JP3330244B2 - Bleach composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Currently, sodium percarbonate and sodium perborate are mainly used as bleaching agents 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 produce organic peracids with strong bleaching power, which is effective in bleaching clothing, but is especially effective in pickling. When performing bleaching, there is a problem that the color and the pattern are easily decolorized.

[0003] Means for solving these problems include:
There are a method using an aminocarboxylic acid described in JP-B-56-21799 and a method using an amino acid described in JP-B-57-30188. However, when an organic peracid precursor is used in combination, it is not sufficient.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that the use of an alkaline earth metal salt of an organic peracid precursor having an anionic group provides excellent decolorization. The present inventors have found that a preventive effect can be obtained and completed the present invention.

That is, the present invention provides: (a) an oxygen-based peroxide; (b) an organic peracid precursor anion having an anion group;
There is provided a bleached composition characterized by containing an organic peracid precursor salt comprising an alkaline earth metal ion.

[0006] As the component (a) of the present invention, an inorganic peroxide selected from sodium percarbonate and sodium perborate are used, the amount thereof 1 overall bleached composition
90% by weight.

The organic peracid precursor salt of the component (b) of the present invention is contained in 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 preferable to mix them, and the amount is particularly preferably 0.005 to 0.5 mol. The organic peracid precursor salt of the component (b) is preferably incorporated 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, and the organic peracid precursor anion and the alkaline earth metal ion are not necessarily neutralized in equivalent amounts. It need not be present, but the molar ratio of alkaline earth metal ion to organic peracid precursor anion is preferably from 0.05 to 1.5, more preferably from 0.1 to 1.0. This molar ratio is
If it is less than 0.05, there is no decolorization preventing property, while if it exceeds 1.5, the bleaching effect is reduced.

As the alkaline earth metal ion forming the component (b), a calcium ion and a magnesium ion are particularly preferable. Among them, an 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 following salts.

[0009]

Embedded image

(Wherein R represents 1 to 18 carbon atoms, preferably 7 carbon atoms)
~ 12 alkyl or alkenyl groups, total carbon number 3 ~
20 alkanoyloxymethylene groups or phenyl groups,
X ^- represents a SO ₃ ^- group or a COO ^- group, and M ²⁺ represents Ca ²⁺ or Mg ²⁺ . The organic peracid precursor salt of the component (b) may be granulated with a binder substance and blended. As the binder substance, those having a binding property by solidifying at about 40 ° C. or less are used. For example, nonionic surfactants such as ethylene oxide and / or propylene oxide adducts of alcohols or fatty acids having 8 to 18 carbon atoms, Molecular weight 2000-30000
And a dibasic acid such as a saturated or unsaturated fatty acid having 8 to 18 carbon atoms, such as succinic acid and glutaric acid, which may be used alone or in combination.

[0011] The binder material is based on the precursor mixture.
It is preferable to use 0.05 to 4 times (weight ratio),
Particularly preferably, the amount is 0.07 to 3 times. At the time of granulation, an inorganic salt such as sodium sulfate may be added for the purpose of improving granulation.

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

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

The bleach composition of the present invention is obtained by mixing an organic peracid precursor salt and an oxygen-based peroxide, and optionally contains other optional components such as an enzyme and sodium carbonate. An inorganic salt, a surfactant, a fluorescent agent, and the like can be added. In particular, it is suitable for obtaining a bleaching detergent composition by incorporating a surfactant. Specific examples of the optional components are shown below.

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

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α
-Olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, N-acyl amino acid type surfactant, alkyl or alkenyl ether carboxylate, amino acid type surfactant, alkyl or alkenyl phosphate or salt thereof Etc. are exemplified.

Examples of the nonionic surfactant include polyoxyalkylene alkyl (or alkenyl).
Ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoside, fatty acid glycerin monoester, and the like. Among these, the following nonionic surfactants (1) to (3) are particularly preferred.

(1) A polyoxyethylene alkyl ether having an alkyl group having an average of 10 to 20 carbon atoms and having 1 to 30 mol of ethylene oxide added thereto. (2) Polyoxyethylene alkyl phenyl ether having an alkyl group having an average of 9 to 12 carbon atoms 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 a number of 0 to 2, G is a 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 the nonionic surfactant is preferably 1 to 60% by weight in the whole composition.

The composition of the present invention may further contain a betaine-type amphoteric surfactant, a sulfonic acid-type amphoteric surfactant, a phosphate ester-based surfactant, a cationic surfactant, and the like.

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

[1] Divalent metal ion scavenger One or two 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) Salts of amino acids such as aspartic acid, glutamic acid and glycine. (5) Aminopolyacetates such as nitrilotriacetate, iminodiacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetate, and diencholate. (6) Polymer electrolytes such as polyacrylic acid, acrylic acid / maleic acid copolymer, polyfumaric acid, polymaleic acid, poly-α-hydroxyacrylic acid, polyacetal carboxylic acid or salts thereof. (7) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxymethyltartaric acid,
Organic carboxylate such as carboxymethyl succinic acid.

[2] Alkali agents or inorganic electrolytes Alkali metal salts are preferred as salts such as silicates, carbonates and sulfates. [3] Anti-redeposition agent Polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose and the like. [4] Enzymes Protease, lipase, amylase, cellulase and the like.
In particular, it is preferable that the protease contains 0.1 to 5% by weight of the composition. [5] Peroxide stabilizers Magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium hydroxide, and boric acid or salts thereof. [6] Perfumes, fluorescent dyes and pigments.

In general, the above-mentioned organic peracid precursor salt is blended into a bleaching detergent, but it may be formed in a bleaching washing bath. For this purpose, for example, before adding hydrogen peroxide or a chelating agent, in a tap water, a sodium salt of an organic peracid precursor of a known substance is previously dissolved, and sufficiently reacted with a hardness component in the tap water to convert a calcium salt. The effect of the present invention can be obtained by adding hydrogen peroxide, a chelating agent, a surfactant, and the like after generation.

[0024]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

Example 1 Using the organic peracid precursor salt shown in Table 1 and an organic peracid precursor for comparison, bleach compositions or bleach 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 washing 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 is dropped onto one piece of cotton cloth # 2003 of 10 cm × 10 cm and air-dried to obtain a bilirubin-contaminated cloth.

Measurement of bleaching ratio of powder bleaching composition (Table 2) 1.5 g of the bleaching composition shown in Table 2 was dissolved in 300 ml of tap water, and the contaminated cloth was immersed at 20 ° C. for 30 minutes. After dehydration by rinsing with tap water, press drying was performed, and the bleaching washing ratio was calculated by the following method. The reflectance of the original cloth and the contaminated cloth before and after cleaning was measured with Nippon Denshoku Industries Co., Ltd. “NDR-101DP” using a 460 nm filter, and the bleaching cleaning rate was calculated by the following formula, and the bleaching cleaning performance was determined. Was evaluated.

[0029]

(Equation 1)

Measurement of Bleaching Ratio of Liquid Bleach Composition (Table 3) 6.0 g of the liquid bleach composition shown in Table 3 and 1.0 g of a commercially available detergent (registered trademark of “Attack” Kao Corporation) were used.
It was dissolved in 300 ml of tap water, the contaminated cloth was immersed at 20 ° C. for 30 minutes, rinsed with tap water, dehydrated, and then press-dried, and the bleach-washing rate was calculated in the same manner as described above.

Measurement of Bleaching Ratio of Bleach Detergent Compositions (Tables 4 and 5) The bleach detergent compositions shown in Tables 4 and 5 were obtained by setting each of the contaminated cloths obtained above to one set of four sheets 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 (rotational speed: 100 rpm) After washing, rinsing with tap water, dehydrating, and press drying, then the same method as above The bleaching washing rate was determined by the above, and the average of four sheets was calculated.

(2) Evaluation of fading property Sprinkling method (composition of Table 2) A 4.5 cm × 4.5 cm R dish was placed on a petri dish having a diameter of 7 cm and a depth of 1.5 cm.
Place the eactive Red-21 dyed cloth and pour 10 ml of tap water at 40 ° C and moisten it sufficiently. Next, 5 g of the bleaching composition shown in Table 2 is sprinkled and left for 30 minutes. Thereafter, the dyed cloth obtained by sufficiently washing with water and air-drying was visually judged at the following evaluation points. <Evaluation point of fading degree (sprinkling method)> 1 point: fairly severe fading 2 points: severe fading 3 points: fading 4 points: slight fading 5 points: almost fading Not available Cumulative washing method (compositions in Tables 3, 4 and 5) Three pieces of the same dyeing test cloth as in the above method were sewn on a 40 cm x 30 cm cotton base cloth, and each bleaching detergent composition shown in Tables 4 and 5 was used. twenty five
g into a washing machine filled with 30 liters of tap water, then put a dyed cloth sewn on a bed cloth, wash at 20 ° C. for 10 minutes, and after dehydration, rinse with running water for 5 minutes. After dehydration for a minute, the whole cloth was air-dried. Repeat this process 10 times,
Commercially available detergent (“Attack” manufactured by Kao Corporation, registered trademark) 25
In comparison with the same 10 times washing in g, the evaluation was made using the following evaluation points.

With respect to the liquid bleaching agents shown in Table 3, 40 ml of the liquid bleaching agents were added to 30 liters of washing water at the same time as 25 g of the above-mentioned commercial detergents. It was repeated 10 times and evaluated according to the following criteria. <Evaluation points of discoloration degree (cumulative washing method)> 1 point: Discoloration is considerably more intense than in a commercial detergent. 2 point: Discoloration is more severe in comparison with a commercial detergent. Discoloration is observed in comparison. 4 points: Discoloration is slightly observed in comparison with commercial detergents. 5 Points: Discoloration is hardly observed in comparison with 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 (capacity: 50 ml) for 30
Fill and store at 40 ° C for 2 weeks, measure the concentration of organic peracid precursor by high performance liquid chromatography before and after storage,
The residual rate was determined by the following equation.

[0034]

(Equation 2)

(4) The evaluation results obtained by the above (1) to (3) are shown in Tables 2 to 5.

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

Continuation of the front page (56) References JP-A-1-306498 (JP, A) JP-A-61-111400 (JP, A) JP-A-61-210053 (JP, A) JP-A-6-49487 (JP, A) JP-A-6-207196 (JP, A) JP-A-5-194995 (JP, A) JP-A-5-65496 (JP, A) JP-A-2-132195 (JP, A) 8-92596 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-19/00 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (A) sodium percarbonate and sodium perborate
Oxygen peroxides selected from um (b) bleach composition characterized by containing an organic peracid precursor salt consisting of an organic peracid precursor anion and an alkali earth metal ion having an anionic group. 2. The organic peracid precursor salt of the component (b),
The bleaching composition according to claim 1, comprising one or two kinds of salts selected from salts of an organic peracid precursor anion represented by the following general formula (I) and calcium ions or magnesium ions. Composition. Embedded image (Wherein R is an alkyl or alkenyl group having 1 to 18 carbon atoms, an alkanoyloxymethylene group or a phenyl group having 3 to 20 carbon atoms in total, X ⁻ is a SO ₃ ⁻ group or a COO ⁻ group, M ²⁺
Represents Ca ²⁺ or Mg ²⁺ . ) 3. The method according to claim 1, wherein 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 2.