KR20000007435A - Novel bleaching activator and bleaching detergent composition containing it - Google Patents

Abstract

PURPOSE: A novel benzimidazolinone bleaching activator is provided which has high bleaching effect even in water at room temperature or at a low temperature, and high solubility in water and high stability in comparison with conventional benzimidazolinone compounds. CONSTITUTION: The bleaching activator is represented by formula III, wherein:R1 and R2 are acetyl, benzoyl, propionyl, pentanoyl, hexanoyl, or nonanoyl; R1 and R2 can have identical or different acyl substituents, preferably acetyl.

Description

Novel bleach activators and bleach detergent compositions containing them

The present invention relates to a novel benzimidazolinone-based bleach activator and a bleach detergent composition containing the same. In particular, the present invention relates to a bleach detergent composition having improved bleaching power containing a benzimidazolinone-based compound such as a compound of the following general formula (III) and hydrogen peroxide or an inorganic peroxide as a novel bleach activating material.

In Formula (III), R ₁ and R ₂ may be acetyl, benzoyl, propionyl, pentanoyl, hexanoyl or nonanoyl, etc., and R ₁ and R ₂ may have the same or different acyl substituents. Most preferred compounds are those in which R ₁ and R ₂ are acetyl groups.

There are many examples in which various N-acyl compounds are used as peroxygen bleach activators in already known documents and patents.

For example, French Patent No. 1,583,330 reports N-acyl derivatives having imidazole, pyrididine and triazole structures as bleach activators, and British Patent No. 1,046,251 describes N-acyl compounds of nitrogen-containing heterocyclic compounds. It is also reported that it can be used as a bleach activator.

The bleach activator is used in combination with inorganic peroxides to produce organic peroxides, which can easily remove contaminants from cloth such as stains on tea, which are not easily removed with detergents containing only inorganic peroxides as bleach.

However, since most of these bleaching agents have little solubility in water at room temperature, they do not show satisfactory bleaching power even at room temperature or at a washing temperature of 50 to 70 ° C. In particular, these substances are unstable when the shelf life of detergent is extended. The problem is that the performance is poor.

Benzimidazolin-based N-acyl compounds (formula IV) similar to the compounds of the present invention are already described in US Pat. No. 3,775,333 as bleach activators, and exhibit excellent bleaching ability at temperatures of 50-70 ° C. In addition, it is described that the long-term storage ability is good, so that the bleaching ability is about 3 times higher than the bleach detergent without the same.

In addition, these activators have the advantage that the damage to the fiber is extremely less than the chlorine-based bleach, and the stability during the storage period is also described that the activity is maintained even after more than one month. However, since most of these compounds have little solubility in water, there is a disadvantage in that the efficacy is not excellent at a washing temperature of less than 60 ℃.

The present invention provides an excellent bleaching effect and good long-term storage, and at the same time provides a bleaching activating material and a bleaching detergent composition including the same, which exhibits excellent bleaching power even at room temperature by increasing the solubility in water. It aims to do it.

In the present invention, in order to achieve the above object, a new compound having increased solubility in water was introduced by introducing a sulfonic acid group into a benzene ring.

The compounds of the present invention not only have the same advantages as the bleach activators as the substances described in the above-mentioned US patent, but also are characterized in that the bleaching action is excellent even at room temperature or lower temperature of 15 to 25 ℃. In addition, the benzimidazole compounds having poor acyl groups may also have excellent solubility in water, thereby preventing the residual bleaching activator in the laundry, and promoting the biodegradability of the residue by introducing sulfonic acid groups.

Synthesis of the compounds of the present invention starts from commercially available 1,3-dihydro-2H-benzimidazol-2-one (I) and sulfonates with concentrated sulfuric acid to quantify the sulfonic acid groups in the benzene ring almost quantitatively. After obtaining the introduced benzimidazolinone sulfonic acid (II), the desired final target compound (III) can be obtained in high yield by reaction with an acid chloride or an acid anhydride of the organic acid to be introduced.

The bleach detergent composition of the present invention may be used by mixing one or more kinds of bleach activators represented by the general formula (III), and the content is 0.1 to 30% by weight, preferably 2 to 15% by weight, based on the total composition. Range.

Hydrogen peroxide, organic peroxide and inorganic peroxide salts may be used as the bleach detergent composition of the present invention, all of which are known to generate hydrogen peroxide in water.

Examples of the organic peroxide compound include urea peroxide, benzoic acid peroxide, methyl ethyl ketone peroxide, and the like.

As the inorganic peroxide bleaching compound, alkali metal perborate, percarbonate, perphosphate, persulfate and the like can be used.

In the bleach detergent composition of the present invention, two or more conventional bleach activators such as tetraacetylethylenediamine, nonanoyloxybenzenesulfonate, and the like can also be used.

In addition, representative surfactants of anionic, cationic, nonionic or amphoteric systems can be used in the bleach detergent composition of the present invention.

Suitable anionic surfactants include fatty acid alkylbenzenesulfonates, fatty acid alkylsulfonates, alkali metals and alkaline earth metal salts of fatty acid monoglyceride sulfates. Suitable cationic surfactants are quaternary fatty acid alkylammonium salts, wherein one of the fatty acid alkyl groups is dodecyltrimethyl ammonium chloride of 12 to 18 carbons or ethyldimethyl octadecyl ammonium methosulfate.

Suitable nonionic surfactants include polyglycol ethers of fatty acids and fatty alcohols.

As the amphoteric surfactant, an amino fatty acid system such as dimethylaminopropanoic acid or an imino fatty acid such as methyliminodilauryl acid is suitable.

The bleaching composition using the bleach activator of the present invention can be used for various purposes, and the main purpose is to use the laundry detergent of general household or industrial textiles.

The following examples illustrate the invention in more detail, and this example does not limit the invention.

Example 1

Preparation of 1,3-dihydro-2H-benzimidazol-2-one-5-sulfonic acid (II)

67 g (0.5 mol) of 1,3-dihydro-2H-benzimidazol-2-one (I) was dissolved in 100 ml of concentrated sulfuric acid at room temperature, and then stirred at 100 ° C. for about 7 hours. The reaction was cooled to room temperature and slowly added to iced water, and then neutralized to pH 6.0 with 50% caustic soda solution. The resulting crystals were filtered off, washed with acetone and dried to give 96 g (90% theoretical yield) of 1,3-dihydro-2H-benzimidazol-2-one-5-sulfonic acid (II).

M.P: 260 ~ 270 ℃

NMR (DMSO-d ₆ ): Phenyl ring 4H (δ7.20, s.), Phenyl ring 6H (δ7.22, d),

Phenyl ring 7H (δ6.82, d)

IR (KBr): 624 (m), 1092 (m), 1174 (s), 1216 (m), 1702 (s), 3192 (m), 3410 (m)

Example 2

Preparation of 1,3-dihydro-1,3-diacetyl-2H-benzimidazol-2-one-5-sulfonic acid (III)

107 g (0.5 mol) of sulfonic acid obtained in Example 1 was suspended in 1 L of acetic anhydride, and 2 g of dimethylaminopyridine was added, followed by heating at 95 to 100 ° C. for 24 hours. After the reaction, the reaction product was cooled to room temperature, the resulting crystals were filtered off, washed with ether and dried to obtain 1,3-dihydro-1,3-diacetyl-2H-benzimidazol-2-one-5-sulfonic acid (III ) 111 g (92% theoretical yield).

M.P:〉 280 ℃

NMR: Phenyl ring 4H (δ8.62, s), Phenyl ring 5H (δ8.24, d),

Phenyl ring 6H (δ7.75, d), N-acetyl group (δ2.79, s)

IR (KBr): 652 (s), 1036 (m), 1168 (m), 1226 (m), 1330 (s), 1740 (s), 1780 (m)

Example 3

Bleaching ability evaluation of 1,3-dihydro-1,3-diacetyl-2H-benzimidazol-2-one-5-sulfonic acid (III) -containing detergent

In order to measure the performance of the compound (III) of the present invention as a bleaching activator, a primary contaminant cloth mainly used in the bleaching ability evaluation test was used.

The amount of perborate compound to compound of Example 2 was 2: 8.

This experiment was carried out at 25 ℃ and 15 ℃, respectively, after washing for 30 minutes with a tagotometer, the wash was measured with a white scale. The results of this evaluation experiment are shown in Table 1 below.

Table 1

Experimental Example Furtherance Before washing (%) After washing (%) white sale(%) % Cleaning rate 15 ℃ 25 ℃ 15 ℃ 25 ℃ One Basic detergent (92% by weight) + sodium perborate (8% by weight) 77.26 79.08 80.12 94.58 10.5 16.5 2 Basic detergent (90% by weight) + sodium perborate (8% by weight) + compound of Example 2 (2% by weight) 77.26 81.51 82.79 94.58 24.56 31.9 3 Basic Detergent (90% by weight) + Sodium Perborate (8% by weight) + Compound IV (2% by weight) 77.26 79.40 81.02 94.58 12.40 21.7

* Basic detergent = Sodium alkylbenzenesulfonate (34.3 wt%) + Fatty alcohol ethoxylate (7EQ) (5.9 wt%) + Sodium fatty acid (2.0 wt%) + Silicone antifoaming agent (5.0 wt%) + Zeolite 4A ( 25.0 weight%) + sodium carbonate (13.7 weight%) + acrylic acid / maleic acid copolymer (4.0 weight%) + sodium silicate (2.6 weight%) + carboxymethyl cellulose rose (1.0 weight%) + water (6.5 weight%) )

* The basic detergent is already spray-dried. Sodium perborate and bleach activator were uniformly mixed to measure the bleaching ability.

As can be seen in Table 1, the bleach detergent (Experimental Example 2) using the bleach activator of the present invention showed a significantly higher washing rate than the conventional bleach detergent (Experimental Example 1 and Experimental Example 3).

Example 4

Granule Bleach Composition

TABLE 2

ingredient A B C D (% by weight) Compound of Example 2 Sodium percarbonate Sodium perborate Monohydrate Sodium perborate Tetrahydrate Tetraacetylethylenediaminenonanoyloxybenzenesulfonate Sodium chloride Alkylbenzenesulfonate Alkyl ethoxylate (7EO) Zeolite sodium silicate Trisodium citrate Acrylic Acid / Maleic Acid Copolymer Sodium Polyacrylate Carboxymethyl Cellulose Prothiazeliporease Sodium Carbonate Water 5 2 10 70 10 5 020 0 10 200 2 0 00 0 0 30 1 3 05 0 19 125 5 1 420 10 7 240 0 10 05 5 2 34 0 4 00 3 0 30.5 0 0.3 01.4 0.3 1.5 0.30.4 0 0 017 14 20 20Total 100 100 100 100

* The composition is prepared by known techniques.

Example 5

Liquid bleach composition

TABLE 3

ingredient A B (% by weight) Compound of Example 2 Hydrogen Peroxide Laurylsulfonate Ethoxylated Alkylsulfonate Lauryl Dimethylamine-N-Oxoxide Citric Acid Abrasive Hydrochloride 6.0 5.010.0 10.05.0 5.01.5 1.51.0 1.05.5 6.015.0 0pH 4.0 Total 100 100

* The composition is prepared by known techniques.

Example 6

Stability test

In order to confirm the stability of the bleach activator over time, the bleach activator of the present invention (compound (III) of Example 2) and the comparative substance contained in the granular detergent composition as in Example 4 over about 3 months ( Ⅳ) Each perhydrolysis was calculated and the change of content was observed. The results are shown in Table 4.

Table 4

time Ⅲ Content (%) Ⅵ content (%) first 100 100 15th 98 98 30 days 95 95 60 days 90 87 90 days 85 80

* 25 ℃, relative humidity 75%

As can be seen in Table 4, the long-term stability of the bleach activator of the present invention was superior to that of the comparative material (IV).

The bleach detergent composition containing the novel bleach activator according to the present invention has excellent bleaching ability even at room temperature or at a low temperature of 15 to 25 ° C., so that it does not damage fabrics or colors and is not easily erased during washing, eg, For example, it has the effect of removing stains and stains caused by coffee and tea, and also has good stability.

Claims (3)

A benzimidazolinone compound having a bleaching activation performance represented by the following general formula. Where R ₁ and R ₂ are acetyl, benzoyl, propionyl, pentanoyl, hexanoyl, or nonanoyl, respectively. A compound according to claim 1, which is 1,3-dihydro-1,3-diacetyl-2H-benzimidazol-2-one-5-sulfonic acid. A bleach detergent composition comprising 0.1 to 30% by weight of the compound according to claim 1 as a bleach activating material.