JPH05271696A - Activator for oxygen bleaching agent, and bleaching agent composition - Google Patents

Abstract

PURPOSE:To provide an activator which gives good bleaching effects even at a low temp. in a short time. CONSTITUTION:This activator contains as the effective component an acetylated or propionylated polyoxy carboxylic acid obtd. by oxidizing a monosaccharide and represented by the formula: XO-[CH(OX)]n-COOY, wherein (n) is an integer of 4-6; X is acetyl, propionyl, or H provided that, on the average, at least 3 of X's are acetyl or propionyl; and Y is H, acetyl, propionyl, alkali metal, alkaline earth metal, ammonium, substd. ammonium, or a mixture of these groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activator for an oxygen-based bleaching agent (hereinafter simply referred to as "activator") and a bleaching agent composition. In particular, the invention is suitable for bleaching fibers at a low temperature and in a good working environment.

[0002]

2. Description of the Related Art In recent years, as a bleaching agent for fibers, an oxygen bleaching agent has been widely used in place of a chlorine bleaching agent (for example, sodium hypochlorite). This is because the chlorine-based bleaching agent has a peculiar irritating odor and is not desirable in the working environment, and there are problems that the usable fibers are limited and that it cannot be used for colored patterns.

The active ingredient of this oxygen-based bleaching agent is a peroxo acid salt such as sodium peroxoborate or sodium peroxocarbonate.

However, these oxygen-based bleaching agents, when used alone at a high temperature of 80 ° C. or more, exhibit a high bleaching effect comparable to that of a chlorine-based bleaching agent, but at a low temperature of 40 ° C. or less, a chlorine-based bleaching agent is used. Less bleaching power than bleach.

Therefore, a sugar sugar and a sugar derivative (polyhydric alcohol) obtained by acylating (mainly acetylating) hydroxyl groups, that is, an ester compound as an activator, is used as an oxygen bleaching agent and further as a surface active agent. It has been proposed to use it in combination with an agent (Japanese Patent Publication No. 54-23364 / 54-2387).
No. 0, JP-A-55-34217, JP-A-59-309.
00).

The term "activator" as used herein means an agent which exerts a bleaching effect based on a peroxo acid even at a low temperature and maintains the bleaching effect of the bleaching agent even after long-term storage.

[0007]

However, the above-mentioned conventional activators often fail to obtain a sufficient bleaching effect when washed at low temperature and for a short time (for example, 25 ° C. for 10 minutes). .. The acetylated product as an activator
It is presumed that the water solubility is low as a result of acetylating all the hydroxyl groups in order to enhance the activity effect (see JP-A-49-48580, page 1, lower right column).

In view of the above, the present invention is to provide an activator and a bleach composition for an oxygen-based bleaching agent, which can obtain a good bleaching effect even under conditions of low temperature and short time.

[0009]

The present inventors have made diligent efforts to develop a bleaching activator derived from a sugar raw material which does not have these problems, and as a result, polyoxyoxysaccharide obtained by oxidizing a monosaccharide is obtained. The inventors have found that acetylated compounds and propionylated compounds of carboxylic acids have high bleaching activation effect, and completed the present invention having the following constitution.

(1) The activator according to claim 1 is characterized in that a derivative of polyhydroxycarboxylic acid represented by the following general formula is used as an active ingredient.

XO- [CH (OX)] _n- COOY ... {In the formula, n is an integer of 4 to 6, X is an acetyl group, a propionyl group or H, and at least three Xs are on average. An acetyl group or a propionyl group; Y
Represents H, an acetyl group, a propionyl group, an alkali metal, an alkaline earth metal, ammonium, or a substituted ammonium, or a mixture thereof. (2) The bleaching composition according to claim 3 is characterized in that the activator according to claim 1 and an oxygen-based bleaching agent are essential components.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. In addition, in the following description, “part” indicating a mixing unit means “part by weight” unless otherwise specified.

A. The compound represented by the above general formula as an active ingredient of the active agent used in the present invention will be explained in detail.

(1) In the general formula, n = an integer of 4 to 6, preferably n = 5. Hydroxycarboxylic acids outside this range are difficult to obtain.

As the precursor of the acetylated product, the following can be used as the polyhydroxycarboxylic acid. Among these, hexonic acid, particularly gluconic acid, is preferable from the viewpoints of price, availability and the like.

(I) Pentonic acid (pentose aldonic acid, n = 5) ... Ribonic acid, arabonic acid, xylonic acid, lyxonic acid, sugar.

(Ii) Hexonic acid (hexanoic aldonic acid, n = 6) ... Gluconic acid, mannonic acid, galactonic acid, taronic acid, gulonic acid, idonic acid, alloic acid, altronic acid, etc.

(Iii) Heptonic acid (aldonic acid of heptose, n = 7) ... Glucoheptonic acid, mannoheptonic acid,
Galaheptonic acid, etc.

(2) In the above general formula, X is an acetyl group, a propionyl group or H, and at least three Xs are an acetyl group or a propionyl group on average. Preferably, four X's on average are acetyl groups or propionyl groups, and more preferably all X's are acetyl groups or propionyl groups.

With an acyl group other than those mentioned above, that is, with a formyl group having a small number of carbon atoms, for example, esterification is not easy. Further, for example, a butyryl group having a large number of carbon atoms has a weak bleaching activation effect, and further, an aromatic benzoyl group is difficult to obtain a sufficient bleaching activation effect.

If the average of three hydroxyl groups is not acylated, it is difficult to obtain the active effect.

(3) In the above general formula, Y is H, acetyl group, propionyl group, sodium, potassium, ammonium, substituted ammonium or a mixture thereof. Preferably, Y is H, an acetyl group, sodium,
Potassium or a mixture thereof, more preferably Y
Is H, an acetyl group, sodium or a mixture thereof.

(4) Such a polyoxycarboxylic acid acetylated compound (organic peracid precursor) as an active ingredient of the activator often has a syrup shape at room temperature.
It can be easily pulverized by mixing with a carrier such as 10 to 30 parts of silicic acid anhydride relative to 0 parts. When Y is an alkali metal salt such as sodium or potassium, the compound is generally a solid that can be easily powdered, is convenient from the viewpoint of handling, and can be used in a desirable mode by selecting Y.

B. The above-mentioned activator is usually used in combination with an oxygen-based bleaching agent to prepare a bleaching agent composition containing these as essential components.

The oxygen-based bleaching agent releases or produces hydrogen peroxide in an aqueous solution and has the function of converting the acetylated product into an organic peracid.

The compounding amount of the above-mentioned activator with respect to 100 parts of the peroxo acid salt which is the active ingredient of this oxygen-based bleaching agent is 1
To 200 parts, preferably 5 to 100 parts. Even if the amount of activator exceeds the range, the bleaching activity effect is uneconomical because it is saturated, and conversely if it is too small, it is difficult to obtain a sufficient bleaching activity effect.

As the peroxo acid salt, sodium peroxoborate, sodium peroxocarbonate, peroxooxidized urea, sodium peroxopyrophosphate, sodium peroxosulfate / sodium chloride double salt can be used. In particular, sodium peroxocarbonate is preferable from the viewpoints of stability, low temperature solubility and the like.

C. The bleaching agent composition may be further mixed with the following various surfactants (desirably nonionic) to prepare a detergent composition.

(A) Nonionic surfactant: alkyl polyoxyethylene ether, alkylphenyl polyoxyethylene ether, fatty acid sucrose ester, higher fatty acid alkanolamide, alkylamine oxide, alkyl glycoside, etc.

(B) Anionic surfactant: alkylbenzene sulfonate, alkyl or alkenyl sulfate, alkyl or alkenyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, fatty acid salt, etc. ..

(C) Cationic surface active agent: alkyltrimethylammonium salt, alkyldimethylbenzylammonium salt, etc. (d) Amphoteric surface active agent: N-alkylbetaine type or sulfobetaine type.

The detergent composition may also contain components added for the purpose of enhancing or supplementing the performance of conventional detergent compositions.

Examples of such components include detergent builders typified by sodium tripolyphosphate, sodium nitrilotriacetate and zeolite; buffers such as sodium carbonate, sodium bicarbonate, sodium borate, sodium silicate; sodium sulfate; Inorganic electrolyte such as sodium chloride;
Other anti-contamination agents such as carboxymethyl cellulose;
Examples include enzymes such as protease, lipase, amylase, and cellulase; fluorescent dyes; fragrances; dyes, etc., but these are not particularly limited and may be appropriately mixed depending on the purpose.

[0034]

The activator and bleaching composition for oxygen-based bleaching agents of the present invention contain, as an activator, an acetylated product or a propionylated product of polyoxycarboxylic acid obtained by oxidizing a monosaccharide. By doing so, a good bleaching activation effect can be obtained even at a low temperature for a short time, as shown in Examples described later.

[0035]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(1) Preparation of Activator <Example 1> 109 g (0.5 mol) of sodium gluconate crushed in a 1000 ml three-neck round bottom flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. Acetic anhydride 3
06 g (3 mol) was added, and the mixture was heated to 40 ° C. with a mantle heater while stirring. Acetyl chloride 3 from the dropping funnel
9.3 g (0.5 mol) was added dropwise over 30 minutes, the reaction temperature was kept at 40 ° C during this, and the reaction was continued for 2 hours at the same temperature. Next, the reaction temperature was gradually raised to 100 ° C., and the reaction was continued for 5 hours at 100 to 110 ° C. After cooling to room temperature, the insoluble matter was filtered off with suction, and the filtrate was removed by evaporation under reduced pressure to obtain 190 g of an acetylated product of gluconic acid. After dissolving 10 g of this product in an appropriate amount of ethanol, it was uniformly mixed with 5 g of silicic acid (Katayama Chemical Co., Ltd.) and ethanol was removed to obtain a powdery material.

<Example 2> 109 g (0.5 mol) of sodium gluconate and 4 parts of acetic anhydride were placed in the same apparatus as in Example 1.
08 g (4 mol) was added, and the mixture was heated to 55 ° C. with a mantle heater while stirring. Acetyl chloride 39.3 g (0.
5 mol) was added dropwise over 40 minutes, during which the reaction temperature was adjusted to 55-6.
The temperature was maintained at 0 ° C., and the reaction was continued at the same temperature for 2 hours. Then, in the same manner as in Example 1, 198 g of a product was obtained. Further, a powdery material was obtained in the same manner as in Example 1.

<Example 3> In the same apparatus as in Example 1, 109 g (0.5 mol) of sodium gluconate and 5 parts of acetic anhydride were added.
10 g (5 mol) was added, and the mixture was heated to 50 ° C while stirring. 35.4 g of 50 wt% sulfuric acid was gradually added to this suspension, and the temperature was kept at 50 to 55 ° C during this period. Thereafter, the reaction temperature was slowly raised to 100 ° C., the reaction was carried out at the same temperature for 4 hours, and then cooled to room temperature. After adding an appropriate amount of ethanol to decompose unreacted acetic anhydride, the insoluble matter was filtered off with suction, the filtrate was concentrated with an evaporator, and then the volatile matter was removed in a vacuum dryer to obtain 177 g of a product. Further, a powdery material was obtained in the same manner as in Example 1.

<Example 4> Product 5 prepared in Example 3
0 g was dissolved in 100 ml of a 70 vol% ethanol aqueous solution and neutralized with 2N sodium hydroxide until a pale red color was obtained with respect to phenolphthalein. Ethanol and water were removed by evaporation with an evaporator and then dried in a vacuum drier to obtain 52 g of a product. The product was obtained as a solid.

<Example 5> 109 g (0.5 mol) of sodium gluconate and 540 g (4 mol) of propionic anhydride were placed in the same apparatus as in Example 1 and stirred at 55 ° C.
Warmed to. 46.3 g of propionyl chloride was added to this suspension.
Was gradually added, and the temperature was kept at 55 to 60 ° C during this period. After reacting at the same temperature for 2 hours, the reaction temperature was 100 ° C. for 10 hours. After cooling to room temperature, an appropriate amount of ethanol was added to decompose unreacted propionic anhydride. After the insoluble matter was filtered off with suction, the furnace liquid was concentrated with an evaporator and the volatile matter was further removed in a vacuum dryer to obtain 208 g of a product. Further, a powdery material was obtained in the same manner as in Example 1.

(2) Analysis Results Table 1 shows the results of analysis of the activators prepared in Examples 1 to 5 by measuring the saponification value and the hydroxyl value. In the table, n, X and Y are numerical values or groups in the above general formula. Moreover, the analysis value shows the value before mixing with silicic acid.

(3) Bleach test Sodium peroxocarbonate 0.2 was added to 500 ml of tap water.
A mixture of 5 g and a bleach activator 0.1 g (weight excluding silicic acid content) was added, and after stirring for 2 minutes, 5 pieces of 5 cm × 5 cm black tea-contaminated cloth were dipped and loosened at 25 ° C. for 10 minutes. Bleached with stirring. The bleached cloth was washed with water, air-dried and then ironed, and then the reflectance at 550 nm was measured, and the bleaching rate was calculated according to the following formula.

Bleaching rate (%) = (reflectance after bleaching-reflecting rate before bleaching) × 100 / (reflecting rate of white cloth before stain-reflecting rate before bleaching) Comparative Examples 1 and 2 are bleaching activities. Pentaacetyl glucose (PAG) and octaacetyl sucrose (OAS) were used as the agent.

From Table 1 showing the bleaching test results, it can be seen that the activator of each Example of the present invention exhibits a good bleaching agent effect.

[0045]

[Table 1]

Claims (2)

[Claims] 1. An activator for a peroxo acid bleaching agent, which comprises a derivative of polyhydroxycarboxylic acid represented by the following general formula as an active ingredient. XO- [CH (OX)] _n- COOY ... (In the Formula, n is an integer of 4-6, X is an acetyl group, a propionyl group, or H, and at least 3 X is an acetyl group or Is a propionyl group; Y
Represents H, an acetyl group, a propionyl group, an alkali metal, an alkaline earth metal, ammonium, or a substituted ammonium, or a mixture thereof. } 2. A bleaching composition comprising the activator according to claim 1 and an oxygen-based bleaching agent as essential components.