KR100544016B1 - Quaternary Ammonium Derivative Compound for Bleaching Activator, Preparing Method thereof and Bleach Composition comprising the same - Google Patents

Abstract

The present invention relates to a quaternary ammonium derivative-based bleaching activating compound, a preparation method thereof, and a bleaching composition comprising the same, and is characterized by containing a quaternary ammonium derivative-based compound represented by the following general formula (1). 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

<Formula 1>

Bleach Activation, Quaternary Ammonium Derivatives, Peroxides, Bleach

Description

Quaternary Ammonium Derivative Compound for Bleaching Activator, Preparing Method Eating and Bleach Composition comprising the same}

1 is a flow chart briefly illustrating a method for preparing a quaternary ammonium derivative-based bleach activating compound according to the present invention.

The present invention relates to a bleaching activating compound, a method for preparing the same and a bleaching composition comprising the same, and more particularly, having excellent storage stability and activating an inorganic peroxide bleaching agent at low temperatures, thereby exhibiting an excellent bleaching and washing effect and bactericidal effect. The present invention relates to a bleach activating compound, a preparation method thereof, 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 bleaching force expression is still insufficient at low temperatures.

In addition, U.S. Patent Nos. 4,634551, 4,852,989, 5,183,584, 5,414,099 and the like have disclosed amido derivative-based bleach activators, but the bleach compositions containing these amido derivatives are limited in hydrophobic contamination. . In addition, in US Patent Nos. 4,179,390, 4,259,201, 5,520,844, and the like, a plurality of organic peroxycarboxylic acids are disclosed as inorganic peroxide activating compounds. Bleaching compositions containing organic peroxycarboxylic acids are unstable with heat and thus have their own activities. The storage stability tends to be poor such as loss of oxygen. 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.

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 A quaternary ammonium derivative-based bleaching activating compound having excellent bactericidal power, a method for preparing the same, and a bleaching composition containing the same are provided.

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

<Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently alkyl or aryl having 1 to 24 carbon atoms, alkenyl having 2 to 24 carbon atoms and 1 to 4 carbon atoms. Any one selected from the group consisting of phosphorus hydroxyalkyl, R ₄ is hydrogen or methyl, L is any leaving group selected from the group consisting of the following formulas (I) to (IV), and X ⁻ is It is any one selected from the group consisting of counter ions, organic anions and inorganic anions.

In formula (I), n is an integer of 3 to 5, R ₅ in formula (II) is alkylene having 1 to 20 carbon atoms, R ₅ in formula (III) is alkyl having 1 to 20 carbon atoms, In formulas (II) to (IV), Y is any one selected from the group consisting of hydrogen, chlorine, bromine, SO ₃ M, CO ₂ M and OSO ₃ M, where M is hydrogen, alkali metal ion, ammonium ion and equivalent Any one selected from the group consisting of alkaline earth metal ions.

Examples of X ⁻ include Cl ⁻ , Br ⁻ , nitrate, monosulfate, bisulfate, tosylate and mesylate, and the like.

The quaternary ammonium derivative compounds represented by the general formula (1) do not decompose by heat, and react with hydrogen peroxide only in aqueous solution, ie, only when contacted with water, to release peroxycarboxylic acid, which is excellent in storage stability and excellent in self-bleaching power. .

Such quaternary ammonium derivative compounds include N-dodecyl-N, N-dimethylammonium methyl amido acetylcaprolactam chloride, N-dodecyl-N, N-dimethylammonium methyl amido acetylvalerolactam chloride, N- Dodecyl-N, N-dimethylammonium methylamido acetylpyrrolidone chloride, N-hexadecyl-N, N-dimethylammonium methylamido acetylcaprolactam chloride, and the like.

In addition, the present invention comprises the steps of (a) reacting caprolactam and chloromethyl amidoacetyl halide in a solvent to obtain chloromethyl amidoacetyl caprolactam; And (b) reacting the obtained chloromethylamidoacetylcaprolactam with a tertiary alkylamine in a solvent. It provides a method for preparing a quaternary ammonium derivative-based bleaching activating compound comprising a.

Hereinafter, a quaternary ammonium derivative-based bleaching activating compound according to the present invention and a method of preparing the same will be described in detail. 1 is a flow chart briefly illustrating a method for preparing a quaternary ammonium derivative-based bleach activating compound according to the present invention.

First, caprolactam is dissolved in a solvent such as toluene, and then reacted by adding chloromethylamidoacetyl halide (S10). At this time, it is preferable that chloromethyl amidoacetyl halide is added at 5-20 degreeC. After raising the temperature slightly and stirring at room temperature for 3 to 7 hours, a precipitate is formed. The precipitate is filtered off and distilled under reduced pressure to obtain chloromethylamidoacetylcaprolactam.

Then, the obtained chloromethylamidoacetylcaprolactam is dissolved in a solvent such as acetone or 2-butanone, and reacted with addition of a tertiary alkylamine at reflux to produce a precipitate. An ammonium derivative system compound is obtained (S20). At this time, the amount of the solvent used is 40 to 95% by weight based on the total weight of the reactants, the weight ratio of tertiary alkylamine to chloromethylamidoacetylcaprolactam is preferably 4 to 6 to 6 to 4. Moreover, it is preferable that reaction temperature is 20-100 degreeC, and reaction time is 3 to 8 hours.

The quaternary ammonium derivative-based 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 total weight of the quaternary ammonium amido derivative-based bleaching activating compound It is preferable to include 0.01 to 15% by weight based on the. If 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. If the content of the quaternary ammonium amido derivative-based bleaching activating compound is more than 15% by weight, the inorganic peroxide may be excessively decomposed. have.

Peroxides commonly used in bleaching compositions are inorganic compounds that generate hydrogen peroxide such as percarbonate salt (M ₂ C ₂ O ₆ ), perborate salt (MBO ₃ ), perphosphate, persulfate, urea peroxide, etc. And organic peroxides. Among them, the peroxide suitable for the present invention is preferably any one selected from percarbonates, perborates and mixtures thereof. The content of such an inorganic peroxide is preferably 1 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 inorganic peroxide and the bleach activating compound are blended using an appropriate amount of the component usually 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. As the anionic surfactant, for example, alkylbenzenesulfonate (R ₆ -CH ₂ -SO ₃ Na, wherein R ₆ is an alkyl group having 9 to 15 carbon atoms), fatty acid salt (R ₇ -CH ₂ -COONa, wherein R ₇ is an alkyl group having 11 to 16 carbon atoms, an alkensulfonate (R ₈ = CH-SO ₃ Na, where R ₈ is an alkyl group having 11 to 18 carbon atoms) or an alphaolefin sulfonate (R ₉ -CH = CH- CH ₂ -SO ₃ Na, wherein R ₉ is an alkyl group having 12 to 18 carbon atoms, and the like. The nonionic surfactant is alkyl polyoxyethylene glycol (R ₆ -CH- (O-CH ₂ -CH ₂ ) _p -OH, where R ₆ is an alkyl group having 11 to 18 carbon atoms, _p is 5 to 25 Integers) and fatty acid polyoxyethylene glycol (R ₇ -CO- (O-CH ₂ -CH ₂ ) _q -OH, wherein R ₇ is an alkyl group having 11 to 18 carbon atoms, _q is an integer of 5 to 25), and the like. Can be used.

Builders are alkali metal salt additives for improving the cleaning ability of surfactants, such as alkali metal salts of polyphosphates such as sodium tripolyphosphate, aluminosilicates such as zeolites, polyacetal carboxylates, polycarboxylates, sodium carbonate ( Carbonates such as Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), silicates or sulfates such as α-Na ₂ SiO ₃ or β-Na ₂ SiO ₃ of layered crystalline, and the like.

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, and the like, which are commonly used in detergents, in addition to the aforementioned 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.

Preparation Example 1 Preparation of Quaternary Ammonium Derivatives

a. Steps for preparing chloromethylamido acetylcaprolactam

 22.6 g of caprolactam was dissolved in 100 mL of toluene, and then slowly added 17.0 g dml chloromethyl amido acetyl chloride, followed by stirring at room temperature for 6 hours. The precipitate formed was filtered off and the filtrate was distilled under reduced pressure to give 22.1 g of an oily reactant.

b. Steps for preparing N-dodecyl-N, N-dimethyl ammonium methylamido acetylcaprolactam chloride

12.3 g of the reaction product obtained above and 10.6 g of N-dodecyl-N, N-dimethyl amine were dissolved in acetone, and the mixture was refluxed for 5 hours, cooled to room temperature, and the precipitate obtained was filtered and dried to obtain 16.2 g of a white solid.

Example 1 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. Bleaching composition is a conventional manufacturing method, first, to prepare a granular powder with ingredients except the additives and bleaching component, and then to add and mix the additive and bleaching component to prepare a bleaching composition. The unit is parts by weight.

Raw material name Example 1 Comparative example One 2 3 Percarbonate 15 15 15 15 DDAMAL 6 - - - NOBS - 6 - - TAED - - 6 - LAS 1.5 10 10 15 Polyoxyethylene alkyl ether 7 5 5 5 Sodium bicarbonate 10 10 10 10 Sodium carbonate to 100 to 100 to 100 to 100 Sodium sulfate 10 10 10 10 Zeolite 4A 20 20 20 20 Fluorescent dyes 0.15 0.15 0.15 0.15 enzyme 0.5 0.5 0.5 0.5

In Table 1, DDAMAL is N-dodecyl-N, N-dimethyl ammonium methyl amido acetylcaprolactam chloride obtained in Preparation Example 1, NOBS is nonyloxybenzene sulfonate, TAED is tetraacetylethylenediamine, LAS is a linear alkylbenzene sulfonate, fluorescent dye was used Tinopal DMA-X (Tinopal DMA-X, manufactured by Ciba Specialty Chemical Co., Ltd.), the enzyme is Sabinase 12.OT (Savinase 12.OT, manufactured by Novozyme) ) Was used.

Bleaching power and washing power of the bleaching compositions prepared in Example 1 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 (water temperature 20 ° C., hardness 50 CaCO ₃ ppm) and the bleaching composition prepared in Examples 1 and 3 in a ratio of 1 g / L in a terg-o-tometer, a washing force measuring instrument. Added. After putting the cotton cloth here and washing for 10 minutes, it rinsed for 3 minutes and dried naturally.

After measuring the whiteness of the cotton cloth before and after the wash using a colorimeter, the bleaching force was calculated by substituting the Kubellka-Munk's eq of Equation 1 as shown in Table 2 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 1 Comparative example One 2 3 Red wine pollution 74% 73% 63% 40% Coffee pollution 81% 72% 61% 43% Pepper pollution 80% 74% 61% 43% Secondary pollution 79% 71% 60% 45%

Looking through Table 2, the bleaching power of the bleaching composition of Example 1 containing the quaternary ammonium derivative-based bleaching activating compound according to the present invention was used as a bleaching activating compound against contamination of red wine, coffee, red pepper, and tea. It can be confirmed that it is superior to the case of Comparative Examples 1 to 3 containing NOBS, TAED or no bleach activating compound.

Washing power evaluation experiment

To a Terg-o-tometer, water having a temperature of 20 ° C. and a hardness of 133 CaCO ₃ ppm and the bleaching compositions of Examples 1 and Comparative Examples 1 to 3 were each added at a rate of 1 g / L, Here, 8 × 8 cm 2 cotton cloth (2 sheets each) contaminated with wfk 10D and wfk 20D and 5 × 5 cm 2 contaminant cloth (8 sheets) were placed. 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 1 Comparative example One 2 3 wfk 10D 80% 74% 69% 79% w 20D 78% 73% 70% 70% Japan Laundry Science Association 80% 74% 68% 68%

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

As described above, the bleaching composition containing the quaternary ammonium derivative-based bleaching activating compound according to the present invention not only has excellent bleaching effect by releasing peroxycarboxylic acid even at low temperature washing water, but also has a washing power against hydrophilic and hydrophobic stains. This is excellent. The bleaching composition containing the quaternary ammonium derivative-based bleaching activating compound according to the present invention can be widely used in industrial bleaching agents, such as household bleaching and paper industry.

Claims (6)

A quaternary ammonium derivative-based bleaching activating compound represented by the following general formula (1); <Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently alkyl or aryl having 1 to 24 carbon atoms, alkenyl having 2 to 24 carbon atoms and 1 to 4 carbon atoms. Any one selected from the group consisting of phosphorus hydroxyalkyl, R ₄ is hydrogen or methyl, L is any leaving group selected from the group consisting of the following formulas (I) to (IV), and X ⁻ is Any one selected from the group consisting of counter ions, organic anions and inorganic anions;

In formula (I), n is an integer of 3 to 5, R ₅ in formula (II) is alkylene having 1 to 20 carbon atoms, R ₅ in formula (III) is alkyl having 1 to 20 carbon atoms, In formulas (II) to (IV), Y is any one selected from the group consisting of hydrogen, chlorine, bromine, SO ₃ M, CO ₂ M and OSO ₃ M, where M is hydrogen, alkali metal ion, ammonium ion and equivalent Any one selected from the group consisting of alkaline earth metal ions. The method of claim 1, wherein the bleach activating compound is N-dodecyl-N, N-dimethylammonium methyl amido acetylcaprolactam chloride, N-dodecyl-N, N-dimethylammonium methyl amido acetylvalerolactam chloride, N-dodecyl-N, N-dimethylammonium methylamido acetylpyrrolidone chloride, and N-hexadecyl-N, N-dimethylammonium methylamido is one selected from the group consisting of acetylcaprolactam chloride Quaternary ammonium derivative-based bleaching activating compound. 2. The method of claim 1, wherein X ^- is Cl ^-, Br ^-, nitrate, mono-sulfate (monosulfate), 4-level, characterized in that one selected from bisulfate (bisulfate), a group consisting of the tosylate and mesylate Ammonium Derivative Bleaching Activated Compound. (a) reacting caprolactam with chloromethylamidoacetylhalide under a solvent to obtain chloromethylamidoacetylcaprolactam; And (b) reacting the obtained chloromethylamidoacetylcaprolactam with a tertiary alkylamine in a solvent; a method for producing a quaternary ammonium derivative-based bleaching activating compound comprising a. An oxygen-based bleaching composition containing an inorganic peroxide, wherein the quaternary ammonium derivative-based bleaching activating compound comprises 0.01 to 15% by weight, based on the total weight of the total composition. 6. The bleaching composition of claim 5, wherein the inorganic peroxide is any one selected from percarbonate salt, perborate salt, and mixtures thereof.

Images