KR20050108188A - Bleaching composition comprising amido derivatives compound - Google Patents

Abstract

The present invention relates to a bleaching composition comprising an amido-based compound as a bleach activator, and more particularly, the amido-based compound represented by the following Chemical Formula 1 emits peroxycarboxylic acid activating an inorganic peroxide only when contacted with water. This is good and can be very useful as a bleaching agent because it activates the inorganic peroxide at low temperature, not only excellent bleaching action, but also excellent washing power for hydrophilic and hydrophobic stains.

[Formula 1]

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

Description

Bleaching Composition comprising Amido derivatives Compound

The present invention relates to a bleaching composition comprising an amido-based compound, and more particularly, to release peroxycarboxylic acid activating the inorganic peroxide only in water of room temperature or low temperature, excellent bleaching power for hydrophilic and hydrophobic stains, storage stability It relates to a bleach composition comprising an amido-based compound which is an excellent 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.

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 the 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 these inorganic peroxides varies greatly with temperature. For example, sodium perborate effectively exhibits bleaching power at 80 ° C or higher and sodium percarbonate at 60 ° C or higher. When washing at 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, a method for expressing the bleaching power of the inorganic peroxide in low temperature water has been proposed, and as a part of this method, a bleach activator has been introduced.

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.

In U.S. Patent Nos. 4,876,046, 4,259,201, 5,089,167, and the like, many organic peroxycarboxylic acids are disclosed as activators of inorganic peroxides. 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, there is an urgent need for the development of a bleach comprising a bleach activator excellent in hydrophilic or hydrophobic contamination by releasing a peroxycarboxylic acid, a bleach activator only at room temperature or low temperature, and having excellent storage stability.

The present invention exhibits excellent storage stability, excellent bleaching effect and bactericidal effect by activating inorganic peroxide bleaching agent at low temperature, as well as excellent sterilizing power, and reacts with inorganic peroxide and washing water to express bleaching power. It is an object of the present invention to provide a bleaching composition containing a bleach activator that does not leave a smell on clothing and is not bothered to use.

In order to achieve the above technical problem, the present invention provides a bleaching composition comprising 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 alkaline earth metal ion.

[Formula 5a]

[Formula 5b]

[Formula 5c]

Amido-based compound represented by the formula (1) is not decomposed by heat, but only in aqueous solution, that is, only in contact with water to release peroxycarboxylic acid by reacting with inorganic peroxide, excellent storage stability and excellent self-bleaching and sterilizing power .

In particular, the present invention provides a bleaching composition comprising 0.01 to 15% by weight of amido-based compound, 3 to 80% by weight of inorganic peroxide, 1 to 40% by weight of surfactant and 10 to 50% by weight of builder.

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

Inorganic peroxides widely used in the bleaching composition include compounds that generate hydrogen peroxide, such as percarbonate salt (M ₂ C ₂ O ₆ ), perborate salt (MBO ₃ ), perphosphate, persulfate, urea peroxide, etc. I use it. Among them, percarbonate, perborate and mixtures thereof are preferably selected. The content of the inorganic peroxide is preferably 3 to 80% by weight based on the total weight of the composition, in consideration of the bleaching effect and economic efficiency.

In the bleaching composition containing the inorganic peroxide according to the present invention, components other than the above-mentioned inorganic peroxide and the amido-based compound which is a bleach activator are blended using an appropriate amount of the component normally used according to the type and purpose of the bleaching composition. For example, in the case of bleach compositions, surfactants and builders may be added.

Anionic surfactants or nonionic surfactants may be used as the surfactant, and the content thereof is not particularly limited, but is preferably 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, the builder is an alkali metal salt additive for improving the cleaning ability of the surfactant, for example, an alkali metal salt such as sodium tripolyphosphate, aluminosilicate such as zeolite, polyacetal carboxylate, polycarboxylate , Carbonates such as sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), silicates such as layered crystalline α-Na ₂ SiO ₃ or β-Na ₂ SiO _3, 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.

In addition to the above materials, the bleaching composition of the present invention may include other additives such as inorganic salts, fluorescent dyes, enzymes, fragrances, and the like commonly used in detergents.

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.

Synthesis Example Synthesis of Nonylaminoethoxycarbonyloxybenzenesulfonate

Scheme 1

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

As shown in the above reaction scheme, 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. The reaction of the chloroformate compound represented by 4 and the compound represented by Chemical Formula 5 is carried out using water as a solvent, and the amount of the solvent used is 40 to 100% by weight of the total amount of the reactants, and 2 at a temperature of 0 to 100 ° C. Reaction for ˜8 hours to synthesize nonylaminoethoxycarbonyloxybenzenesulfonate.

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 was separated using water. Then, after removing water with magnesium sulfate anhydride, the organic solvent was distilled under reduced pressure to prepare a chloroformate compound represented by the formula (4). The chloroformate compound and the compound represented by Formula 5 are dissolved in water, stirred at 70 ° C. for 2 hours, cooled to room temperature, filtered, and dried to form an amido-based compound represented by Formula 1 used as a raw material of Examples. Was prepared.

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.

<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 for preparing a bleaching composition, first, a granular powder was prepared from the ingredients except for the additive and the bleaching component, and then the additive and the bleaching component were added and mixed to prepare a bleaching composition. Unit is weight percent, NAECOBS is nonylaminoethoxycarbonyloxybenzenesulfonate, NOBS is nonyloxybenzene sulfonate, TAED is tetraacetylethylenediamine, LAS is linear alkylbenzenesulfonate, and fluorescent dyes Tinopal DMA-X (Tinopal DMA-X, manufactured by Ciba Specialty Chemical Co., Ltd.) was used, and Sabinase 12.OT (Savinase 12.OT, manufactured by Novozyme Co., Ltd.) was used as an enzyme. The content of sodium carbonate was adjusted to 100% by weight.

Raw material name Example Comparative example One 2 One 2 3 Percarbonate 15 15 15 15 15 NAECOBS 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 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

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. 1 g of a bleaching composition prepared in Examples 1, 2 and Comparative Examples 1 to 3 and water having a temperature of 20 ° C. and a hardness of 50 ppm CaCO ₃ in a terg-o-tometer, which is a washing force measuring device. Add at a rate of / L. The cotton cloth was put here, washed for 10 minutes, rinsed for 3 minutes, and naturally dried.

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

[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

In Equation 1, 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 Comparative example One 2 One 2 3 Red wine pollution 93% 87% 84% 73% 65% Coffee pollution 92% 90% 86% 71% 67% Pepper pollution 93% 89% 88% 73% 66% Secondary pollution 90% 88% 87% 72% 65%

From Table 2, the bleaching composition of Examples 1 and 2, which is a bleaching composition containing an amido-based compound as a bleach activator, contains NOBS, TAED, or a bleach activator against all contaminations such as red wine, coffee, red pepper, and tea. It was confirmed that it is excellent compared with the bleaching power of Comparative Examples 1 to 3 containing no.

Experimental Example 2 Evaluation of Washing Power of Bleaching Composition

1 g / L of a bleach composition prepared in Examples 1, 2 and Comparative Examples 1 to 3 and water having a temperature of 20 ° C. and a hardness of 133 CaCO ₃ ppm in a terg-o-tometer. Each of them was added in a ratio, and 8 × 8 cm 2 of cotton cloth (2 sheets each) and 5 × 5 cm 2 of Japan contaminated with wfk 10D (cotton contaminated cloth) and wfk 20D (mixed fiber contaminated cloth). A laundry science contaminant (8 sheets) was put in. 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 80% 78% 76% 71% 71% WFK 20D 81% 80% 75% 72% 72% Japan Laundry Science Association 79% 78% 76% 70% 70%

From Table 3, Comparative Example 1 in which the cleaning power for the hydrophilic and hydrophobic stains of Examples 1 and 2, which are bleaching compositions containing an amido-based compound as a bleach activator, contains NOBS, TAED or no bleach activator It was confirmed to be excellent compared to the washing power of 3 to.

Experimental Example 3 Evaluation of Bleaching Composition

Sterilization evaluation experiments P. eotaxin rugi Labor (P. aeruginosa, Pseudomonas aeruginosa), E. coli (E. coli, E. coli), the keurep when Ella pneumoniae (Klepsiella pneumoniae, Klebsiella pneumoniae), fatigue star nose Syracuse epi more pieces ( Staphylococcus epidermis, the skin flora), star fatigue nose Syracuse aureus (Staphylococcus aureus, hwanonggyun), Vibrio para H. Emory Tea Syracuse (Vibrio parahaemolyticus, Vibrio bacteria), Shigella Prex Tenerife (Shigella flexneri, Shigella), Aki neo bakteo Bauer Mani (Acineobacter baumannii), Aero Pseudomonas dihydro pillar (Aeromonas hydrophyla), Enterobacter aero jeneseu (Enterobacter aerogenes), salmo Ella typhimurium bunch was used sikjungdokgyun of 11, etc. Titanium (Salmoella typhimurium), medium cis-tone (Casitone) 30 g, Tween-80 5 g, Soyton 5 g, Salt (NaCl) 5 g, Lecithin 0.7 g, Agar 15 g added to 1 L of water Configured SDC medium was used.

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

After 15 minutes and 20 minutes, 1 mL of each bleach composition was added, serial dilution was performed using 0.85% aqueous NaCl solution as a dilution buffer, and then inoculated in a solid medium and incubated in an incubator at 37 ° C. for 24 hours. . Example 1, Example 2, Comparative Examples 1 to 3 and the control group was colony counted (colony counting), and compared with the control group to determine the bacterial mortality. 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

From Table 4, Example 1 and Example 2, which is a bleaching composition containing an amido-based compound as a bleach activator, are initially killed than Comparative Examples 1 to 3, which are bleaching compositions containing NOBS, TAED or no bleach activator. It was confirmed that the rate is excellent.

As described above, the bleaching composition containing the amido-based compound as the bleaching activator according to the present invention has good storage stability, excellent bleaching power, excellent cleaning power for hydrophilic and hydrophobic stains, and excellent self sterilization power. It can be widely used in industrial bleach such as household bleach and paper industry. Especially, it does not bother to use because there is no smell in washing water and laundry by reacting with inorganic peroxide.

Claims (4)

A bleaching composition comprising an amido-based compound represented by Formula 1 below; [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] The bleaching composition of claim 1, wherein the amido-based compound is included in an amount of 0.01 to 15 wt% based on the total weight of the bleaching composition. The bleaching composition of claim 1, wherein the composition comprises 0.01 to 15 wt% of an amido compound, 3 to 80 wt% of an inorganic peroxide, 1 to 40 wt% of a surfactant, and 10 to 50 wt% of a builder. 4. The bleaching composition of claim 3, wherein the inorganic peroxide is selected from the group consisting of percarbonates, perborates, and mixtures thereof.