JPH1150092A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching detergent composition capable of maintaining an excellent bleaching washing force for a long period. SOLUTION: This bleaching detergent comprises (a) sodium percarbonte coated with a nonionic surfactant, an anionic surfactant or boric acid or its salt and (b) a cobalt complex of the formula: [Co(NH3 )n M6-n ].mX [(n) is the number of 1-6; (m) is the number required for neutralizing the electric charge; M is a halogen; X is an anion]. Since the decomposition of the sodium percarbonate is suppressed, the bleaching and washing force is not lowered.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching detergent composition which has high bleaching power and does not decrease in bleaching power even when stored for a long period of time.

[0002]

2. Description of the Related Art Bleaching detergents are classified into chlorine-based and oxygen-based ones. Chlorine-based bleaching detergents are limited in the types of fibers that can be used. As a result, oxygen-based bleaching detergents free of these drawbacks have recently become very popular. As the oxygen-based bleach, sodium percarbonate and sodium perborate are used as a powder bleach, and hydrogen peroxide is used as a liquid bleach. Oxygen-based bleaching detergents have weaker bleaching power than chlorine-based bleaching detergents, and are therefore used in combination with various bleaching activators, metal complex catalysts, and the like. For example, in US Pat. No. 5,246,612, activation of hydrogen peroxide by a manganese catalyst is performed.
5, WO97 / 00131 and WO97 / 00132 disclose cobalt ammine complexes in which carboxylate is liganded in addition to ammonium.

[0003] However, while such a metal complex gives a very high bleaching effect to a bleaching detergent, when combined with powdered or granular sodium percarbonate, the stability of sodium percarbonate during storage is reduced. Significantly lower,
As a result, there is a problem that the bleaching performance is reduced.

[0004]

Attempts have been made to coat the cobalt ammine complex with other components in order to improve the stability of such powdered or granular sodium percarbonate. For example, Japanese Patent Publication No. 47-32200 discloses a method of coating sodium percarbonate with paraffin, and Japanese Patent Publication No. 53-15717 discloses a method of coating sodium percarbonate with sodium perborate. ,
U.S. Pat. No. 4,131,562 discloses a method of coating sodium percarbonate with sodium perborate and an ethylene oxide adduct of an alcohol.
No. 12 discloses a method of coating sodium percarbonate and sodium perborate with polyethylene glycol, and German Patent No. 2712139 discloses a method of coating sodium percarbonate with silicate. No. 2,800,916 discloses a method of coating sodium percarbonate with boric acid, EP 30759 discloses a method of coating sodium percarbonate with wax, and JP-A-58-217599 discloses a method of coating sodium percarbonate with wax. Discloses a method of coating sodium percarbonate with borate,
JP-A-59-196399 discloses a method of coating sodium percarbonate with a borate.
No. 1498 discloses a method in which sodium percarbonate is separately sprayed and coated with boric acid and silicate.

However, most of the sodium percarbonates obtained by these methods cannot solve the problem that the stability is lowered when combined with a cobalt ammine complex.

[0006] Therefore, the present invention provides sufficient bleaching performance by sodium percarbonate and cobalt ammine complex, and can stably store sodium percarbonate even when stored for a long period of time. It is an object to provide a bleaching detergent composition that can be maintained.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies to find a specific component for coating sodium percarbonate and a specific cobalt ammine complex to be combined with the sodium percarbonate. Was piled up. As a result, first, a specific component covering sodium percarbonate was found, and further, sodium percarbonate coated with the specific component, WO97 / 00131, WO97 / 0031
In combination with a cobalt ammine complex having a carboxylate ligand other than ammonium as disclosed in No. 2 and a manganese catalyst disclosed in US Pat. No. 4,810,410, the object of the present invention cannot be achieved. It has been found that the object of the present invention can be achieved for the first time by the combination of sodium percarbonate coated with, and a cobalt ammine complex in which ammonium is the main ligand and the other is halogen, and the present invention has been completed. .

That is, the present invention relates to (a) sodium percarbonate coated with a nonionic surfactant, an anionic surfactant or boric acid or a salt thereof, and (b) a compound represented by the general formula (I): [Co (NH ₃ ) _n M _6-n ] · mX (I) [wherein, n represents a number of 1 to 6, m represents a number necessary for neutralizing the charge, M represents halogen, X Represents an anion. ] It is intended to provide a bleaching detergent composition containing a cobalt complex compound represented by the formula:

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) used in the present invention is one in which sodium percarbonate serving as a bleaching active species is coated with a nonionic surfactant, an anionic surfactant or boric acid or a salt thereof. is there.

The nonionic surfactant used for the production of the component (a) has a melting point of 40 ° C. or less and a viscosity at 20 ° C. (value measured by a Brookfield viscometer) of 10 to 100 mP.
The HLB determined by Davis' method in a.s is 4.
The following general formula (II) of 5 to 12: R— (OC ₂ H ₄ ) _n —OH (II) wherein R is an alkyl or alkenyl group having 6 to 18 carbon atoms or a C 1 to C 12 An aryl group which may be substituted with an alkyl group is shown, and n represents a number selected so that the HLB obtained by the method of Davis is 4.5 to 12. ]. Such a general formula (II)
Examples of the nonionic surfactant represented by the following can be mentioned, and these can be used alone or in combination of two or more. As the nonionic surfactant satisfying the above conditions, C ₁₀ H ₂₁ (OC ₂ H ₄ ) _n -OHn = 6 to 18, HLB = 6.13 to 10.09 C ₁₂ H ₂₅ (OC ₂ H ₄ ) _n -OH n _{= 4~25, HLB = 4.52~11.45 C 14} H 29 (OC 2 H 4) n -OH n = 10~25, HLB = 5.55~10.50 C 16 H 33 (OC 2 H 4) n -OH n = 12 _{~30, HLB = 5.26~11.20 C 18 H} 37 (OC 2 H 4) n -OH n = 15~35, and the like can be given HLB = from 5.30 to 11.9.

As the anionic surfactant used in the production of the component (a), alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated salts Saturated fatty acid salts, alkyl or alkenyl ether carboxylate salts, α-sulfo fatty acid salts, α-sulfo fatty acid esters and the like can be mentioned, and these can be used alone or in combination of two or more. Alkylbenzene sulfonates of C ₁₀ -C ₁₈ Among these, polyoxyethylene alkyl ether sulfates or fatty alcohol sulfates are preferred.

The boric acid or salts thereof used in the production of the component (a) include sodium, potassium, magnesium, and calcium salts of metaboric acid, orthoboric acid or diboric acid. Species or a combination of two or more can be used.

As a method for producing the component (a) using a surfactant, a method in which a surfactant is sprayed on sodium percarbonate, a method in which sodium percarbonate and a nonionic surfactant or an anionic surfactant are tumbled. A method of mixing and granulating with a granulator, a method of rapidly stirring sodium percarbonate and a nonionic surfactant or an anionic surfactant with a mixer, and the like can be applied. The amount of the surfactant used in this production method is preferably 0.01 to 50% by weight based on sodium percarbonate in order to increase the stability of sodium percarbonate in consideration of the compatibility with other components. The amount is particularly preferably 0.05 to 10% by weight, and more preferably 0.1 to 3% by weight.

A method for producing component (a) using sodium percarbonate by using boric acid or a salt thereof is disclosed in
No. 217,599, page 9 and the following Examples and JP-A-59-159.
The method described in the examples on page 5 and following pages of 196399 can be applied. The method is as follows. 100 g of sodium percarbonate is put into a stirring mixer and stirred at 250 rpm while sodium metaborate tetrahydrate (NaB
_{0 2 · 4H 2 O) 25} % aqueous solution of 5 g (heated and melted to prepare)
Is sprayed and stirred for 10 minutes, and then dried with hot air to obtain sodium percarbonate coated with sodium metaborate / tetrahydrate.
The amount of boric acid or salts thereof used in this production method is
In order to enhance the stability of sodium percarbonate in consideration of the compatibility with other components, the amount is preferably 0.01 to 20% by weight based on sodium percarbonate, particularly preferably 0.1 to 10% by weight. %, More preferably 0.5 to 10% by weight.

The content of the component (a) in the bleaching detergent composition is from 1 to 99% by weight, preferably from 1 to 99% by weight, for facilitating blending with other components and providing sufficient bleaching detergency. 90% by weight, particularly preferably 2 to 90% by weight
It is.

The cobalt complex compound of the component (b) used in the present invention has ammonium as its main ligand and the others as halogens. In the general formula (I) representing the component (b), n is preferably a number of 3 to 6, M is preferably chlorine, and X is preferably a halogen ion. Examples of the compound represented by the general formula (I) include the following formulas [Co (NH ₃ ) ₆ ] · Cl ₃ [Co (NH ₃ ) ₅ Cl] · Cl ₂ [Co (NH ₃ ) ₄ Cl ₂ ] -A compound represented by Cl 2 is preferable.

The content of the component (b) in the bleaching detergent composition is from 0.001 to 1% by weight, preferably from 0.1 to 1% by weight, in order to prevent the fiber from deteriorating and to give a sufficient bleaching detergency. 005 to 0.5% by weight, particularly preferably 0.1 to 0.5% by weight.
01 to 0.5% by weight.

The bleaching detergent composition of the present invention may further contain a bleaching activator represented by the following general formula (III) or (IV).

[0019]

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[M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R ¹ and R ^{2 each} have 7 carbon atoms.
To 18 alkyl or alkenyl groups or 1 carbon atom
Represents an aryl group which may be substituted with an alkyl group of 1 to 12; Among the bleaching activators represented by the general formula (III) or (IV), in particular, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, 3,5 , 5-Trimethylhexanoyloxybenzoic acid is preferred.

The amount of the bleach activator in the bleaching detergent composition is preferably from 0.01 to 0.01 in order to prevent precipitation or an increase in viscosity and to impart sufficient bleaching detergency. 20% by weight, particularly preferably 0.1 to
It is 10% by weight, more preferably 0.5 to 10% by weight.

The following components can be further added to the bleaching detergent composition of the present invention, if necessary.

(1) Sequestering Agents Sequestering agents other than the above-mentioned aluminosilicates, crystalline silicates and carboxylic acid polymers include organic chelating agents, such as diglycolic acid, oxydisuccinic acid and citric acid. Polycarboxylic acid salts such as acids or salts thereof,
Nitrilotriacetic acid, ethylenediaminetetraacetic acid, iminodiacetic acid, hydroxyimidinodiacetic acid, aminopolycarboxylic acid such as hydroxyiminodisuccinic acid or a salt thereof, ethane-1,
Salts of phosphonic acids such as 1-diphosphonic acid and ethane-1,2-triphosphone, and the like, and particularly preferred are organic chelating agents having a pKCa value of 4 or more. Examples of the inorganic sequestering agent include phosphates such as orthophosphate, pyrophosphate, and tripolyphosphate. In the case of a salt, sodium and potassium are preferred as counter ions.

(2) Phosphorus compound As the phosphorus compound, a conventionally known compound that supplements a metal ion is preferable. Especially tripolyphosphate,
Orthophosphates and metaphosphates are preferred, and sodium tripolyphosphate is particularly preferred.

(3) Alkali agent As the alkaline agent, there are alkali metal carbonates such as calcium carbonate, magnesium carbonate, etc., in addition to sodium carbonate generally called dense ash and light ash, and JIS Nos. 1, 2 and 3,
And other amorphous alkali metal silicates. These inorganic alkaline agents are effective as a skeleton forming component of the particles when the detergent is dried, and a relatively hard detergent having excellent fluidity can be obtained.

(4) Extender [Neutral Salt] As the extender [neutral salt], sodium sulfate generally called sodium sulfate can be blended. Sodium sulfate is effective in forming the skeleton of the detergent particles after drying, like the inorganic alkaline agent. Other preferred neutral salts include sodium chloride and potassium chloride.

(5) Enzymes Enzymes (enzymes which essentially perform an enzymatic action during the washing step) can be classified into hydrolases, oxidoreductases, lyases, transferases and isomerases by classifying them based on their reactivity. And any of them can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain,
Promerin, carboxypeptidases A and B, aminopeptidase, aspergillopeptidases A and B, and commercially available products such as Savinase, Alcalase (Novo Industries), API21 (Showa Denko KK), and Maxacal (Gystprokei) Death Corporation), JP-A-5-2549
Protease K-14 or K-16 described in JP-A No. 2 can be mentioned. Specific examples of esterases include:
Examples include gastric lipase, bankreatic lipase, plant lipases, phospholipases, cholinesterases, and phosphotases. Specific examples of the lipase include commercially available lipases such as lipolase (Novo Industries) and liposam (Showa Denko KK). As cellulase, commercially available cellzyme (Novo Industry Co., Ltd.),
The cellulase described in claim 4 of JP-A-3-264699 can be mentioned, and as the amylase, commercially available termamyl (Novo Industry Co., Ltd.) can be mentioned. Enzymes are separately granulated as stable particles and used in a dry-blended state with detergent fabric (particles).

(6) Fluorescent dyes Fluorescent dyes include 4,4'-bis- (2-sulfostyryl) -biphenyl salt and 4,4'-bis- (4-chloro-3-
Sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbenzyl sulfonic acid derivative, Whitex SA ( Sumitomo Chemical Co., Ltd.), Tinopearl CBS (Ciba Geigy) and the like. One or two or more of these fluorescent dyes can be incorporated in the composition in an amount of 0 to 2% by weight.

(7) Fragrance As a fragrance, a fragrance conventionally blended in a detergent, for example, a fragrance described in JP-A-63-101496, dimethylbenzylcarbinyl acetate, tricyclo [5.2.1.0
^2,6 ] -dec-3-en-8-yl acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-ene-8-isopropionate, 3-amyl-4-acetoxytetrahydropyran, 4-tert-butylcyclohexyl acetate, 2-
tert-butylcyclohexyl acetate, p-tert-butyl-α-methylhydrocinnamic aldehyde, 4-
(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, α-amylcinnamic aldehyde, α, α′-dimethyl-p-ethylhydrocinnamic aldehyde, and the like. Can be mentioned. Of course, in order to prevent deterioration due to other detergent components, the type of each flavor component to be blended and, if necessary, the blending ratio and blending amount are considered.

(8) Antifoaming agent As the antifoaming agent, a conventionally known silicone / silica-based antifoaming agent can be mentioned, for example, as described in JP-A-3-186307 described below. An antifoaming agent granule produced by the method described in the lower left column of page 4 of the publication may be used. First, 20 g of a silicone (compound type, PS antifoam) manufactured by Dow Corning as an antifoaming component is added to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nisse Chemical Co., Ltd., and mixed to obtain a homogeneous mixture. Next, after mixing 50% of the obtained homogeneous mixture, 25% of polyethylene glycol (PEG-6000, melting point 58 ° C) and 25% of neutral anhydrous boron nitrate at 70 to 80 ° C, extrusion granulation manufactured by Fuji Paudal Co., Ltd. Granulate with a machine (model EXKS-1) to obtain a granulated product.

[0031]

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

Examples 1 to 8 and Examples 1 to 12 Coated sodium percarbonate of the following a-1 to a-3:
Cobalt complex compounds of b-1 to b-3, c-1 to c-4
, Bleach activators d-1 to d-3 and the components shown in Tables 1 and 2 were used to obtain bleaching cleaning compositions of Examples and Comparative Examples. In addition, sodium percarbonate a'-1, a'-2 coated with a component different from the component (a), and a cobalt complex compound b'-1 different from the component (b) were used for comparison. Each composition was tested for bleaching performance and stability by the following methods. The results are shown in Tables 1 and 2.

A-1: 100 g of sodium percarbonate was added to a high speed mixer, and 5 g of sodium alkylbenzenesulfonate (C ₁₂ ) was gradually added with stirring.
What was obtained by mixing. a-2: Polyoxyethylene lauryl ether (POE = 9, HLB = 6.2, mp) instead of alkylbenzene sulfonic acid
= 18, viscosity = 32 mPa · s), except that a-1 was used. a-3: obtained by coating with sodium metaborate according to Example 1 of JP-A-59-196399. a'-1: obtained by coating with sodium perborate according to Example 1 of JP-B-53-15717. The details are as follows. While flowing 1,000 g of sodium percarbonate in the fluidized bed, 100 g of dioctyl phthalate was spray-adsorbed at room temperature at room temperature, and when dioctyl phthalate uniformly wetted sodium percarbonate, sodium perborate passed through 100 mesh. 50 g of the fine powder was charged, and the sodium perborate fine powder was adhered to the surface of the sodium percarbonate while flowing again. a'-2: Example 1 of JP-A-56-155003
Obtained by coating with sodium silicate according to the above. The details are as follows. A rotating trommel (diameter 250 mm, height 250 mm) having four 15 mm-width entraining ribs at the same interval and rotating at a rotation speed of 30 rpm, and 145.5 g of sodium par The carbonate is pre-added and then sprayed with 210 ml of a water glass solution (sodium silicate) (containing 65.9 g of water glass, viscosity 36 ° Be ′), 316 g of anhydrous Na ₂ SO ₄ and The sodium percarbonate was coated with a homogeneous mixture consisting of 120 g of sodium perborate. After the final processing stage,
It was dried at a temperature of about 55-60 ° C. for 1 hour in a drying room. b-1: [Co (NH 3) 6] · Cl 3 ( Experimental Chemistry 4th ed. Vol. 17 P94-95) b-2: [Co (NH 3) 5 Cl] · Cl 2 ( same P102) b -3: [Co (NH ₃ ) ₄ Cl ₂ ] · Cl (P107-10
8) b'-1: [Co (NH ₃ ) ₅ OAc] · Cl ₂ (USP 5581
005) c-1: sodium alkyl (C ₁₂ ) benzenesulfonate c-2: sodium lauryl sulfate c-3: polyoxyethylene lauryl ether (PEO
= 10) c-4: fatty acid soap (C _12, sodium salt)

[0034]

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(Bleaching Performance) First, a black tea-stained cloth to be used in the test was prepared by the following method. 80 g of Nitto black tea (yellow package) was boiled with 3 liters of ion-exchanged water for about 15 minutes, and rubbed with desizing bleached cotton. Next, cotton gold cloth # 2003 was immersed in this liquid and boiled for about 15 minutes. Remove from the fire as it is, leave it for about 2 hours, wash with water until the washing liquid does not color, and after dehydration and pressing, 10 × 1
It was cut to 0 cm to obtain a black tea-contaminated cloth for testing. The test of the bleaching performance was performed by the following method. First, 10 g of each composition shown in Tables 1 and 2 was dissolved in 2 liters of tap water, and five pieces of the black tea-stained cloth were immersed for 15 minutes. Next, after thoroughly rinsing with tap water, drying was performed, and the bleaching rate was calculated from the following equation, and the bleaching performance was evaluated. In measuring the reflectance,
460nm of NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd.
A filter was used.

[0036]

(Equation 1)

(Stability) The liquid bleach composition before storage and after storage at 40 ° C. for 3 months was titrated with a 0.1N potassium permanganate solution, and the effective oxygen concentration was calculated from the following formula. Was evaluated for stability.

[0038]

(Equation 2)

[0039]

[Table 1]

[0040]

[Table 2]

As is clear from Tables 1 and 2, Example 1
Each of the compositions Nos. To 8 exhibited an excellent bleaching and washing action, and also had an excellent stability of sodium percarbonate. In contrast, the compositions of Comparative Examples 1 to 3 and 7 to 9 in which sodium percarbonate not coated with a nonionic surfactant and the like and the cobalt complex compound of the component (b) were used in combination, and components different from the present invention. The compositions of Comparative Examples 4, 5, 10 and 11 coated with sodium percarbonate, and the compositions of Comparative Examples 6 and 12 using a cobalt complex compound different from the component (b) were all low in stability. .

From these results, it can be seen from the results that the bleaching detergent composition of the present invention has excellent bleaching performance due to the synergistic action of the component (a) and the component (b). , (A) It was recognized that the stability of sodium percarbonate in the component was enhanced. On the other hand, the compositions of the comparative examples have some performance although the bleaching power at the beginning of production is somewhat insufficient, but because the stability is low, sodium percarbonate is decomposed during storage. However, the bleaching performance after a long period of time will be significantly inferior.

[0043]

The bleaching detergent composition of the present invention has excellent bleaching detergency, and can maintain the bleaching detergency for a long period of time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/20 C11D 3/20 3/33 3/33 3/34 3/34 3/39 3/39 3/395 3/395 (72) Inventor Susumu Yamaguchi 1334 Minato, Wakayama City, Wakayama Prefecture Inside Kao Corporation Research Institute (72) Inventor Kazuyoshi Ozaki 1334 Minato, Wakayama City Minato 1334 Kao Corporation Research Institute 1334 Minato Kao Research Laboratory

Claims (5)

[Claims] (1) sodium percarbonate coated with a nonionic surfactant, an anionic surfactant or boric acid or a salt thereof; and (b) a compound represented by the general formula (I): [Co
(NH ₃ ) _n M _6-n ] · mX (I) [wherein, n represents a number of 1 to 6, m represents a number necessary for neutralizing the charge, M represents halogen, X Represents an anion. ] A bleaching detergent composition comprising a cobalt complex compound represented by the formula: 2. A nonionic surfactant having a melting point of 40 ° C.
Below, the viscosity at 20 ° C. is 10 to 100 mPa · s,
The following general formula (II), wherein the HLB determined by the method of Davis is 4.5 to 12, R- (OC ₂ H ₄ ) _n —OH (II) wherein R is 6 to 18 carbon atoms. Represents an aryl group which may be substituted with an alkyl group or alkenyl group or an alkyl group having 1 to 12 carbon atoms, and n is a number selected so that the HLB obtained by the method of Davis is 4.5 to 12. Is shown. The bleaching detergent composition according to claim 1, which is represented by the formula: 3. The bleaching detergent composition according to claim 1, wherein the anionic surfactant is an alkylbenzene sulfonate, a polyoxyethylene alkyl ether sulfate or an aliphatic alcohol sulfate. 4. A compound of the following general formula (III) or (IV): [M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R ¹ and R ² are substituted with an alkyl group or alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Represents an optionally substituted aryl group. The bleaching detergent composition according to any one of claims 1 to 3, further comprising a bleaching activator represented by the formula: 5. The method according to claim 1, further comprising a sequestering agent.
A bleaching detergent composition according to any one of claims 3 to 7.