JPH1135985A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching detergent composition which is excellent in bleaching and deterging ability and neither deteriorates nor decolorizes the fibers. SOLUTION: This bleaching detergent composition comprises (a) 1-99 wt % of hydrogen peroxide or an inorganic peroxide which generates hydrogen peroxide in water, (b) 0.001-1 wt % of a cobalt complex compound represented by the formula: [Co(NH3 )n M6-n ].mX [wherein (n) represents 1-6; (m) represents the number required to neutralize the electric charge; M represents halogen; and X represents an anion], and (c) 0.1-30 wt.% of a polymer compound derived from an allyl carboxylic acid having a pKca >3 (preferably acrylic acid, methacrylic acid and hydroxyacrylic acid).

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 performance and does not cause fiber deterioration or decolorization.

[0002]

BACKGROUND OF THE INVENTION Bleaching detergents are classified into chlorine-based and oxygen-based bleaching detergents, but chlorine-based bleaching detergents are limited in the types of fibers that can be used, and cannot be used for colored products. Oxygen-based bleaching detergents that do not have these drawbacks have recently become very popular because of their inherent irritating odor. 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 and US Pat. No. 4,810,410, activation of hydrogen peroxide with a manganese catalyst is carried out, and is described in WO 97/0031.
No. 1 and WO 97/00132 disclose cobalt ammine complexes. However, such a metal complex has a very high bleaching effect on a bleaching detergent, but has a problem of causing fiber deterioration and decolorization of a dye dyed on the fiber. Coveted.

[0003] Accordingly, an object of the present invention is to provide a bleaching detergent composition which sufficiently exerts the effect of improving the bleaching performance of a metal complex and does not cause fiber deterioration or decolorization. .

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by combining a cobalt ammine complex with a chelating agent of a specific polymer compound, the bleaching performance of the cobalt ammine complex has been improved. The present inventors have found that it is possible to sufficiently exert the improving effect and do not cause deterioration or decoloration of the fiber, and thus completed the present invention.

That is, the present invention relates to (a) 1 to 99% by weight of an inorganic peroxide which releases hydrogen peroxide in hydrogen peroxide or water, and (b) 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 a halogen, and X represents an anion. Bleach washing comprising 0.001 to 1% by weight of a cobalt complex compound represented by the following formula: and (c) 0.01 to 30% by weight of a polymer compound derived from an allylcarboxylic acid having a pKca> 3. The present invention provides an agent composition.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The component (a) used in the present invention is hydrogen peroxide or an inorganic peroxide which releases hydrogen peroxide in water. Examples of the inorganic oxide include inorganic peroxide salts such as percarbonate, perborate and perphosphate, and among these, percarbonate is preferred.

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 3 to 90% by weight
It is.

In the general formula (I) representing the component (b) used in the present invention, n is preferably a number of 3 to 6,
Is preferably chlorine and X is preferably a halogen ion. As the compound represented by the general formula (I), a compound represented by the following formula is preferable.

[Co (NH ₃ ) ₆ ] .Cl ₃ [Co (NH ₃ ) ₅ Cl] .Cl ₂ [Co (NH ₃ ) ₄ Cl ₂ ] .Cl

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.

As the allylcarboxylic acid for deriving the polymer compound (c) used in the present invention, acrylic acid,
Methacrylic acid or hydroxyacrylic acid can be mentioned. These allylcarboxylic acids may form a homopolymer or a copolymer with other ethylene derivatives. Examples of other ethylene derivatives include maleic acid, fumaric acid, itaconic acid, ethylene, propylene, acrylonitrile, allyl alcohol, allyl acetate and the like.

The polymer compound of the component (c) is pK
Although ca> 3, this pKca uses a calcium ion electrode, a chelating agent 0.1% solution, pH 10, 2
It was measured at 5 ° C. using a 0.1 M NH ₄ Cl—NH ₄ OH buffer. The molecular weight of the polymer compound (c) is preferably from 5,000 to 100,000.

As the component (c), sodium polyacrylate (pKca = 3.2, molecular weight 8,000), acrylic acid / maleic acid copolymer (pKca = 5.0, molecular weight 70,000) or polyα-hydroxyacrylic Sodium acid salt (pKca = 5.3, molecular weight 50,000) is preferred.

The content of the component (c) in the bleaching detergent composition is from 0.01 to 30% by weight, preferably from 0.1 to 30% by weight, in order to give a sufficient decoloring prevention effect while considering economy. It is from 0.5 to 20% by weight, particularly preferably from 0.1 to 20% by weight.

In the present invention, one or more selected from anionic surfactants and nonionic surfactants can be further blended. Examples of the anionic surfactant include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylate salts. , Α-sulfo fatty acid salts, α-sulfo fatty acid esters and the like.

Examples of the nonionic surfactant include polyoxyethylene or polyoxypropylene or a copolymer thereof, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxides thereof. Products, sucrose fatty acid esters, alkyl glucosides and the like. Nonionic surfactants include polyoxyethylene or polyoxypropylene or copolymers thereof, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose Fatty acid esters, alkyl glucosides and the like can be mentioned. Among these, alkylbenzenesulfonic acid salts (C ₁₀ ~ _20), alkyl or alkenyl sulfates (C ₁₀ ~ _20), alkyl or alkenyl ether sulfates (C ₁₀ ~ _20), polyoxyethylene alkyl or alkenyl ethers (added moles 4~30, C ₁₀ ~ ₂₀₎
And the following general formula (IV): R ³ — (OC ₂ H ₄ ) _n —OH (IV) wherein R ³ is an alkyl or alkenyl group having 6 to 18 carbon atoms or 1 to 12 carbon atoms. Represents an aryl group which may be substituted with an alkyl group, and n represents a number selected so that the HLB obtained by the method of Davis is 4.5 to 10. ] Is particularly preferable. Specific examples of the nonionic surfactant represented by the general formula (IV) include the following compounds.

C ₁₀ H ₂₁ (OC ₂ H ₄ ) _n -OH n = 6 to 18, HLB = 6.13 to 10.09 C ₁₂ H ₂₅ (OC ₂ H ₄ ) _n- OH n = 4 to 25, HLB = 4.52 to 11.45 C ₁₄ H ₂₉ (OC ₂ H ₄ ) _n -OH n = 10 to 25, HLB = 5.55 to 10.50 C ₁₆ H ₃₃ (OC ₂ H ₄ ) _n -OH n = 12 to 30, HLB = 5.26 to 11.20 C _{18 H 37 (OC 2 H 4} ) n -OH n = 15~35, HLB = 5.30~11.9.

The amount of the surfactant in the bleaching detergent composition is preferably from 0.1 to 50 in order to maintain an appropriate viscosity for easy use and to obtain a sufficient detergency.
%, Particularly preferably 0.5 to 30% by weight, more preferably 0.5 to 20% by weight.

The bleaching detergent composition of the present invention may further contain a bleach-activating compound represented by the following general formula (II) or (III).

[0020]

Embedded image

[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 bleach-activating compounds represented by the general formula (II) or (III), in particular, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, 3,5, Five
-Trimethylhexanoyloxybenzoic acid is preferred.

The amount of the bleaching activator compound 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% by weight.
1 to 10% by weight, more preferably 0.5 to 10%.
% By weight.

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

(1) Sequestering Agent As a sequestering agent other than the above-mentioned aluminosilicates, crystalline silicates and carboxylic acid-based polymers, organic chelating agents can be mentioned. For example, diglycolic acid, oxydisuccinic acid, 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 In addition to sodium carbonate, which is collectively called dense ash and light ash, alkali metal carbonates such as calcium carbonate and magnesium carbonate, 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 that inherently perform 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 used in detergents, 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-amyl cinnamic 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, for example, can be used. This antifoaming agent is 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.

[0032]

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 Sodium percarbonate, cobalt complex compound of b-1 to b-3, polymer compound of c-1 to c-3, d-1 to d-4
, The bleach-activating compounds e-1 to e-3 and the components shown in Tables 1 and 2 were used to obtain bleach-cleaning compositions of Examples and Comparative Examples. Note that a cobalt complex compound b′-1 different from the component (b) of the present invention was used for comparison. Each composition was tested for bleaching performance and decolorization by the following methods. The results are shown in Tables 1 and 2.

B-1: [Co (NH ₃ ) ₆ ] .Cl ₃ (Experimental Chemistry Lecture, 4th edition, Vol. 17, P94-95) b-2: [Co (NH ₃ ) ₅ Cl] .Cl ₂ (same as above) 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 polyacrylate (pKca = 3.2,
Molecular weight 8,000; oligomer D manufactured by Kao Corporation) c-2: acrylic acid / maleic acid copolymer (pKc
a = 5.0, molecular weight 70,000; socalane CP5 manufactured by BASF) c-3: sodium poly-α-hydroxyacrylate (pKca = 5.3, molecular weight 50,000; manufactured by Solvay Interox) d-1: sodium alkyl (C ₁₂ ) benzenesulfonate d-2: sodium lauryl sulfate d-3: polyoxyethylene lauryl ether (PEO = 1
0) d-4: fatty acid soap (C _12, sodium salt)

[0035]

Embedded image

(Bleaching Performance) First, a tea-stained cloth used for 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.

[0037]

(Equation 1)

(Decolorization) First, a test cloth was prepared by the following method. A 100% cotton knit smooth, mercerized cloth was dyed exhaustively with CIReactive Red 41 as a dye to a concentration of 4%. Next, this was subjected to ordinary washing and soaping, and then cut after pressing to obtain a 10 × 10 cm test cloth. The decolorization test was performed by the following method.
First, each composition 1 shown in Tables 1 and 2 was added to 2 liters of tap water.
0 g was dissolved and the test cloth was soaked for about 30 minutes. Then, it was washed with water, dehydrated and dried. This series of processing is
It was repeated 0 times and the bleaching property was evaluated according to the following criteria.
Further, the same treatment was performed using a commercially available powder detergent (Attack manufactured by Kao Corporation) in place of each composition, and evaluation was performed.

1: equivalent to a commercially available powder detergent 2: slightly decolorized compared to a commercially available powder detergent 3: decolorized compared to a commercially available powder detergent 4: considerably comparable to a commercially available powder detergent Decolored 5: Significantly decolored compared to commercial powder detergent

[0040]

[Table 1]

[0041]

[Table 2]

As is clear from Tables 1 and 2, Example 1
Each of the compositions Nos. To 8 exhibited an excellent bleaching / cleaning action and did not decolorize. Also, no deterioration of the fibers was observed visually or by touch at all. On the other hand, Comparative Examples 1 and 7, which did not contain the cobalt complex compound as the component (b), had remarkably inferior bleaching performance.
Comparative Examples 5, 6, and 1 containing a cobalt complex compound other than the component
In Nos. 1 and 12, the bleaching performance was good, but the bleaching was remarkable. In Comparative Examples 2, 3, 4, 8, 9 and 10, which did not contain the polymer compound as the component (c), the bleaching performance was good but the decolorization was remarkable.

[0043]

The bleaching detergent composition of the present invention has excellent bleaching detergency, but does not degrade or decolor fibers. Therefore, bleaching and washing of colored products at home become easier.

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Susumu Yamaguchi 1334 Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd.

Claims (5)

[Claims] 1. (a) 1 to 99% by weight of an inorganic peroxide which releases hydrogen peroxide in hydrogen peroxide or water, (b) 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 a halogen, and X represents an anion. Bleach washing comprising 0.001 to 1% by weight of a cobalt complex compound represented by the following formula: and (c) 0.01 to 30% by weight of a polymer compound derived from an allylcarboxylic acid having a pKca> 3. Composition. 2. The bleaching detergent composition according to claim 1, wherein the polymer compound (c) is derived from acrylic acid, methacrylic acid or hydroxyacrylic acid. 3. The bleaching detergent composition according to claim 1, further comprising an anionic surfactant or a nonionic surfactant. 4. The bleaching detergent composition according to claim 1, further comprising a bleach activating compound represented by the following general formula (II) or (III). Embedded image [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. ] 5. The bleaching detergent composition according to claim 1, further comprising a sequestering agent.