KR100470889B1 - Bleach Detergent Composition Containing Manganese Complex - Google Patents

Abstract

The present invention relates to a bleach detergent composition containing a manganese complex compound. More specifically, the present invention relates to a bleach detergent composition which improves the bleaching effect even at room temperature and low temperature washing temperature containing a manganese complex compound acting as a bleach activator.

Description

Bleach Detergent Composition Containing Manganese Complex

The present invention relates to a bleach detergent composition containing a manganese complex compound. More specifically, the present invention relates to a bleach detergent composition which improves the bleaching effect even at room temperature and low temperature washing temperature containing a manganese complex compound acting as a bleach activator.

For the bleaching effect, Korea has been using washing and drying processes using boiled or sunshine ultraviolet rays for the past several decades. The method not only enhances the cleaning power, but also promotes oxidation, so that the bleaching performance can be felt and sterilization is possible. This method, however, had to be uncomfortable for the laundry person to boil, wash, and dry on the clothesline.

The use of bleach in Europe has made it easier to remove bleachable contaminants, such as fruit juice, coffee, wine, and grass. However, the sodium perborate used as the bleaching agent exhibits performance at 80 degrees or higher, and sodium percarbonate also exhibits effective bleaching performance at 60 degrees or higher.

Most of domestic washing conditions are performed at room temperature, and washing is performed in cold water of 20-25 ° C. in summer and even 5 ° C. in winter. It is very difficult to achieve the bleaching effect when using bleach alone in such domestic washing conditions. Therefore, domestic consumers could feel the bleaching effect only when they used it for boil or used excessive bleach in hot water.

In the past decades, it has been known that most transition metals act as catalysts for peroxides, making the peroxides more active. Therefore, when the transition metal salt is used immediately, it causes a phenomenon of promoting decomposition of the bleaching agent rather than bleaching due to the radical catalyst phenomenon. In the past, the transition metal salt was complexed (chelating) to prevent the rapid decomposition of the bleaching agent. In addition, when the transition metal salt is stored together with the bleach, the effect is reduced due to the decomposition of the bleach, so the bleach detergent has to complex (chelating) the transition metal that may be present in the detergent powder. Therefore, it has been suggested that it is preferable to use a chelating agent to prevent rapid catalytic phenomenon rather than using a transition metal salt directly.

However, most transition metals and chelated complexes did not show a bleaching effect. Rather, the laundry can be made darker. This is because the glass transition metal ions react rapidly with the peroxide to generate oxygen, rather than the active oxygen produced in the peroxide, which is useful for bleaching, or the ion itself is oxidized. That is, in order to effectively exhibit bleaching performance using a peroxide, the transition metal used as a catalyst should not react rapidly with the bleach (peroxide). Oxygen must be liberated slowly from the peroxide so that free radicals can be produced to achieve a sufficient bleaching effect. In other words, the transition metal acting as a catalyst should be synthesized as a bleach activator which gradually induces active oxygen from the peroxide.

However, slowly activating peroxides before hydrolysis and oxidation has been almost impossible to solve with existing proposals.

In addition, according to the experimental results of the present inventors, cadmium and cobalt showed the best effect among the various transition metals, but due to environmental problems, manganese (Mn) was selected as the next best solution.

Manganese has long been used in many patent documents as a transition metal that can be used as a catalyst for activating bleach. For example, European Patent No. 237111 uses manganese gluconate (III) chelated with gluconic acid or saccharic acid. However, in this experiment (about 10-20 ° C), European B. It is not shown. U.S. Patent No. 5246621 and EP 458398 also propose and invent a series of manganese complexes in which dinuclear manganese is surrounded by a coordination ligand such as 1,4,7-trimethyl-1,4,7-triazaclononane. However, the price of intermediates (ligands) of this material is very expensive and is practically difficult to apply to the product.

Accordingly, the present inventors can activate or bleach oxygen, bleach, sodium percarbonate, sodium perborate, sodium perphosphate, urea peroxide, etc. at low temperature to oxidize or bleach contamination of coffee, tea, fruit juice, grass, wine, etc. Manganese complexes have been developed and used as bleach activators to produce bleach detergents with excellent bleaching ability to complete the present invention.

Therefore, the present invention is a bleach detergent composition containing anionic surfactant, nonionic surfactant, at least one builder and peroxide, and containing 0.00001 to 0.1% by weight of a manganese complex compound of the following formula (1) as Mn content as a bleach activator Provides:

[(salen) Mn ^IV (μ-O) ₂ Mn ^IV (salen)]

Wherein salen is N, N'-bis (salicylidene) ethylenediamine.

Manganese complexes of the present invention are very effective bleaching agents for bleaching substrates by activating peroxides. In addition, unlike conventional compounds, the raw material cost is cheap and can be actually used, and shows higher performance in contamination of coffee, pepper, etc., compared to gluconate Mn (III).

An example of such a manganese complex compound can be represented by the following formula:

The complex of the present invention is a useful bleach activator that effectively bleaches contaminants by coffee or red pepper with peroxide when washed at low temperatures in a much more effective way than the Mn based bleach activators known in the art. Another feature is that the bleach activator can be used with detergent enzymes such as proteolytic enzymes.

Therefore, the present invention provides a method of bleaching or washing with peroxides, i.e., sodium percarbonate and sodium perborate, as bleach, wherein the bleach is activated by the Mn complex of the present invention. Therefore, another feature of the present invention is that an effective amount of a peroxide compound and a bleach activator containing the manganese complex compound of formula (1) interact with each other to provide a cleaning effect on the contaminated substrate and to bleach the substrate.

The manganese complex compound as an active ingredient as the bleach activator is a novel feature of the present invention. The Mn complex compound of the present invention has an effective amount of catalyst in the range of 0.00001 to 0.1 wt%, preferably 0.0005 to 0.05 wt% in Mn content.

The improved bleaching compositions of the present invention contain percarbonate bleaching agents, such bleach activators, surfactants, general detergents and builders, and may also contain other known ingredients added in such compositions. These bleaching compositions are used in laundry detergents and bleaches. Peroxides such as sodium percarbonate or sodium perborate and compositions containing the aforementioned bleach activator catalysts are effective in the pH range from neutral to alkali, ie in the range of pH 7-13, with an optimum effect of pH 8.5-11. Appear in range.

As the peroxide used in the present invention, alkali metal peroxides such as sodium perborate, sodium percarbonate, calcium percarbonate, etc. which are widely used may be used, and organic peroxides such as perphosphate, persulfate, and urea peroxide may be used, but price and performance The difference in is not used as a detergent composition. Mixtures of two or more of these peroxides may be used. Sodium perborate monohydrate is more preferable because the solubility and oxygen generation amount is superior to the tetrahydrate, and sodium perborate is excellent in terms of environmental friendliness, but it has not been as stable as the perborate compound yet. These peroxides may be used alone or in combination with detergents or by adding tetraacetylethylenediamine (TAED, tetraacetylethylendiamine). The addition of TAED not only increases the effect of bleaching activity but also has a bactericidal effect, which is preferable in terms of hygiene.

In the present invention, the bleach detergent composition comprises 1 to 40% by weight of high oxide, preferably 5 to 20% by weight. TAED contains 0.1 to 10% by weight, preferably 1 to 5% by weight.

Bleaching detergents of the present invention may use pore-formed surfactants and builders.

Anionic, nonionic, soap, and the like may be used as the surfactant, and examples of builders include alkali salts of polyphosphoric acid, aluminum silicates, polyacetal carboxylates, polycarboxylates, and the like. Can be. As the anionic surfactant, at least one selected from linear alkylbenzene sulfonate, fatty acid salt, alkanesulfonate salt and alpha olefin sulfonate salt can be used, and as nonionic surfactant, oxo alcohol polyethylene glycol ether, fatty acid alkanolamide, alkyl ethoxyl One or more of these may be contained, such as a rate.

The surfactant can be used at 1 to 50% by weight, preferably 10 to 40% by weight, and the builder is used at 1 to 70% by weight, preferably 10 to 40% by weight relative to the composition.

In addition to the above substances, inorganic salts such as soda ash and forage, which are generally used in powder detergents, and additives such as fluorescent dyes, enzymes, and flavors may also be used.

Peroxides and bleach activators used in the present invention can be used in detergents in the form of powders or granules prepared by known techniques as non-flowing particles. That is, peroxide and [(salen) Mn ^IV (μ-O) ₂ Mn ^IV (salen)] are added to detergent powders prepared by spray drying, non-top, injection, granulation, and concentration processes. It can manufacture.

Rather than using [(salen) Mn ^IV (μ-O) ₂ Mn ^IV (salen)] in the form of powder or granules, it is preferable to use detergent powder and peroxide separately by granulation process or coating after injection process. The reason for this is that, upon contact with detergent powders or peroxides, the bleach activator is hydrated or oxidized and the peroxides decompose and the effective oxygen content is drastically reduced. As the material to be used for coating, silicone oil, wax, soap (or fatty acid before neutralization) and the like can be used.

Preparation Example 1 Preparation of [(salen) Mn ^IV (μ−O) ₂ Mn ^IV (salen)]

To a suspension of 3.2 g (8.2 mmol) of [Mn (salen) (H ₂ O)] (ClO ₄ ) in 200 ml of CHCl _3, 125 ml of 0.2 M NaOH solution was added, followed by 5 days at room temperature without clogging the flask. Stir while. The reaction is filtered, the solvent in the filtrate is evaporated and the remaining residue washed with a mixed solvent of ether / acetone and dried to give a black red compound in near quantitative yield. In the present invention, an automatic evaporator was used for drying.

<Examples 1-3 and Comparative Examples 1 and 2>

Preparation of Bleach Detergent Composition and Evaluation of Bleaching Performance for Artificial Contaminated Cloth Contaminated by Coffee.

In 1 L of distilled water, a standard amount of concentrated detergent (0.67 g) was added as shown in Table 1, followed by addition of peroxide sodium percarbonate (0.075 g), followed by the bleach prepared in Preparation Example 1. The activator was added and stirred for 1 minute on a Torg-O-Tometer to dissolve the detergent, and then put two contaminated artificial contaminants with coffee and wash again for 10 minutes. After the dried artificial dirt cloth is naturally dried, the degree of bleaching is calculated by using the difference between the ΔE (H) value before washing and the ΔE (H) value after washing. ΔE (H) values are measured using a colorimeter. Bleaching force of Comparative Example 2 and Examples 1 to 3 was obtained based on Comparative Example 1 based on 100, and the results are shown in Table 2 below.

(Unit: weight%) Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Anionic surfactant 18 18 18 18 18 Nonionic surfactant  6 6 6 6  6 Soda ash 36 35 35 34 30 Zeolite 25 25 25 25 25 Fluorescent dyes 0.2 0.2 0.2 0.2 0.2 Detergent additives (enzyme, defoamer) 2.3 2.3 2.3 2.3 2.3 Sodium percarbonate 12.5 12.5 12.5 12.5 12.5 TAED  One  One  One Bleach activator (production example 1)  One  One  5 system 100 100 100 100 100

Bleach composition ΔE (H) difference Comparative Example 1 Detergent + Sodium Percarbonate 100 Comparative Example 2 Detergent + Sodium Percarbonate + TAED 110 Example 1 Detergent + Sodium Percarbonate + [(salen) Mn ^IV (μ-O) ₂ Mn ^IV (salen)] 133 Example 2 Detergent + sodium percarbonate + TAED + [Mn III (Salen) (H ₂ O)] (ClO ₄ ) 141

As can be seen from the results of the above table, Examples 1 and 2 were more excellent than Comparative Examples 1 and 2, which are conventional bleaching systems using sodium percarbonate or sodium percarbonate and TAED as the bleaching compound. The ΔE (H) difference of Example 3 was too high in manganese content, resulting in a phenomenon in which manganese was colored on the cloth.

The bleach detergent composition of the present invention exhibits a better bleaching effect than the conventional bleach detergent even at low or normal temperature by containing a manganese complex compound as a bleach activator.

Claims (3)

A bleach detergent composition containing an anionic surfactant and a nonionic surfactant, at least one builder and a peroxide, and containing 0.00001 to 0.1% by weight of a manganese complex compound of formula (1) as Mn content: [Formula 1] [(salen) Mn ^IV (μ-O) ₂ Mn ^IV (salen)] Wherein salen is N, N'-bis (salicylidene) ethylenediamine. The bleach composition according to claim 1, wherein the peroxide is sodium percarbonate or sodium perborate and the content is 1 to 40% by weight. The bleach detergent composition according to claim 1, wherein the manganese complex is a substance coated with soap, silicone oil or wax after the granulation process or the injection process.