorganic peroxide only in water at room temperature or low temperature, excellent in bleaching power for hydrophilic and hydrophobic stains, and excellent storage stability. Therefore, the present invention relates to an amido-based compound represented by Formula 1, which is useful as a bleach activator.

In Korea, the bleaching effect has been used for several decades to wash and dry using ultraviolet rays of sunlight or sunlight. This method not only enhances the cleaning effect, but also promotes oxidation to exhibit a bleaching effect and enables sterilization, but there is a problem in that the person who washes has to take the inconvenience of boiling, washing and drying.

Washing methods using inorganic peroxides, which have been used in Europe, can more easily remove bleachable contaminants such as fruit juice, coffee, wine, and grass juice. As the inorganic peroxides that release hydrogen peroxide in the aqueous solution, sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, sodium peroxophosphate, urea peroxohydrate, sodium peroxide and mixtures thereof may be used. However, sodium perborate exhibits a bleaching effect at 80 ° C or higher, and sodium percarbonate also exhibits a bleaching effect at 60 ° C or higher.

Most of domestic washing conditions are performed at room temperature, and the washing is performed in cold water of 20-25 ° C. in summer and even 5 ° C. in winter. It is very difficult to obtain a satisfactory bleaching effect by using bleach alone under such domestic washing conditions. Therefore, domestic consumers could feel the bleaching effect only by using bleach when boiled or by using excessive bleach in hot water.

To overcome this problem, a number of organic compounds have been studied that release peroxycarboxylic acid, which is a bleaching activator that reacts with hydrogen peroxide during the washing process and has a bleaching effect at low temperatures.

Tetra acetyl ethylene diamine (TAED) is the most commonly used bleach activator. However, in the case of tetraacetylethylenediamine, the bleaching effect on the hydrophilic juice stain is excellent, but the bleaching effect on oily stains such as sebum and blood from the human body has a limit.

U.S. Patent No. 4,412,934, U.S. Patent 4,483,778, U.S. Patent 4,606,838, U.S. Patent 4,671,891, and the like disclose a bleach using an acyl compound as a bleach activator. However, the acyl compound has to use a large amount compared to tetraacetylethylenediamine, which not only has a problem in economical efficiency, but also does not sufficiently express the bleaching power at low temperatures, and washes the water after reacting with an inorganic peroxide and an aqueous solution to express the bleaching power. And there is a disadvantage that is difficult to use, leaving a strong smell on clothing and the like.

Although US Patent No. 4,634,551, US Patent No. 4,852,989, US Patent 5,414,099, US Patent No. 5,183,584, and the like also describe amido derivative bleach activators, there is a limit to the bleaching effect on hydrophobic contamination.

In addition, a number of organic peroxycarboxylic acids are described as bleach activators for detergents in U.S. Patent No. 4,179,390, U.S. Patent 4,259,201, U.S. Patent 5,098,598, U.S. Patent 5,520,844, U.S. Patent 5,575,947, and the like. However, various problems arise when organic peroxycarboxylic acids are contained in commercially available bleach compositions. That is, there is a tendency to lose stability of its own active oxygen due to the stability of the heat due to the instability. To solve this problem, coating and granulating techniques of organic peroxycarboxylic acid are described in European Patent No. 396,341 and European Patent No. 256,443, but when applied to a bleach composition, the price is high and the low temperature solubility worsens and remains in the garment. There is a disadvantage that occurs.

Therefore, it is necessary to develop a bleach activator excellent in bleaching ability against hydrophilic or hydrophobic contamination by releasing a peroxycarboxylic acid which is a bleach activator only in water of room temperature or low temperature.

The present invention is an amido-based compound which is capable of releasing peroxycarboxylic acid activating an inorganic peroxide only in water at room temperature or low temperature, and having excellent bleaching power against hydrophilic contamination as well as hydrophobic contamination, and having excellent storage stability, and preparation thereof. The purpose is to provide a method.

Thus, the present inventors release peroxycarboxylic acid activating the inorganic peroxide only in water of room temperature or low temperature, storage stability, easy to store for a long time, and is a bleach activator excellent bleaching power for hydrophobic contamination as well as hydrophilic contamination The present invention has been completed by synthesizing a high yield compound by a simple reaction.

In order to achieve the above object, the present invention provides an amido-based compound represented by the following formula (1).

[Formula 1]

Wherein R ₁ and R ₂ are one or a mixture of two or more selected from linear or branched alkyl or alkenyl having 1 to 19 carbon atoms; n is 1 or 2; when n is 1 R ₃ is hydrogen or a methyl group; L is any one of Formulas 5a to 5c, R ₄ is alkyl or alkylene having 1 to 20 carbon atoms, Y is hydrogen, chlorine, bromine, -SO ₃ M, -CO ₂ M and -OSO ₃ M M is an alkali metal or an alkaline earth metal.

[Formula 5a]

[Formula 5b]

[Formula 5c]

 In addition, the present invention comprises the step of preparing a chloroformate compound represented by the formula (4) by reacting the amide represented by the formula (2) and the diphosgene or triphosgene represented by the formula (3) and the chloroformate compound It provides a method for producing an amido-based compound represented by the formula (1) comprising the step (second step) of preparing a compound represented by the formula (1) by reacting with a compound represented by the formula (5).

Scheme 1

Wherein R ₁ , R ₂ , n, R ₃ , L, R ₄ , Y are the same as defined in Formula 1.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The amide represented by the formula (2) and the diphosgene or triphosgene represented by the formula (3) react for 0.5 to 10 hours at a low temperature of -10 to 4 ° C. at an equivalent ratio of 2.5 to 4: 1, and are chloroformates represented by the formula (4). The reaction between the compound and the compound represented by Chemical Formula 5 is performed using water as a solvent, and the amount of the solvent is 40 to 100% by weight of the total amount of the reactants, and the reaction is performed at a temperature of 0 to 100 ° C. for 2 to 8 hours.

That is, after adding an organic solvent, an amide represented by the formula (2), and a suitable base to the reactor, the phosgene represented by the formula (3), for example, diphosgene or triphosgene, is slowly added while maintaining the temperature at 0 to 4 ° C. After stirring at a temperature of 4 ° C. for 5 hours, the organic layer is separated using water. Then, after removing water with magnesium sulfate anhydride, the organic solvent is distilled under reduced pressure to prepare a chloroformate compound represented by the formula (4). The chloroformate compound and the compound represented by the formula (5) are dissolved in water, stirred at 70 ° C. for 2 hours, cooled to room temperature, the precipitate is filtered and dried to prepare an amido compound represented by the formula (1).

The bleaching composition comprising the amido-based compound of the present invention has excellent storage stability and releases peroxycarboxylic acid activating inorganic peroxide only in water at room temperature or low temperature, and has excellent bleaching power against hydrophobic contamination as well as hydrophilic contamination.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited by the following examples.

Example 1 Preparation of Caprylaminobisethoxycarbonyloxybenzenesulfonate

1) Preparation of the first step (caprylaminobisethoxychloroformate)

Capryl diethanolamide 34.65g, diisopropylethylamine 26.13g, and diphosgene 11.85g were dissolved in 50mL of methylene chloride, and reacted at -10 ~ 4 ℃ for 5 hours, and then the organic layer was separated using water, and then magnesium sulfate Water was removed using anhydride. Thereafter, the solvent was removed and dried to yield 37.8 g of a brown liquid. The preparation of the amide in the above was prepared using a common amide synthesis method.

2) Preparation of the Second Step (Caprylaminobisethoxycarbonyloxybenzenesulfonate)

5.28 g of NaOH and 61.2 g of 4-hydroxybenzenesulfonate sodium salt dihydrate were dissolved in 120 ml of water at 0-4 ° C., and 32.8 g of the compound prepared in the first step was added, followed by stirring at 70 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature and filtered to remove the solvent and salt, followed by drying to obtain 81 g of a white solid product.

<Example 2 and Comparative Examples 1 to 4> Preparation of the bleaching composition

To prepare a bleaching composition in the composition ratio as shown in Table 1. The preparation of the bleach composition was prepared by conventional methods. That is, the granule powder was first prepared with the ingredients except the additive and the bleaching component, and then the additive and the bleaching component were added and mixed to prepare a bleaching composition. The unit is parts by weight. In this case, LAS is linear alkylbenzenesulfonate, NOBS is nonyloxybenzenesulfonate, TAED is tetraacetylethylenediamine, and CABECOBS is caprylaminobisethoxycarbonyloxybenzenesulfonate, and fluorescent dyes are typal DMA-X. (Tinopal DMA-X, manufactured by Ciba Specialty Chemical Co., Ltd.), Sabinase 12.OT (Savinase 12.OT, manufactured by Novozyme Co., Ltd.) was used as an enzyme.

division Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 LAS 1.5 - 10 10 15 Polyoxyethylene alkyl ether 7 7 5 5 5 Sodium bicarbonate (sodium bicarbonate) 10 10 10 10 10 Soda ash (sodium carbonate) Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Forget-me-not (sodium sulfate) 10 10 10 10 10 Zeolite 4A 20 20 20 20 20 Percarbonate 15 15 15 15 15 NOBS - - 6 - - TAED - - - 6 - CABECOBS 6 6 - - - Other additives Fluorescent dyes 0.15 0.15 0.15 0.15 0.15 enzyme 0.5 0.5 0.5 0.5 0.5

Experimental Example 1 Evaluation of Bleaching Power of Bleaching Composition

Red wine (EMPA 114), coffee (wfk BC-2), red pepper (wfk 10P), and tea (wfk BC-3) were uniformly applied to 8 × 8 cm 2 white cotton cloth and dried. Water (water temperature 20 ° C., hardness 50 CaCO ₃ pm) and 1 g / L of the bleach composition prepared in Examples 1 and 4 were added to a Terg-o-tometer. The cotton cloth was put here, washed for 10 minutes, rinsed for 3 minutes, and naturally dried.

The whiteness before and after washing the cotton cloth was measured using a colorimeter, and then bleaching power was calculated by substituting Equation 1 as follows, and the results are shown in Table 2.

[Equation 1]

Bleaching rate (%) = [(1-R _s ² / 2R _s )-(1-R _b ² / 2R _b )] / [(1-R _s ² / 2R _s )-(1-R _o ² / 2R _o )] × 100

Wherein R _s is the surface reflectivity of the contaminated cotton cloth, R _b is the surface reflectivity of the cotton cloth after decontamination, and R _o is the surface reflectivity of the white cotton cloth.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Red wine pollution 74% 65% 73% 63% 40% Coffee pollution 81% 64% 72% 61% 43% Pepper pollution 80% 63% 74% 61% 43% Secondary pollution 79% 71% 73% 60% 45%

Through Table 2, Comparative Example 2, the bleaching composition of the bleaching composition prepared in Example 2 including the amido-based bleach activator and the anionic surfactant LAS is the same as the bleaching composition containing NOBS, TAED in the same amount And compared to Comparative Example 3 or Comparative Example 4, which is a bleaching composition that does not contain a bleach activator, showed better bleaching power in all contamination of red wine, coffee, pepper, tea. In addition, it was confirmed that the bleaching power of the case of further including LAS, which is an anionic surfactant as in Example 1, was further superior to Comparative Example 1 including only the amido-based bleach activator and the nonionic surfactant of the present invention.

Experimental Example 2 Evaluation of Washing Power of Bleaching Composition

Water (water temperature 20 ° C., hardness 133 CaCO ₃ pm) and 1 g / L of the bleach composition prepared in Examples 1 and 4 were added in a terg-o-tometer, and wfk was added thereto. 8 × 8 cm 2 cotton cloth (2 sheets each) and 5 × 5 cm 2 soiled cloth (10 sheets) contaminated with 10D (cotton contaminated cloth) and wfk 20D (mixed fiber contaminated cloth) Put it. It was washed for 10 minutes, rinsed for 3 minutes, and then dried naturally.

After measuring the whiteness before and after washing the contaminated cotton cloth using a colorimeter, the washing power was calculated by substituting Equation 1 of Experimental Example 1, and the results are shown in Table 3 below.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Wfk 10D 80% 72% 74% 69%  79% Wfk 20D 78% 72% 73% 70% 70% Japan Laundry Science Association 80% 76% 74% 68%   68%

Through Table 3, Comparative Example 2 and Comparative Example 3 in which the bleaching composition of the bleaching composition prepared in Example 1 including the amido-based bleaching activator and the anionic surfactant according to the present invention is the same as that of the NOBS and TAED in the same amount Or it was confirmed that the washing power is superior to Comparative Example 4, which is a bleaching composition that does not contain a bleach activator, and also superior to the washing power of Comparative Example 1 containing an amido-based bleach activator and a nonionic surfactant at the same time.

As described above, the amido-based compound of the present invention is a bleaching agent because it releases peroxycarboxylic acid, a bleach activator only in water at room temperature or low temperature, and has excellent bleaching effect, good storage stability, and excellent bleaching power of hydrophilic or hydrophobic stain. It can be usefully used as a bleach activator added to bleach to enhance the bleaching effect of.

Claims (6)

Amido-based compound represented by the formula (1). [Formula 1] Wherein R ₁ and R ₂ are one or a mixture of two or more selected from linear or branched alkyl or alkenyl having 1 to 19 carbon atoms; n is 1 or 2; when n is 1 R ₃ is hydrogen or a methyl group; L is any one of Formulas 5a to 5c, R ₄ is alkyl or alkylene having 1 to 20 carbon atoms, Y is hydrogen, chlorine, bromine, -SO ₃ M, -CO ₂ M and -OSO ₃ M M is an alkali metal or alkaline earth metal ion. [Formula 5a] [Formula 5b] [Formula 5c] Reacting an amide represented by Formula 2 with a diphosgene or a triphosgene represented by Formula 3 to prepare a chloroformate compound represented by Formula 4 (first step) and the chloroformate compound represented by Formula 5 A method for preparing the amido-based compound of claim 1, comprising the step (second step) of preparing a compound represented by Chemical Formula 1 by reacting with a compound. Scheme 1 Wherein R ₁ , R ₂ , n, R ₃ , L, R ₄ , Y are the same as defined in claim 1. The method according to claim 2, wherein the amide represented by the formula (2) and the diphosgene or triphosgene represented by the formula (3) are reacted at an equivalent ratio of 2.5 to 4: 1. According to claim 2, wherein the reaction of the chloroformate compound represented by the formula (4) and the compound represented by the formula (5) is carried out using water as a solvent, the amount of the solvent is characterized in that 40 to 100% by weight of the total amount of the reactants The manufacturing method to make. The method of claim 2, wherein the reaction temperature of the first step is -10 ~ 4 ℃ and the reaction time is 0.5 to 10 hours. The method of claim 2, wherein the reaction temperature of the second step is 0 ~ 100 ℃ and the reaction time is 2 to 8 hours.