KR100253419B1 - Bleaching activator and cleaning composition - Google Patents

Abstract

PURPOSE: A new bleaching activator and detergent composition containing the bleaching activator and a hydrogen peroxide-containing bleaching agent in a mole ratio of 1.5:1 to 3:1 are provided. Therefore, the detergent composition is useful in a wide cleaning temperate and effective in hydrophilic and hydrophobic stains. CONSTITUTION: This detergent composition comprises 1-30% by weight of a bleaching activator of formula(I) and 1-40% by weight of a bleaching agent containing hydrogen peroxide. In formula, R is C8-12 straight alkyl; a phenyl group of an alkylbenzene group may be o-, m- or p-; L is selected from the formula (II)(III)(IV)(V)(VI); R1 is C1-3 alkyl chain; Y is a soluble group of H or -SO3, SO4M; and M is alkali metal, ammonium or substituted ammonium cation.

Description

Bleach Activator and Bleach Detergent Composition Comprising the Same

The present invention relates to a bleaching agent and a bleaching detergent composition including the same, and particularly relates to a bleaching agent composition containing a new bleaching agent which is useful at a wide washing temperature and is effective for hydrophilic stains and hydrophobic stains. Generally, the use of bleach detergent is essential to remove stains such as black tea, coffee, tomato juice, etc., which are difficult to remove with a laundry detergent. As a bleach that can be used in a domestic washing machine, the peracid bleach is effective in removing stains and stains of fabrics. However, it is disadvantageous that it requires a relatively high washing temperature in comparison with known facts and convenience of handling. Although the bleach solution requires a temperature of 60 ° C. or higher in order for the peracid bleach to exhibit effective bleaching performance, only a part of the bleach shows a bleaching performance in a bleach solution at about 60 ° C. Therefore, there is a problem of using excess to obtain the desired level of bleaching effect. In addition, since the household washing machine washes below 60 ° C., it is almost impossible to bleach the household washing machine using only the peracid bleach. Accordingly, in order to improve the performance of the peracid bleach, a bleach activator has been used together and various types of bleach activators have been developed. For example, N, N, N ', N-tetraacetylethylenediamine, tetra acetylglycoluril uril, N-benzylimidazole, di-N-acetyldimethylglyoxime described in US Pat. Nos. 3912648 and 3919102, etc. N-acetylates such as 1-phenyl-3-acetylhydantoin, N, N-diacetylanaline and the like; Nitriles such as acetonitrile, malononitrile, tallonitrile and benzoyliminoacetonitrile and the like described in Korean Patent No. 930527, US Patent No. 5069821, UK Patent No. 1178371, and the like; Acid anhydrides such as phthalic anhydride, succinic anhydride, benzoic anhydride, glutaric anhydride, higher fatty acid anhydrides, and mixed anhydrides of carboxylic acids and organic sulfonic acids described in US Pat. 0-acetic acid salts of carbohydrates such as penta acetylglucose, octaacetylsucrose and the like described in International Patent No. 9110719 and the like; Benzoyloxybenzenesulfonic acid and carbonates described in British Patent No. 864798 and US Pat. No. 4,412,934.

However, even when used with the bleach described above, the performance of the peracid bleach is poor and it is difficult to use a sufficient amount due to economic conditions.

Thus, the inventors of the present invention have been conducted for the purpose of developing an oxygen-based bleaching composition having enhanced bleaching power, and found that the above object can be achieved by using a peroxide together with an alkylacid peroxide precursor. .

Accordingly, it is an object of the present invention to provide new bleach compositions and bleach detergent compositions, and the present invention also includes providing new compounds that act as bleach activators, such as the following formula (I).

Wherein R is a mixture of straight alkyl groups having about 8 to 10 carbon atoms and straight alkyl groups having 12 carbon atoms, L is a leaving group, and pKa of the conjugate acid thereof is in the range of about 4 to 13.

In the above formula, the phenyl group does not necessarily need to come to one end of the linear alkyl chain, it may be in the middle of the linear alkyl chain, or a mixture thereof may be used. The leaving group undergoes a nucleophilic reaction with hydrogen peroxide ions from the peracid bleach to produce a so-called perhydrolysis reaction that forms peroxybenzoic acid. In general, the leaving group is better to exhibit electrons, and the reactivity should be good enough to cause a perhydrolysis reaction within a reasonable time, but too reactive is difficult to store stably. The leaving group is preferably 4 to 13, more preferably 8 to 11, in the pKa value of the conjugate acid. Preferred bleaching agents are those of the general formula (I) in which L is selected from the following group.

Wherein R is as defined in formula (I), R 'is an alkyl chain of about 1 to 3 carbon atoms, Y is H or a solubilizing group such as -SO ₃ M, -COOM, -SO ₄ M and the like.

M is an alkali metal, ammonium or substituted ammonium cation, preferably sodium and potassium cations. Particularly preferred bleaching agents are those wherein R is a straight alkyl group having from about 8 to 12 carbon atoms, and L is selected from the following group.

Wherein R 'and Y are as defined above.

Most preferred bleaching agents have the general formula:

Wherein R is a straight chain alkyl group having about 8 to 10 carbon atoms or an alkyl straight chain having an average carbon number of 12, and M is sodium or potassium.

The method for preparing the bleach activator used in the present invention may be carried out by a method commonly used in the field of organic chemistry. In particular, bleach activators having an average carbon number of 12 can be prepared from a material generally called LAB. For example, the method of changing alkyl benzene to alkyl benzoic acid, etc. can be performed by the method of the following document.

Masaya Ogawa, J. Chem. Soc. Jpn., Ind. Chem. Sect., 59,134-5 (1956).

Alkyl benzoic acid synthesized according to the method of this document forms ester easily with the leaving group p-hydroxybenzene sulfonate.

The bleaching activator provided in the present invention has superior bleaching performance compared to known compounds known in the art, for example, N, N, N'N'-tetraacetyl ethylene diamine (TAED) and the like. Although the surface bleaching mechanism is not fully understood, it is known that percarboxylic acid must be produced under the attack of hydrogen peroxide ions produced by the peracid bleach in order for the bleach activator to perform. The resulting percarboxylic acid forms a dimer to release the generator oxygen, which is a bleaching component. In order for the bleach activator to perform, generator oxygen must be generated where it is needed. Since staining and staining of fibers are mostly hydrophobic, generator oxygen can be effectively generated on the fiber surface, that is, bleaching site, by giving the bleaching agent a suitable hydrophobicity. Therefore, the bleach activator presented in the present invention has a superior bleaching activity effect when compared to TAED. This principle is similar to that of general surfactants.

In order to obtain a preferable bleaching effect, the molar ratio of hydrogen peroxide to bleach activator produced by the peracid bleach is preferably from 1.5: 1 to 3: 1. Considering only the reaction of hydrogen peroxide produced by the peracid bleach with the bleach activator, the molar ratio of 1: 1 seems sufficient, but in reality there are many factors that change depending on the concentration, temperature, and component of the bleach solution. A molar ratio of 3: 1 is preferred. The use of more peroxide bleach does not have a significant effect on the bleaching effect and is uneconomical.

In order for the bleach activator of the present invention to exhibit optimum bleaching performance, the pH is preferably in the range of about 8.5 to 10.5, more preferably at pH 9.5 to 10.5.

The peracid bleach used as an essential component of the present invention is a substance capable of generating hydrogen peroxide in an aqueous solution, and as described above, it may exhibit bleaching performance even without a bleach activator. These peracid bleaches are well known compounds in the art, and common examples thereof include sodium perborate monohydrate and tetrahydrate, sodium percarbonate and 2KHSO 5 · K 2 SO 4 · KHSO 4, and preferably sodium perborate monohydrate and tetrahydrate and sodium percarbonate. Sodium perborate monohydrate is particularly preferred given that it is stable during storage and dissolves very quickly in the bleach solution. The amount of peracid bleach suitable for the present invention is about 1 to 95%, preferably 1 to 60%.

In addition, when the bleaching composition of the present invention is used as a detergent composition, the level of the peracid bleaching agent is preferably about 1 to 20%.

When the bleaching composition of the present invention is used as a detergent composition, it may contain a detergent composition such as a detergent surfactant and a detergent enhancer. Detergent surfactants may use one or more mixtures selected from surfactants such as anionic, nonionic and zwitterionic.

Surfactant types useful in the present invention are as follows. Soaps, ie, water-soluble salts of higher fatty acids, can be used. These include sodium, potassium and ammonium salts of higher fatty acids having about 12-18 carbon atoms, and particularly useful are the sodium salts of fatty acids mixed with about 20:80 fatty acids derived from coconut oil and tallow oil.

Useful anionic surfactants include water soluble salts of organic sulfur reaction products containing alkyl sulfonic acid or sulfate ester groups of about 10-20 carbon chains in length and the like. Surfactants of this category are sodium and potassium alkylsulfates obtained by sulfated higher alcohols such as those produced by reduction of tallow or coconut oil: sodium and potassium alkyl benzenes having from about 9 to 15 carbon atoms in the straight or branched chain alkyl groups. Preference is given to sulfonates, especially linear alkylbenzene sulfonates, abbreviated C11 to C13 LAS, wherein the average carbon number of the alkyl groups is about 11 to 13. Still other useful anionic surfactants include water-soluble salts of esters of alpi-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; Water-soluble salts of olefins having about 12 to 20 carbon atoms and paraffin sulfonate, and the like.

Water soluble nonionic surfactants are also useful in the compositions of the present invention. Suitable nonionic surfactants include polyethylene oxide condensates of alkyl phenols, such as condensates of about 3 to 12 moles of ethylene oxide per molecule of alkyl phenols and alkylphenols having alkyl groups having about 6 to 15 carbon atoms in a straight or branched chain structure. do. Preferred nonionic surfactants are water-soluble and water-dispersible condensation products of about 3 to 12 moles of ethylene oxide per mole of alcohol and aliphatic alcohols of about 8 to 22 carbon atoms in straight or branched chain structure. Especially preferred are condensation products of about 4 to 8 moles of ethylene oxide and alcohols having alkyl groups of about 9 to 15 carbon atoms per mole of alcohol.

Amphoteric surfactants are aliphatic or aliphatic of heterocyclic secondary and tertiary amines in which the aliphatic moiety is linear or branched, one of the aliphatic substituents has about 8 to 18 carbon atoms, and the at least one aliphatic substituent contains an anionic water-soluble group. Derivatives of derivatives are included. Detergent surfactant levels that can be used are 0-50%, preferably about 1-30%, most preferably about 10-25% of the total composition.

Detergent enhancers can be used in the bleaching compositions in the present invention. Water soluble inorganic or organic electrolytes are suitable enhancers. The enhancer may also be a water insoluble calcium ion exchange material, and examples of suitable water soluble inorganic detergency enhancers include alkali metals of carbonic acid, boric acid, phosphoric acid, bicarbonate and silicic acid. Examples of these salts are the sodium and potassium salts of tetraboric acid, bicarbonate, carbonate, tripolyphosphoric acid and metaphosphoric acid. Examples of suitable organic basic detergency enhancers include 1) water soluble amino carboxylates such as EDTA; 2) water-soluble polyphosphonic acid salts such as sodium salt of ethane-1-hydroxy-1,1-diphosphonic acid; 3) water-soluble polycarboxylic acid salts such as maleic acid, citric acid, carboxymethyl oxysuccinic acid, and the like.

Another detergency enhancer useful in the present invention contains materials capable of forming water insoluble reaction products with cations in hard water and are generally known as insoluble sodium aluminosilicates and have the general formula:

Na _z (AlO ₂ ) _z (SiO ₂ ) _y .XH ₂ O

Wherein Z and Y are integers greater than or equal to 6, the molar ratio of Z to Y ranges from 1.0: 1 to 0.5: 1, X is an integer from about 15 to 264, and the aluminosilicate is 20 mg equivalent / g or more calcium It has ion exchange capacity.

The cleaning promoter level of the bleaching composition is 0-70%, preferably 10-60%, most preferably 20-60%.

Buffers can be used to maintain the desired pH of the bleach solution. Buffers include, but are not limited to, many detergency enhancers described herein. Suitable buffers for use herein are already well known in the cleaning arts.

In order to improve the cleaning property, materials generally used widely, such as enzymes, photobleaches, colorants, and bubble stabilizers, may also be used in the present invention.

The bleaching composition of the present invention is prepared as described below and the component ratios are all by weight. The detergent composition is preferably prepared in powder or granule form. The method for preparing such a detergent composition may be prepared by a conventional publicly known method. An organic bleaching active material, an inorganic peroxide, and other optional materials are sprayed and dried in an aqueous slurry mixed with a basic composition such as a surfactant, zeolite, and inorganic salt. It can be prepared by the addition of components, in particular components which are heat labile.

Example 1

A granular detergent having the following composition was prepared.

Each composition is prepared by spray drying an aqueous slurry containing 60% by weight of a mixture containing all of the above components except the enzyme and bleach compositions. The spray dried product obtained has a particle size in the range of 8 to 150 mesh and the moisture content is about 9 to 9.5%. The above spray-dried product is combined with a peroxide, a bleaching agent and an enzyme in a rotary drum to prepare a granular detergent composition having a water content of about 7.5 to 8%.

Example 2

Each composition described in Example 1 was buffered with 8 g per 1 L of water at 30 ° C., pH 9.5 in a tergotometer, and washed with a standard stain test specimen for 30 minutes. Standard stain specimens and stains used for cleaning are as follows.

The stain test piece is prepared by passing the unpolluted fabric through a padding and drying apparatus containing each stain and drying at 100 ° C. The dried fabric was cut into 3 ″ × 4 ″ pieces and used for washing.

Washed fabric specimens are washed with 20 ° C. tap water and then dried. % Staining is measured by reading the reflection scales for pre- and post-wash stain specimens using a Gardner Color Difference Meter.% Staining is calculated by the following equation.

In the above formula, "Rd before washing" means Rd after staining.

The above results were obtained by measuring the bleaching characteristics for each contamination by the above method.

The test results show that the cleaning composition containing the bleach activator provided in the present invention has an excellent bleaching effect.

Claims (3)

A detergent composition comprising 1 to 30% by weight of a bleach activator represented by the following general formula (I) and 1 to 40% by weight of a hydrogen peroxide-containing bleach: Wherein R is a straight chain alkyl group having 8 to 10 carbon atoms or a straight chain alkyl group having 12 carbon atoms, the phenyl group of the alkylbenzene group may be o-, m- or p- of the alkyl group, and L is represented by the following formula (II) ( III) (IV) (V) (VI) is selected from: Wherein R 'is an alkyl chain of 1 to 3 carbon atoms, Y is a solubilizing group of H or -SO ₃ , SO ₄ M and M is an alkali metal, ammonium or substituted ammonium cation. The detergent composition according to claim 1, which is represented by General Formula (VII). Wherein R is a straight chain alkyl group having 8 to 10 carbon atoms or a straight chain alkyl group having 12 carbon atoms, and the phenyl group of the alkylbenzene group may be o-, m- or p- of the alkyl group. The detergent composition according to claim 1 or 2, wherein the molar ratio of the bleach activator and the hydrogen peroxide-containing bleach is 1.5: 1 to 3: 1.