KR100454737B1 - Quaternary Ammonium Amido Derivative Composition for Activation of Bleaching and Bleaching Composition comprising the same - Google Patents

Abstract

The present invention relates to a bleach activating compound and a bleaching composition comprising the same, characterized in that it contains a quaternary ammonium amido derivative compound. Since the bleaching activating compound according to the present invention reacts with hydrogen peroxide only when it comes in contact with water to release peroxycarboxylic acid, the storage stability is good and the bleaching action is excellent by activating the inorganic peroxide even at low temperature, and also for hydrophilic and hydrophobic staining. Excellent cleaning power

Description

Quaternary Ammonium Amido Derivative Composition for Activation of Bleaching and Bleaching Composition comprising the same}

The present invention relates to a bleaching activating compound and a bleaching composition comprising the same. More particularly, the bleaching activating compound having excellent storage stability and activating an inorganic peroxide bleaching agent even at low temperatures can exhibit excellent bleaching and washing effects and bactericidal effects. And a bleaching composition containing the same.

In Korea, in order to achieve the bleaching effect of laundry, the laundry has been put in water with detergent, boiled, dried in the sun and UV sterilized. This method is relatively excellent in the bleaching and cleaning effect, but the disadvantages of the cumbersome and dangerous process of boiling the laundry process.

Therefore, a method of using an inorganic peroxide that generates hydrogen peroxide when dissolved in water, such as sodium perborate and sodium percarbonate, has been developed. Inorganic peroxides that release hydrogen peroxide in aqueous solution include sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, sodium peroxophosphate, urea peroxohydrate, sodium peroxide, and the like. Contamination by wine, grass, etc. can be easily bleached.

However, the bleaching power of such inorganic peroxides varies greatly with temperature, for example, sodium perborate exhibits effective bleaching performance at 80 ° C. or higher and 60 ° C. or higher for sodium percarbonate. When washing in a general home, most tap water is used for washing immediately, considering that the temperature of tap water is about 20 to 25 ° C. in summer and about 5 ° C. in winter, the bleaching power of the inorganic peroxide is not sufficiently expressed. Therefore, methods have been proposed to express the bleaching power of inorganic peroxide even in low temperature water. As part of this process, bleach activating compounds have been introduced.

As a general bleach activator, tetraacetyl ethylene diamine (TAED) is the most commonly used, and US Pat. Nos. 4,412,934, 4,483,778, 4,606,838, 4,671,891, etc. Bleach is disclosed. In the case of tetraacetylethylenediamine, the bleaching power for hydrophilic juice stains is excellent, but there is a limit to the removal of oily stains such as sebum and blood from the human body. Acyl compounds have a certain effect in removing oily stains, but a large amount of acyl compounds must be used in comparison with tetraacetylethylenediamine and there is a problem that the bleaching power is still insufficient at low temperatures.

In addition, US Pat. Nos. 4,876,046, 4,259,201, 5,089,167, and the like, many organic peroxycarboxylic acids are disclosed as inorganic peroxide activating compounds. However, bleaching compositions containing organic peroxycarboxylic acids tend to be poor in storage stability, such as loss of their active oxygen due to heat instability. In order to solve this problem, coating and granulating techniques of organic peroxycarboxylic acid have been described in European Patent Nos. 396,341 and 256,443. However, the bleaching composition according to this is expensive and has low solubility in water at low temperatures. There is a disadvantage that occurs.

Recently, as a compound capable of activating the bleaching power of the inorganic peroxide bleaching agent, various efforts such as the research on the transition metal complex have been continued.

Accordingly, the technical problem to be achieved by the present invention is to solve the conventional problems as described above, excellent storage stability, and by activating the inorganic peroxide bleach at low temperatures, not only shows excellent bleaching and sterilizing effect, but also by itself To provide a bleach activating compound having excellent bactericidal power and a bleaching composition containing the same.

In order to achieve the above technical problem, the present invention provides a quaternary ammonium amido derivative-based bleaching activating compound represented by the following general formula (1).

<Formula 1>

or

In Formula 1, R1, R2, and R3 are each independently alkyl, aryl, alkenyl, hydroxyalkyl, and akarylene having 1 to 20 carbon atoms. Any one selected from the group consisting of R 4 is hydrogen, chlorine, bromine, OH, alkyl having 1 to 15 carbon atoms, aryl, and alkaryl, and R 5 is Any one selected from the group consisting of alkyl, alkaryl, alkylene, aryl, arylene, and akarylene having 1 to 20 carbon atoms, and L is Any one leaving group selected from the group consisting of the following formulas (I) to (III), Z- is Cl-, Br-, OH-, citric acid, acetate, sulfate, boric acid ( borate) and any one selected from the group consisting of phosphate;

In formulas (I) to (III), R6 is alkyl or alkylene having 1 to 20 carbon atoms, and Y is selected from the group consisting of hydrogen, chlorine, bromine, SO ₃ M, CO ₂ M and OSO ₂ M As one, M is any one selected from the group consisting of hydrogen, alkali metal ions, ammonium ions and equivalent alkaline earth metal ions.

Such quaternary ammonium amido derivative-based bleaching activating compounds include N-octyl N, N-dimethylammonium amino butyloxybenzene sulfonate, N, N, N-trimethylammonium amino butyloxybenzene sulfonate, N-nonyl N, N -Dimethylammonium amino methyloxybenzene sulfonate, N, N, N-trimethylammonium amino nonyloxybenzene sulfonate, N, N, N-trimethylammonium amino octylbenzene sulfonate, and the like.

The quaternary ammonium amido derivative compounds represented by the general formula (1) do not decompose by heat and react with hydrogen peroxide only when they come into contact with water to release peroxycarboxylic acid, which has good storage stability and excellent self-bleaching and sterilizing power. .

Such a bleaching activating compound is used in addition to an oxygen-based bleaching composition containing an inorganic peroxide. Considering the activating effect and decomposition rate for the peroxide, the quaternary ammonium amido derivative-based bleaching activating compound is 0.01 based on the total weight of the composition. It is preferably included to 15% by weight. When the content of the quaternary ammonium amido derivative-based bleaching activating compound is less than 0.01% by weight, the effect of activating the inorganic peroxide may not be sufficient. When the content of the quaternary ammonium amido derivative-based bleaching activating compound is greater than 15% by weight, the activation rate of the inorganic peroxide may be excessively increased. There is.

Peroxides widely used in the bleaching composition include inorganic compounds that generate hydrogen peroxide such as percarbonate salt (M ₂ C ₂ O ₆ ), perborate salt (MBO ₃ ), perphosphate, persulfate, urea peroxide, and the like. Organic peroxides and the like. Among them, the peroxide suitable for the present invention is preferably any one selected from percarbonates, perborates and mixtures thereof. In particular, the content of the inorganic peroxide is preferably 5 to 80% by weight relative to the total weight of the composition, considering the bleaching effect and economic efficiency.

In the bleaching composition containing the inorganic peroxide according to the present invention, components other than the inorganic peroxide and the bleach activating compound are blended using an appropriate amount of the component normally used according to the kind and purpose of the bleaching composition. Hereinafter, a surfactant, builders, which may be added to the bleach composition according to the present invention, for example, to the bleach detergent composition will be described.

Anionic surfactants or nonionic surfactants may be used as the surfactant, and the content thereof is not particularly limited but is preferably included in an amount of 1 to 40% by weight based on the total weight of the composition. As the anionic surfactant, for example, alkylbenzene sulfonate, fatty acid salt, alkyl monosulfonate salt or alpha olefin sulfonate salt can be used. As the nonionic surfactant, oxo alcohol polyethylene glycol, fatty acid polyoxyethylene glycol, alkylphenyl polyoxyethylene glycol or polyoxyethylene glycol may be used.

In addition, builders are alkali metal salt additives for improving the cleaning ability of the surfactant, such as alkali metal salts of polyphosphates such as sodium tripolyphosphate, aluminosilicates such as zeolites, polyacetal carboxylates, polycarboxylates, Carbonates such as sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), silicates such as α-Na ₂ SiO ₃ or β-Na ₂ SiO ₃ of layered crystalline, and the like. The builder is preferably added in an amount of 10 to 50% by weight based on the total weight of the composition in consideration of improving the cleaning power of the surfactant.

The oxygen-based bleaching composition of the present invention may include other additives such as inorganic salts such as sodium carbonate and sodium sulfate, fluorescent dyes, enzymes, flavorings, etc., which are commonly used in detergents, in addition to the above materials.

Hereinafter, examples will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Examples 1 and 2 and Comparative Examples 1 to 3

To the bleaching composition was prepared according to the composition ratio according to the components and contents shown in Table 1. In the method of preparing the bleaching composition, first, a granular powder was prepared from the components except the additive and the bleaching component, and then the additive and the bleaching component were added and mixed to prepare the bleaching composition. The unit is weight percent.

Raw material name Example Comparative example One 2 One 2 3 Percarbonate 15 15 15 15 15 TMANOBS 5 3 - - - NOBS - - 5 - - TAED - - 5 - LAS 10 10 10 10 15 Polyoxyethylene alkyl ether 5 5 5 5 5 Alpha olefin sulfonate 3 3 3 3 - Sodium carbonate to 100 to 100 to 100 to 100 to 100 Sodium sulfate 10 10 10 10 10 Zeolite 4A 20 20 20 20 20 Fluorescent dyes 0.15 0.15 0.15 0.15 0.15 enzyme 0.5 0.5 0.5 0.5 0.5

In Table 1, TMANOBS is N, N, N-trimethylammonium amino nonyloxybenzene sulfonate, NOBS is nonyloxybenzene sulfonate, TAED is tetraacetylethylenediamine, LAS is linear alkylbenzenesulfonate, fluorescent Dinopal DMA-X (Tinopal DMA-X, manufactured by Ciba Specialty Chemical Co., Ltd.) was used as a dye, and an enzyme was used Sabinase 12.OT (Savinase 12.OT, manufactured by Novozyme).

The bleaching power, the washing power and the sterilizing power of the bleaching compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated by the following evaluation test method.

Bleaching power evaluation experiment

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. 1 g / L of a bleaching composition prepared in Examples 1, 2, and Comparative Examples 1 to 3 with water having a temperature of 20 ° C. and a hardness of 50 CaCO ₃ ppm in a terg-o-tometer. It injected | poured in the ratio, and it put the cotton cloth here, wash | cleaned for 10 minutes, and then rinsed for 3 minutes and dried naturally.

After measuring the whiteness of the cotton cloth before and after the washing using a colorimeter, and substituted in Kubellka-Munk's eq of Equation 1 as shown below to calculate the bleaching power and the results are shown in Table 2. It was.

<Equation 1>

Bleaching rate (%) = [(1-Rs) ² / 2Rs- (1-Rb) ² / 2Rb] / [(1-Rs) ² / 2Rs- (1-Ro) ² / 2Ro] × 100

In Equation 1, Rs is the surface reflectivity of the contaminated cotton cloth, Rb is the surface reflectivity of the cotton cloth after decontamination, and Ro is the surface reflectivity of the white cotton cloth.

division Example Comparative example One 2 One 2 3 Red wine pollution 94% 89% 86% 75% 65% Coffee pollution 93% 90% 87% 72% 67% Pepper pollution 92% 90% 88% 73% 66% Secondary pollution 91% 88% 87% 72% 65%

Looking through Table 2, the bleaching power of the bleaching composition prepared in Examples 1 and 2 containing the quaternary ammonium amido derivative-based bleaching activating compound according to the present invention is contaminated with contamination of red wine, coffee, red pepper, and tea. On the other hand, it can be confirmed that it is superior to the case containing NOBS, TAED or no bleach activating compound.

Washing power evaluation experiment

A ratio of 1 g / L of water having a temperature of 20 ° C. and a hardness of 133 CaCO ₃ ppm to a bleach composition prepared in Examples 1, 2, and Comparative Examples 1 to 3 in a terg-o-tometer. 8 x 8 cm 2 cotton cloth (2 sheets each) and 5 x 5 cm 2 contaminated cloth (8 sheets) were placed therein, respectively, contaminated with wfk 10D and wfk 20D. 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 bleaching force was calculated by substituting the Kubelka Munch equation of Equation 1, and the results are shown in Table 3 below.

division Example Comparative example One 2 One 2 3 wfk 10D 81% 80% 76% 71% 71% wfk 20D 83% 83% 75% 72% 72% Japan Laundry Science Association 82% 81% 76% 70% 70%

Looking through Table 3, the cleaning power for the hydrophilic and hydrophobic staining of the bleaching composition prepared in Examples 1 and 2 containing the quaternary ammonium amido derivative-based bleaching activating compound according to the present invention, contains NOBS, TAED or Or it can be confirmed that the excellent compared to the washing power of Comparative Examples 1 to 3 containing no bleach activating compound.

Bactericidal evaluation test

Tests for bactericidal activity were P. aeruginosa (Pseudomonas aeruginosa), E. coli (E. coli), Klepsiella pneumoniae (pneumococcus pneumoniae), and Staphylococcus epidermis (P. aeruginosa). Staphylococcus epidermis, Staphylococcus aureus, P. aeruginosa, Vibrio parahaemolyticus, Shigella flexneri, Achineobacter Eleven species were used, including Acineobacter baumannii, Aeromonas hydrophyla, Enterobacter aerogenes, and Salmoella typhimurium (above, food poisoning). 30 g of Casitone, 5 g of Tween-80, 5 g of Soyton, 5 g of NaCl, 0.7 g of Lecithin, and 15 g of Agar Added to water SDC medium consisting of the composition was used.

1 L of 0.85% aqueous sodium chloride solution (20 ° C.) was prepared in 6 beakers, and the bacteria were added at a concentration of 2.0˜5.0 × 10 ⁵ / mL, followed by stirring. The bleaching compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were added thereto at a rate of 1.0 g / L, and the number of bacteria was measured over time. At this time, the beaker without addition of the bleach composition was used as a control group.

After the addition of the bleaching composition, 1 mL each of 15 and 20 minutes was added thereto, followed by serial dilution using an aqueous 0.85% NaCl solution as the dilution buffer. It was. Examples 1, 2, and Comparative Examples 1 to 3 were colony counted and colony counting was compared with the control group to determine bacterial mortality, and the results are shown in Table 4 below.

division 15 minutes later 20 minutes later Example Comparative example Example Comparative example One 2 One 2 3 One 2 One 2 3 P. aeruginosa 99.9 99.9 99.9 90.3 75.3 99.9 99.9 99.9 99.9 99.9 E. coli 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 K. pneumoniae 99.9 99.9 92.6 82.6 75.6 99.9 99.9 99.9 99.9 99.9 S. epidermis 99.9 99.9 96.3 82.5 72.3 99.9 99.9 99.9 99.9 99.9 S. aureus 99.9 99.9 90.9 87.6 53.2 99.9 99.9 99.9 99.9 99.9 V.parahaemolyticus 99.9 99.9 90.2 82.6 54.0 99.9 99.9 99.9 99.9 99.9 S. flexneri 99.9 99.9 93.3 85.4 66.6 99.9 99.9 99.9 99.9 99.9 A. baumannii 99.9 99.9 94.5 86.2 61.3 99.9 99.9 99.9 99.9 99.9 A. hydrophyla 99.9 99.9 92.3 86.7 82.4 99.9 99.9 99.9 99.9 99.9 E. aerogenes 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 S. typhimurium 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9

When looking through Table 4, the bleaching composition prepared in Examples 1 and 2 containing a quaternary ammonium amido derivative-based bleach activator according to the present invention, does not contain NOBS, TAED or bleach activating compound Compared with the bleaching compositions of Comparative Examples 1 to 3, it can be seen that the initial mortality is excellent.

As described above, the bleaching composition containing the bleaching activating compound according to the present invention not only has good storage stability and excellent bleaching power, but also has excellent washing power against hydrophilic and hydrophobic stains. In addition, since the self-sterilization power is very good, it can be widely used in industrial bleach, such as household bleach and paper industry.

Claims (4)

A quaternary ammonium amido derivative-based bleaching activating compound represented by the following general formula (1); <Formula 1> or In Formula 1, R1, R2 and R3 are each independently alkyl, aryl, alkenyl, hydroxyalkyl and akarylene having 1 to 20 carbon atoms. Any one selected from the group consisting of R 4 is hydrogen, chlorine, bromine, OH, alkyl having 1 to 15 carbon atoms, aryl, and alkaryl, and R 5 is Any one selected from the group consisting of alkyl, alkaryl, alkylene, aryl, arylene, and akarylene having 1 to 20 carbon atoms, and L is Any one leaving group selected from the group consisting of the following formulas (I) to (III), Z- is Cl-, Br-, OH-, citric acid, acetate, sulfate, boric acid ( borate) and any one selected from the group consisting of phosphate; In formulas (I) to (III), R6 is alkyl or alkylene having 1 to 20 carbon atoms, and Y is selected from the group consisting of hydrogen, chlorine, bromine, SO ₃ M, CO ₂ M and OSO ₂ M As one, M is any one selected from the group consisting of hydrogen, alkali metal ions, ammonium ions and equivalent alkaline earth metal ions. The method of claim 1, wherein the bleach activating compound is N-octyl N, N-dimethylammonium amino butyloxybenzene sulfonate, N, N, N-trimethylammonium amino butyloxybenzene sulfonate, N-nonyl N, N-dimethyl Bleaching activation, characterized in that any one selected from the group consisting of ammonium amino methyloxybenzene sulfonate, N, N, N-trimethylammonium amino nonyloxybenzene sulfonate and N, N, N-trimethylammonium amino octylbenzene sulfonate compound. An oxygen-based bleaching composition containing an inorganic peroxide, wherein the bleaching activating compound of claim 1 comprises 0.01 to 15% by weight based on the total weight of the total composition. The bleaching composition of claim 3, wherein the inorganic peroxide is any one selected from percarbonate salt, perborate salt, and mixtures thereof.