JPH08170097A - Bleaching agent composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition having high bleaching force and excellent decolor-inhibiting effect without inducing decoloring of colored or patterned materials by mixing a specific organic peroxyacid precursor salt into an oxygen-based peroxide. CONSTITUTION: This composition contains (A) an oxygen-based peroxide (e.g. hydrogen peroxide) and (B) an organic peroxyacid precursor salt composed of an anion-containing organic peroxyacid precursor anion and an alkaline earth metallic ion [preferably a salt of the formula (R is a 1-18C alkyl or alkenyl, etc.; X<-> is SO3 <-> or COO<-> ; M<2+> is Ca<2+> or Mg<2+> )]. Mixing amount of the component A is preferably 1-90wt.% of the whole composition. The component B is preferably mixed in a ratio of 0.005-0.5mol based on mol of hydrogen peroxide generating from the component A and to be 0.5-60wt.% in the composition. The molar ratio of the organic peroxyacid precursor anion to the alkaline earth metallic ion in the component B is preferably 0.1-1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching agent composition or a bleaching detergent composition which has a high bleaching power and does not cause decolorization of colors and patterns.

[0002]

2. Description of the Related Art Sodium percarbonate and sodium perborate are mainly used as bleaching bases in bleaching agents and bleaching detergents. However, since sufficient bleaching performance cannot be obtained with these bases alone, organic peracid precursors such as TAED (tetraacetylethylenediamine) and AOBS (sodium alkanoyloxybenzenesulfonate) have come to be used in combination. . These organic peracid precursors react with hydrogen peroxide generated from peroxides such as sodium percarbonate to form organic peracids with strong bleaching power, which is effective for bleaching clothes, but especially for pickling. There is a problem that decolorization of the color / pattern is likely to occur when bleaching is carried out.

As means for solving these problems,
There is a method using an aminocarboxylic acid described in Japanese Patent Publication No. 56-21799 and a method using an amino acid described in Japanese Patent Publication No. 57-30188, but when the oxygen peroxide is used alone, it is effective. However, it is not sufficient when the organic peracid precursor is used in combination.

[0004]

Means for Solving the Problems As a result of earnest studies for achieving the above object, the present inventors have found that excellent decolorization is achieved by using an alkaline earth metal salt of an organic peracid precursor having an anion group. The present invention has been completed with the finding that a preventive effect can be obtained.

That is, the present invention comprises: (a) an oxygen-based peroxide; (b) an organic peracid precursor anion having an anion group;
It is intended to provide a bleaching detergent composition characterized by containing an organic peracid precursor salt composed of an alkaline earth metal ion.

As the component (a) of the present invention, hydrogen peroxide or sodium percarbonate, sodium perborate, sodium sulfate / salt / hydrogen peroxide adduct, inorganic peroxide such as potassium monopersulfate, etc. are used. The blending amount is 1 to 90% by weight based on the whole bleaching detergent composition.

The organic peracid precursor salt of the component (b) of the present invention is added to the composition in a molar ratio of 0.001 to 0.7 mol with respect to hydrogen peroxide generated from the oxygen-based peroxide of the component (a). It is preferably compounded, and 0.005 to 0.5 mol is particularly preferable. The organic peracid precursor salt as the component (b) is preferably blended in the composition in an amount of 0.3 to 80% by weight, more preferably 0.5 to 60% by weight. The component (b) is composed of an organic peracid precursor anion having an anion group and an alkaline earth metal ion, but the organic peracid precursor anion and the alkaline earth metal ion are not necessarily equal in neutralization amount. Although not required to be present, the molar ratio of alkaline earth metal ion to organic peracid precursor anion is preferably 0.05 to 1.5, more preferably 0.1 to 1.0. This molar ratio is
If it is less than 0.05, there is no anti-bleaching property, while if it exceeds 1.5, the bleaching effect is reduced.

As the alkaline earth metal ion forming the component (b), calcium ion and magnesium ion are particularly preferable, and among them, the organic peracid precursor anion represented by the following general formula (I) and calcium ion or magnesium ion. It is preferable to use one or two kinds of salts selected from the above salts.

[0009]

Embedded image

(Wherein R is a carbon number of 1 to 18, preferably 7)
~ 12 alkyl or alkenyl groups, total carbon number 3 ~
20 alkanoyloxymethylene groups or phenyl groups,
X ⁻ represents a SO ₃ ⁻ group or COO ⁻ group, and M ²⁺ represents Ca ²⁺ or Mg ²⁺ . The component (b) of the organic peracid precursor salt may be granulated with a binder substance and mixed. As the binder substance, one having a binding property by being solidified at about 40 ° C. or lower is used. For example, a nonionic surfactant such as an ethylene oxide and / or propylene oxide adduct of an alcohol or a fatty acid having 8 to 18 carbon atoms, an average Molecular weight 2000-30000
Polyethylene glycol, saturated or unsaturated fatty acids having 8 to 18 carbon atoms such as succinic acid and dibasic acid such as glutaric acid are used, and these may be used alone or in a mixture.

The binder material is based on the precursor mixture.
It is preferable to use 0.05 to 4 times the amount (weight ratio),
Particularly preferably, the amount is 0.07 to 3 times. Further, in the case of granulation, an inorganic salt such as Glauber's salt can be added for the purpose of improving granulation and the like.

Since the organic peracid precursor salt is slightly insoluble in water, it produces an organic peracid at an appropriate rate and does not generate a high concentration of organic peracid on the color / patterned fiber. In order not to cause fading, the effect is exhibited by making the organic peracid precursor a salt with an alkaline earth metal. Further, the bleaching detergent composition and method of the present invention are characterized by using the above components.

The composition of the present invention may be in the form of liquid or powder, but in the case of liquid, an aqueous solution of hydrogen peroxide is used as the component (a), and the component (b) is added thereto, and if necessary, added. Then, a stabilizer, a surfactant, etc. may be added. The composition obtained by adding the component (b) to the aqueous hydrogen peroxide solution is also very excellent in the storage stability of the organic peracid precursor.

The bleaching composition of the present invention is obtained by mixing an organic peracid precursor salt and an oxygen-based peroxide, and if necessary, other optional components such as an enzyme and sodium carbonate. Inorganic salts, surfactants, fluorescent agents and the like can also be added. In particular, it is suitable for blending a surfactant to obtain a bleaching detergent composition. Specific examples of the optional components are shown below.

[B] Surfactant The composition of the present invention may contain a surfactant such as an anionic surfactant or a nonionic surfactant.

As the anionic surfactant, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate ester salt, α
-Olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, N-acyl amino acid type surfactant, alkyl or alkenyl ether carboxylic acid salt, amino acid type surfactant, alkyl or alkenyl phosphate ester or salt thereof Etc. are illustrated.

The nonionic surfactant may be, for example, polyoxyalkylene alkyl (or alkenyl).
Examples thereof include ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, fatty acid glycerin monoesters and the like. Of these, the following nonionic surfactants (1) to (3) are particularly preferable.

(1) A polyoxyethylene alkyl ether having an alkyl group having an average carbon number of 10 to 20 and having 1 to 30 mol of ethylene oxide added thereto. (2) A polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 9 to 12 and having 1 to 25 mol of ethylene oxide added thereto. (3) An alkyl glycoside represented by the following general formula (1). _{R '(OC 2 H 4)} p G q (1) ( wherein, R' is an alkyl group having 9 to 14 carbon atoms, p is the number of 0 to 2, G is glucose, fructose, maltose or sucrose residue, q is a number of 1 to 4, preferably 1, 2 or 3.) The amount of the anionic surfactant and nonionic surfactant blended is preferably 1 to 60% by weight in the entire composition.

In addition to the composition of the present invention, a betaine type amphoteric surfactant, a sulfonic acid type amphoteric surfactant, a phosphate ester type surfactant, a cationic surfactant and the like may be added.

(B) Builder The composition of the present invention may contain the following washing builder which can be generally added to a detergent or a bleaching agent.

[1] Divalent metal ion scavenger One or more builder components of the following various alkali metal salts and alkanolamine salts can be blended in an amount of 0 to 50% by weight. (1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate. (2) ethane-1,1-diphosphonate, ethane-1,
1,2-triphosphonate, ethane-1-hydroxy-
1,1-diphosphonate and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-
Salts of phosphonic acids such as dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid. (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Salts of phosphonocarboxylic acids such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid. (4) Amino acid salts such as aspartic acid, glutamic acid and glycine. (5) Aminopolyacetates such as nitrilotriacetic acid salts, iminodiacetic acid salts, ethylenediaminetetraacetic acid salts, diethylenetriaminepentaacetic acid salts, glycol etherdiaminetetraacetic acid salts, hydroxyethyliminodiacetic acid salts, triethylenetetramine hexaacetic acid salts and dienecoric acid salts. (6) Polymer electrolytes such as polyacrylic acid, acrylic acid / maleic acid copolymer, polyfumaric acid, polymaleic acid, poly-α-hydroxyacrylic acid, polyacetalcarboxylic acid or salts thereof. (7) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethyl tartaric acid,
Organic carboxylic acid salts such as carboxymethyl succinic acid.

[2] Alkaline Agent or Inorganic Electrolyte Alkali metal salts are preferable as salts such as silicates, carbonates and sulfates. [3] Anti-redeposition agent Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. [4] Enzyme Protease, lipase, amylase, cellulase and the like.
Particularly, it is preferable to add 0.1 to 5% by weight of the protease in the composition. [5] Peroxide Stabilizer Magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium fluorosilicate, magnesium oxide and magnesium hydroxide, and boric acid or salts thereof. [6] Perfume, fluorescent dye, pigment.

Further, a method of incorporating the above organic peracid precursor salt into a bleaching detergent is generally used, but it may be formed in a bleaching bath. For that purpose, for example, before adding hydrogen peroxide or a chelating agent, the sodium salt of the organic peracid precursor of a known substance is dissolved in tap water in advance, and the calcium salt is sufficiently reacted with the hardness component in tap water. The effect of the present invention can be obtained by adding hydrogen peroxide, a chelating agent, a surfactant, etc. after the formation.

[0024]

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

Example 1 Using the organic peracid precursor salt shown in Table 1 and a comparative organic peracid precursor, bleaching agent compositions or bleaching detergent compositions shown in Tables 2 to 5 were prepared. The performance was evaluated by the method.

[0026]

[Table 1]

(1) Method for measuring bleaching cleaning rate <Preparation of bilirubin-contaminated cloth> Bilirubin (C ₃₃
The H ₃₆ N ₄ O _6, MERK Co.) 0.061 g dissolved in chloroform 100 cc. 0.4 ml of this solution was dropped on a piece of 10 cm × 10 cm cotton cloth # 2003, and naturally dried to obtain a bilirubin-contaminated cloth.

Bleaching Rate Measurement of Powder Bleaching Composition (Table 2) 1.5 g of the bleaching agent composition shown in Table 2 was dissolved in 300 ml of tap water, and a contaminated cloth was soaked at 20 ° C. for 30 minutes. After rinsing with tap water and dehydration, press drying was carried out, and the bleaching washing rate was calculated by the following method. The reflectance of the original cloth and the contaminated cloth before and after washing was measured with "NDR-101DP" manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter, and the bleaching washing rate was calculated using the following formula. Was evaluated.

[0029]

[Equation 1]

Bleaching Rate Measurement of Liquid Bleaching Composition (Table 3) 6.0 g of the liquid bleaching agent composition shown in Table 3 and 1.0 g of a commercial detergent (“Attack” Kao Co., Ltd., registered trademark) were used.
It was dissolved in 300 ml of tap water, and the contaminated cloth was soaked at 20 ° C. for 30 minutes, rinsed with tap water, dehydrated and press-dried, and the bleaching washing rate was calculated by the same method as above.

Bleaching Detergent Composition (Tables 4 and 5) Bleaching Rate Measurement The bleaching detergent composition shown in Tables 4 and 5 is a set of 4 pieces of each contaminated cloth obtained above under one condition. Wash with. The cleaning conditions at this time are as follows. Washing temperature: 20 ° C Bath ratio: 1/60 Detergent concentration: 0.0833% by weight (using tap water) Targotometer 10 minutes (rotation speed 100 rpm) After washing, rinse with tap water, dehydrate, and press-dry. The bleaching and washing ratio was obtained by calculating the average of four sheets.

(2) Evaluation of fading property Sprinkling method (composition of Table 2) 4.5 cm × 4.5 cm R on a petri dish having a diameter of 7 cm and a depth of 1.5 cm.
Place an eactive Red-21 dyed cloth and pour 10 ml of tap water at 40 ° C to moisten it sufficiently. Next, 5 g of the bleaching agent composition shown in Table 2 is sprinkled and left for 30 minutes. Then, the dyed cloth obtained by thoroughly washing with water and air-drying was visually judged at the following evaluation points. <Evaluation score of fading degree (sprinkling method)> 1 point: fairly fading is observed 2 points: violent fading is seen 3 points: fading is seen 4 points: slightly fading is seen 5 points: almost fading No cumulative washing method (compositions in Tables 3, 4 and 5) 40 cm x 30 cm cotton base cloth, 3 sewn dyeing test cloths same as the above method were sewn, and each bleaching detergent composition shown in Tables 4 and 5 twenty five
g into a washing machine filled with 30 liters of tap water, then put a sewn cloth on the base cloth, wash at 20 ° C for 10 minutes, dehydrate, rinse with running water for 5 minutes, 3 After dehydration for a minute, the base cloth was air-dried. Repeat this process 10 times,
Commercial detergent ("Attack" Kao Corporation, registered trademark) 25
It was evaluated by using the following evaluation points in comparison with the same 10 times cumulative washing in g.

Regarding the liquid bleaching agents shown in Table 3, 40 ml of the liquid bleaching agent was added to 30 liters of washing water at the same time as 25 g of the commercial detergent, and the above washing was carried out. It was repeated 10 times and evaluated according to the following criteria. <Evaluation score of fading degree (cumulative washing method)> 1 point: considerably fading is observed as compared with the commercially available detergent 2 points: Violent fading is observed as compared with the commercially available detergent 3 points: Commercial detergent K In comparison, fading is observed 4 points: Slightly fading compared to commercial detergents 5 points: Almost no fading compared to commercial detergents (3) Storage stability of liquid bleach Evaluation (Composition of Table 3) The composition shown in Table 3 was placed in a plastic container (volume: 50 ml).
It is filled with ml and stored at 40 ° C for 2 weeks. Before and after storage, the concentration of the organic peracid precursor is measured by high performance liquid chromatography.
The residual rate was calculated by the following formula.

[0034]

[Equation 2]

(4) Tables 2 to 5 show the evaluation results obtained by the above (1) to (3).

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C11D 17/08 D06L 3/02

Claims (7)

[Claims] 1. A bleaching method comprising: (a) an oxygen-based peroxide; and (b) an organic peracid precursor salt composed of an organic peracid precursor anion having an anion group and an alkaline earth metal ion. Agent composition. 2. The organic peracid precursor salt of the component (b),
The bleaching according to claim 1, which contains one or two salts selected from salts of an organic peracid precursor anion represented by the following general formula (I) and calcium ion or magnesium ion. Agent composition. Embedded image (Wherein, R represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, alkanoyloxy methylene group or a phenyl group having a total carbon number of 3 to 20, X ^- is SO ₃ ^- group or COO ^- groups, M
²⁺ represents Ca ²⁺ or Mg ²⁺ . ) 3. The molar ratio of the alkaline earth metal ion to the organic peracid precursor anion is 0.05 to 1.5.
Or the bleaching composition according to item 2. 4. The bleaching composition according to claim 1, which is in a liquid form. 5. A bleaching characterized by using an organic peracid precursor salt consisting of (a) an oxygen-based peroxide (b) an organic peracid precursor anion having an anion group and an alkaline earth metal ion. Cleaning method. 6. The organic peracid precursor salt of the component (b) is one or two selected from salts of an organic peracid precursor anion represented by the general formula (I) and calcium ion or magnesium ion. 6. The bleaching and washing method according to claim 5, wherein the salt is a salt of Embedded image (Wherein, R represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, alkanoyloxy methylene group or a phenyl group having a total carbon number of 3 to 20, X ^- is SO ₃ ^- group or COO ^- groups, M
²⁺ represents Ca ²⁺ or Mg ²⁺ . ) 7. The molar ratio of the alkaline earth metal ion to the organic peracid precursor anion is 0.05 to 1.5.
Or the bleaching washing method described in 6 above.