KR20040006082A - Composition for Activation of Bleaching Ability containing Benzendiol as a Leaving Group and Bleaching Composition comprising the same - Google Patents

Abstract

PURPOSE: A bleaching activator compound is provided to produce a bleaching agent composition having excellent storage stability, bleaching performance, washing power and sterilizing property. CONSTITUTION: The bleaching activator compound having a benzenediol leaving group is represented by the general formula 1, wherein each of R1s is independently selected from the group consisting of hydrogen, chlorine, bromine, OH and a C1-C20 alkyl group, and L is a benzenediol leaving group. In addition, the oxygen-based bleaching agent composition comprises an inorganic peroxide and 0.01-15 wt% of the bleaching activator compound based on the total weight of the composition.

Description

Composition for Activation of Bleaching Ability containing Benzendiol as a Leaving Group 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 on the removal of oily stains, but a large amount of tetraacetylethylenediamine must be used, and there is a problem that the expression of bleaching power is still insufficient at low temperatures.

In addition, in U.S. Patent Nos. 4,876,046, 4,259,201, 5,089,167, and the like, many organic peroxycarboxylic acids are disclosed as inorganic peroxide activating compounds. The storage stability tends to be poor, such as loss of free radicals. 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 bleaching activating compound comprising a benzenediol (Benzendiol) of the general formula 1 as a leaving group.

<Formula 1>

In Formula 1, R 1 is independently selected from hydrogen, chlorine, bromine, OH and an alkyl group having 1 to 20 carbon atoms (alkyl group may be branched or straight chain), and L is Any one selected from benzenediol leaving groups represented by formulas (I) to (XII);

In the above formulas (I) to (XII), R2 is alkyl or alkylene having 1 to 20 carbon atoms, and Y1 and Y2 are independently of each other hydrogen, chlorine, bromine, SO ₃ M, CO ₃ M and OSO ₃ M As any one selected from the group consisting of, M is any one selected from the group consisting of hydrogen, alkali metals, ammonium ions and equivalent alkaline earth metals.

Such bleach activating compounds include 1-decanoyloxy-4-acetoxy benzenesulfonate, 1-decanoyloxy-3-acetoxy benzenesulfonate, 1-decanoyloxy-2-acetoxy benzenesulfonate, 1- Octanoyloxy-4-acetoxy benzenesulfonate, 1-octanoyloxy-3-acetoxy benzenesulfonate, 1-octanoyloxy-2-acetoxy benzenesulfonate, 1,4-bissteanoyloxybenzene Sulfonate, 1,3-bisstecanoyloxybenzenesulfonate, 1,2-bissteanoyloxybenzenesulfonate, 1,4-bisoctanoyloxybenzenesulfonate, 1,3-bisoctanoyloxybenzene Sulfonate, 1,2-bisoctanoyloxybenzenesulfonate, and the like.

The bleach activating compound having benzendiol represented by the general formula (1) as a leaving group is excellent in storage stability because it reacts with hydrogen peroxide to release peroxycarboxylic acid only in aqueous solution, that is, only in contact with water. In addition, since the amount of peroxycarboxylic acid produced from one molecule of the compound is twice as high as the bleach activating compound of the acyl compound, its own bleaching and bactericidal power is very excellent.

The bleaching activating compound is used in addition to the oxygen-based bleaching composition containing an inorganic peroxide, and considering the activating effect and decomposition rate for the peroxide, the content of the bleaching activating compound including the benzenediol as a leaving group is the total composition. It is preferably 0.01 to 15% by weight based on the weight. When the content of the bleaching activating compound is less than 0.01% by weight, the effect of activating the inorganic peroxide may not be sufficient, and when it exceeds 15% by weight, the activation rate of the inorganic peroxide may be too high.

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, alkylmonosulfonate salt or alpha olefin sulfonate salt and the like can be used. Phenyl polyoxyethylene glycol, polyoxyethylene glycol, etc. can 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. 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 a bleaching composition. The unit is weight percent.

Raw material name Example Comparative example One 2 One 2 3 Percarbonate 15 15 15 15 15 Bleach Activation Compound 5 5 - - - NOBS - - - 5 - TAED - - - - 5 Surfactants LAS 15 20 15 15 15 Polyoxyethylene alkyl ether 5 5 5 5 5 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 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

In Table 1, the bleach activating compound is 1,4-bisdecanoyloxybenzenesulfonate, NOBS represents nonyloxybenzenesulfonate, TAED represents tetraacetylethylenediamine, and LAS represents straight-chain alkylbenzenesulfonate , Fluorescent dye was used Tinopal DMA-X (Tibapal DMA-X, manufactured by Ciba Specialty Chemical Co., Ltd.), the enzyme was used Sabinase 12.OT (Savinase 12.OT, Novozymes).

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. Water (temperature 20 ° C., hardness 50 CaCO ₃ ppm) and bleach composition prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were used in a terg-o-tometer, a cleaning force measuring instrument, in a ratio of 1 g / L. It was put in, put the cotton cloth here, washed for 10 minutes, then rinsed for 3 minutes and naturally dried.

Whiteness was measured using a colorimeter before and after washing the cotton cloth, and bleaching power was calculated by substituting Kubelka-Munk's eq of Equation 1 below and the results are shown in Table 2.

<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 92% 92% 62% 86% 76% Coffee pollution 92% 93% 65% 85% 74% Pepper pollution 90% 92% 63% 81% 70% Secondary pollution 89% 91% 62% 80% 75%

Referring to Table 2, the bleaching compositions prepared in Examples 1 and 2 containing the bleach activating compound comprising benzendiol according to the present invention as a leaving group, do not use a bleach activating compound or nonyloxybenzene It can be seen that the bleaching power for contamination of red wine, coffee, red pepper, and tea is better than that of sulfonate or tetraacetylethylenediamine.

Washing power evaluation experiment

Water (temperature 20 ° C., hardness 133 CaCO ₃ ppm) and the bleach composition prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were added to a terg-o-tometer at a rate of 1 g / L. Then, 8 × 8 cm 2 cotton cloth (2 sheets each) and 5 × 5 cm 2 contaminated cloth (8 sheets) were 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 78% 84% 73% 76% 72% wfk 20D 75% 86% 72% 75% 73% Japan Laundry Science Association 79% 85% 75% 77% 74%

Referring to Table 3, the bleaching composition prepared in Examples 1 and 2 containing the bleach activator compound containing benzendiol according to the present invention as a leaving group did not contain a bleach activator compound, or nonyloxy It can be confirmed that washing power is superior to Comparative Examples 1 to 3 using benzenesulfonate or tetraacetylethylenediamine.

Bactericidal evaluation test

Tests for bactericidal activity include P. aeruginosa (P. aeruginosa), E. coli (E. coli, E. coli), Klepsiella pneumoniae (pneumococcus pneumoniae), Staphylococcus epidermis ( Staphylococcus epidermis, Staphylococcus aureus, Staphylococcus aureus, Vibrio parahaemolyticus, Shigella flexneri, Achineobacter Eleven species were used, including Acineobacter baumannii, Aeromonas hydrophyla, Enterobacter aerogenes, and Salmoella typhimurium (above, food poisoning). 1 L of 30 g of Casitone, 5 g of Tween-80, 5 g of Soyton, 5 g of NaCl, 0.7 g of Lecithin, 15 g of Agar SDC medium consisting of a composition added to water was used.

1 L of 0.85% aqueous sodium chloride solution (20 ° C.) was prepared in 7 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.

After the addition of the bleaching composition, 1 mL of each solution was taken at 15 and 20 minutes, followed by serial dilution using an aqueous 0.85% NaCl solution as a dilution buffer, serial dilution, and then inoculated in a solid medium for 24 hours in an incubator at 37 ° C. Incubated. Examples 1 and 2, Comparative Examples 1 to 3 and the control group was colony counted (colony counting), and compared to the control group and the bacterial mortality was measured 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 75.4 92.3 82.3 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 75.6 95.6 86.9 99.9 99.9 99.9 99.9 99.9 S. epidermis 99.9 99.9 76.3 94.3 86.6 99.9 99.9 99.9 99.9 99.9 S. aureus 99.9 99.9 56.9 93.2 72.0 99.9 99.9 99.9 99.9 99.9 V.parahaemolyticus 99.9 99.9 53.2 94.0 74.8 99.9 99.9 99.9 99.9 99.9 S. flexneri 99.9 99.9 68.3 86.6 85.0 99.9 99.9 99.9 99.9 99.9 A. baumannii 99.9 99.9 62.5 87.3 80.3 99.9 99.9 99.9 99.9 99.9 A. hydrophyla 99.9 99.9 80.3 92.4 86.6 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

Referring to Table 4, the bleaching composition prepared in Examples 1 and 2 containing the bleach activating compound leaving benzendiol according to the present invention does not include a bleach activator or nonyloxybenzenesulfonate. Or it can be seen that the initial mortality is superior to the bleaching composition prepared in Comparative Examples 1 to 3 containing tetraacetylethylenediamine.

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 bleaching activating compound comprising benzenediol of Formula 1 below as a leaving group; <Formula 1> In Formula 1, R1 is independently selected from hydrogen, chlorine, bromine, OH and alkyl group having 1 to 20 carbon atoms, L is benzene represented by the following formula (I) to (XII) Any one selected from benzendiol leaving groups; In formulas (I) to (XII), R 2 is alkyl or alkylene having 1 to 20 carbon atoms, and Y 1 and Y 2 are independently of each other hydrogen, chlorine, bromine, SO ₃ M, CO ₂ M and OSO ₂ M. As any one selected from the group consisting of, M is any one selected from the group consisting of hydrogen, alkali metals, ammonium ions and equivalent alkaline earth metals. The method of claim 1, wherein the bleach activating compound is 1-decanoyloxy-4-acetoxy benzenesulfonate, 1-decanoyloxy-3-acetoxy benzenesulfonate, 1-decanoyloxy-2-acetoxy benzene Sulfonate, 1-octanoyloxy-4-acetoxy benzenesulfonate, 1-octanoyloxy-3-acetoxy benzenesulfonate, 1-octanoyloxy-2-acetoxy benzenesulfonate, 1,4-bi Stecanoyloxybenzenesulfonate, 1,3-bisstecanoyloxybenzenesulfonate, 1,2-bissteanoyloxybenzenesulfonate, 1,4-bisoctanoyloxybenzenesulfonate, 1,3- Bleaching activating compound, characterized in that any one selected from the group consisting of bisoctanoyloxybenzenesulfonate and 1,2-bisoctanoyloxybenzenesulfonate. 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.