JPH11106790A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching detergent composition which maintains a high bleaching detergency over a long period of time. SOLUTION: A bleaching detergent composition contains (a) from to 99 wt.% inorganic peroxide which releases hydrogen peroxide in an aqueous solution, (b) from 0.001 to 1 wt.% cobalt complex compound represented by the formula: [Co(NH3 )n M6-n ].mX(wherein n is 1-6; m is the number of an anion required for neutralizing the electric charge; M is a halogen; and X is an anion) and (c) from 0.01 to 50 wt.% organic metal sealing compound having a pKCa of 4 or smaller. Components (a) and (b) confer a high bleaching detergency to the composition, and component (c) enables the composition to maintain the bleaching detergency for a long period of time.

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 a high bleaching power and does not decrease its bleaching power even when stored for a long time.

[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, activation of hydrogen peroxide by a manganese catalyst is performed, and in US Pat. No. 5,581,005, WO97 / 0031.
1 and WO 97/00132 disclose cobalt ammine complexes in which carboxylate is liganded in addition to ammonium.

[0003] However, while such metal complexes provide a very high bleaching effect to bleaching detergents, 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] Therefore, the present invention is to provide a high bleaching performance by the sodium percarbonate and cobalt ammine complex, and to 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.

[0005]

Means for Solving the Problems The inventors of the present invention have found that when two components of an inorganic peroxide and a cobalt ammine complex are used in combination,
The present inventors have found that the coexistence of a specific organic sequestering agent enhances the storage stability of the two components and can maintain excellent bleaching detergency, thereby completing 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 an aqueous solution, 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. 0.001 to 1% by weight of a cobalt complex compound represented by the following formula: and (c) 0.01 of an organic sequestering agent having a pK _Ca ≦ 4.
It is intended to provide a bleaching detergent composition characterized by containing about 50% by weight.

In the present invention, pK _Ca is measured using a calcium ion electrode, a 0.1% aqueous solution of a chelating agent,
It was measured using a 0.1 M NH ₄ Cl-NH ₄ OH buffer at 10, 25 ° C.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic peroxide releasing hydrogen peroxide in the aqueous solution of the component (a) used in the present invention includes inorganic peroxides such as percarbonate, perborate and perphosphate. And percarbonate is preferable.

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, in order to facilitate blending with other components and to impart 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 is a compound in which ammonium is the main ligand and the others are 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 organic sequestering agent of the component (c) used in the present invention has a pK _Ca ≦ 4, preferably pK _Ca ≦ 3 in order to enhance the storage stability of the components (a) and (b). .
Five. Such organic sequestering agents of component (c) include iminodiacetic acid (pK _Ca = 2.4), tartaric acid (pK _Ca = 2.8), and diglycolic acid (pK _Ca = 3.
1), citric acid (pK _Ca = 3.2), gluconic acid (pK _Ca = 3.2)
_Ca = 2.8), polyacrylic acid (MW = about 8,000, pK
_Ca = 3.3) or a salt thereof, among which citric acid or a salt thereof and polyacrylic acid or a salt thereof are preferable.

The content of the component (c) in the bleaching detergent composition is from 0.01 to 50% by weight in order to improve the storage stability of the composition while considering economy.
The content is 1 to 30% by weight, particularly preferably 0.3 to 25% by weight.

In the bleaching detergent composition of the present invention, a sequestering agent having a pK _Ca > 4, for example, ethylenediaminetetraacetic acid, nitrilotri Acetic acid, aminoacetic acid-based sequestering agent such as hydroxyethyliminodiacetic acid, 1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1, It is unavoidable to mix phosphonic acid sequestering agents such as 2-diphosphonic acid and methanehydroxyphosphonic acid, carboxylic acid polymers such as acrylic acid / maleic acid copolymer, and polyphosphoric acid sequestering agents such as tripolyphosphoric acid. In such a case, it is necessary to reduce their content as much as possible in order to prevent a decrease in bleaching performance. Therefore, the content of the sequestering agent having a pK _Ca > 4 in the bleaching detergent composition of the present invention must be adjusted to 4% by weight or less, preferably 2% by weight.
The content is adjusted as follows, and is not substantially contained in order to achieve the object of the present invention.

The bleaching detergent composition of the present invention may further contain one or more selected from anionic surfactants and nonionic surfactants. 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, polyoxypropylene or a copolymer thereof, polyoxyethylene alkyl or alkenyl ethers, and polyoxyethylene. Oxyethylene 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,
In particular, alkylbenzene sulfonates (C ₁₀ -C ₂₀ ),
Alkyl or alkenyl sulfates (C ₁₀ -C ₂₀ ), alkyl or alkenyl ether sulfates (C ₁₀ -C ₂₀ ),
Polyoxyethylene alkyl or alkenyl ethers (addition molar number 4~30, C ₁₀ ~C ₂₀₎ are preferred, and the following general formula ^{(IV): R 3 - (} OC 2 H 4) p -OH (IV) [ In the formula, R ³ represents an alkyl group or alkenyl group having 6 to 18 carbon atoms or an aryl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, and p is 4 when HLB determined by the method of Davis is 4 Shows a number chosen to be between 0.5 and 12. ]. Such a general formula (I
The nonionic surfactant represented by _{V), C 10 H 21 (} OC 2 H 4) p-OH p = 6~18 (HLB = 6.13~10.09) C 12 H 25 (OC 2 H 4) p -OH p = 4~25 (HLB = 4.52~11.45 ) C 14 H 29 (OC 2 H 4) p-OH p = 10~25 (HLB = 5.55~10.50) C 16 H 33 (OC 2 H 4) p -OH p = 12~30 (HLB = 5.26~11.20 ) C 18 H 37 (OC 2 H 4) p-OH p = 15~35 (HLB = 5.30~11.9) and the like.

The amount of these surfactants is preferably 0.1 to 50% by weight, particularly preferably 0.5 to 50% by weight.
It is 30% by weight, more preferably 0.5 to 20% by weight.

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

[0018]

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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
And aryl groups which may be substituted with an alkyl group of 1 to 12].

Among the bleaching activators represented by the general formula (II) or (III), sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, 5,5,5-Trimethylhexanoyloxybenzoic acid is preferred.

The amount of the bleaching activator is preferably 0.01 to 20% by weight in order to prevent precipitation or increase in viscosity and to provide sufficient bleaching detergency. Particularly preferably, it is 0.1 to 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) Alkali agent As the alkaline agent, in addition to sodium carbonate generally referred to as 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.

(2) Acid Agent In order to prevent the pH of the washing liquid from becoming too high, an acid agent can be blended. As the acid agent, the same as the component (c) can be used, and polycarboxylic acids such as lactic acid, succinic acid, malic acid, and gluconic acid can be used.

(3) 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.

(4) Other Polymers Polyethylene glycol having an average molecular weight of 200 to 200,000 is used as a binder or a powder physical agent in the case of increasing the density, and to impart an effect of preventing re-contamination of hydrophobic fine particles. Polyvinyl alcohol or the like can be blended. Further, polyvinylpyrrolidone can be blended in order to impart a color transfer prevention effect.

(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) Enzyme stabilizer As an enzyme stabilizer, a reducing agent such as sodium sulfite or sodium hydrogen sulfite, a calcium salt, a magnesium salt, a polyol, a boron compound or the like is blended to remove chlorine in tap water. Can be. In addition, sodium sulfite can also function as an antioxidant.

(7) Blueing agent JP-B-49-8005, JP-B-49-26286
And the bluing agent described in JP-B-53-45808 can be blended.

(8) Anti-caking agent As anti-caking agent, paratoluenesulfonic acid salt,
Xylene sulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, magnesium oxide and the like can be blended.

(9) As antioxidants, tert-butylhydroxytoluene, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2′-butylidenebis- (6
-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis- (4-
(Hydroxyphenyl) cyclohexane and the like can be blended.

(10) Fluorescent dye As a fluorescent dye, 4,4'-bis- (2-sulfostyryl)-
Biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl)
A stilbene derivative, a bis (triazinylamino) stilbenzylsulfonic acid derivative, Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.), Tinopearl CBS (manufactured by Ciba Geigy) and the like can be blended. These fluorescent dyes can be incorporated in the composition in an amount of 0 to 2% by weight.

(11) 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.
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.

(12) Antifoaming agent As the antifoaming agent, a conventionally known silicone / silica-based antifoaming agent can be used, for example. 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 sodium sulfate at 70 to 80 ° C, an extrusion granulator manufactured by Fuji Paudal Co., Ltd. (Model EXKS-1) to obtain granules.

[0035]

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 1-7 and 1-12 Sodium percarbonate, cobalt complex compound of b-1 to b-3, sequestering agent of c-1 to c-3, and d-1 to d-4 Surfactants, bleach activators of e-1 and e-2 and Tables 1 and 2
The bleaching cleaning compositions of Examples and Comparative Examples were obtained by using the components shown in (1) and (2). Note that a cobalt complex compound b′-1 different from the component (b) and a sequestering agent c′-1 different from the component (c).
~ C'-4 was used as a comparison. Each composition was tested for bleaching performance and stability by the following methods.
The results are shown in Tables 1 and 2.

B-1: [Co (NH ₃ ) ₆ ] · Cl ₃
(Experimental Chemistry Course, 4th edition, Vol. 17, P94-95) b-2: [Co (NH ₃ ) ₅ Cl] .Cl ₂ (P102) b-3: [Co (NH ₃ ) ₄ Cl ₂ ] .Cl (Same as P107-10
8) b'-1: [Co (NH ₃ ) ₅ OAc] · Cl ₂ (USP 55810)
05) c-1: sodium polyacrylate (MW8000, pKCa =
3.4) c-2: Trisodium citrate (pKCa = 3.2) c-3: Imino-2-succinic acid (pKCa = 3.9) c'-1: Acrylic acid / maleic acid copolymer (70/30, MW = 70000) , BA
C--2: Sodium tripolyphosphate (pKCa = 5.0) c'-3: Human peroxyethyl phosphate phosphonic acid (Monquest Sanctuary 201)
6, pKCa = 6.8) c'-4: ethylenediaminetetraacetic acid / 4 sodium (p
KCa = 12.0) d-1: alkyl (C ₁₂₎ sodium benzenesulfonate d-2: sodium lauryl sulfate d-3: polyoxyethylene lauryl ether (POE = 1
0) d-4: fatty acid soap (C _12, sodium salt)

[0038]

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Evaluation of bleaching performance before and after storage Preparation of black tea-stained cloth 80 g of Nitto black tea (yellow package) was boiled with 3 liters of ion-exchanged water for about 15 minutes, and rubbed with bleached cotton after desizing. Next, soak cotton gold cloth # 2003 in this liquid,
Boil for about 15 minutes. After being removed from the fire as it was and allowed to stand for about 2 hours, it was washed with water until the washing liquid was not colored, dewatered and pressed, and then cut into 10 × 10 cm to prepare a black tea-stained cloth for testing. Measurement of bleaching performance 10 g of each of the bleaching detergent compositions shown in Tables 1 and 2 were dissolved in 2 liters of tap water, and the above-mentioned black tea-stained cloths were immersed in five pieces for 15 minutes. Thereafter, after thoroughly rinsing with tap water, the reflectance of the dried product was measured, the bleaching ratio was calculated from the following formula, and the bleaching performance before storage was evaluated. Next, 10 g of each bleaching detergent composition was stored for one month in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 80%, and the reflectance was measured in the same manner as before storage to calculate the bleaching rate. The bleaching performance after storage was evaluated. The reflectance was measured using a NDR-101DP 460 nm filter manufactured by Nippon Denshoku Industries Co., Ltd.

[0040]

(Equation 1)

[0041]

[Table 1]

[0042]

[Table 2]

As is clear from Tables 1 and 2, Example 1
Each of the compositions Nos. To 7 exhibited excellent bleaching detergency and also had excellent storage stability. On the other hand, in Comparative Examples, those containing more than 4% by weight of a sequestering agent with pK _Ca > 4 (Comparative Examples 1 to 4, 7 to 10) are (a)
Despite containing component (b), the bleaching performance was low before storage, and further decreased after storage. Also,
Those containing no sequestering agent (Comparative Examples 5, 11)
Although the bleaching performance before storage was excellent due to the action of the components (a) and (b), the bleaching performance after storage was significantly reduced.

Thus, from these results, the bleaching detergent composition of the present invention exhibits excellent bleaching detergency due to the synergistic action of the component (a) and the component (b), and further comprises the component (c). It was recognized that the storage stability was enhanced and the bleaching detergency at the beginning of the production was maintained by the combined use. Also, pK _Ca > which may be mixed as an impurity>
By analyzing and controlling the content of the sequestering agent of No. 4, the quality stability of the product can be improved.

[0045]

The bleaching detergent composition of the present invention has excellent bleaching detergency, and can maintain the bleaching detergency for a long period of time. Therefore, at the time of manufacture and distribution, it is easy to manage products by manufacturers and sellers, and the bleaching and detergency at the time of purchase can be maintained for a long time, so that there is a great benefit to consumers.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/39 C11D 3/39 D06L 3/02 D06L 3/02 (72) Inventor Muneo Aoyagi 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Kao Corporation In the laboratory

Claims (3)

[Claims] (1) 1 to 99% by weight of an inorganic peroxide releasing hydrogen peroxide in an aqueous solution, (b) a 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 electric charge, and M represents a halogen. , X represents an anion. 0.001 to 1% by weight of a cobalt complex compound represented by the following formula: and (c) 0.01 of an organic sequestering agent having a pK _Ca ≦ 4.
A bleaching detergent composition characterized by containing about 50% by weight. 2. The bleaching detergent composition according to claim 1, wherein the organic sequestering agent having pK _Ca ≦ 4 as the component (c) is polyacrylic acid, citric acid or a salt thereof. 3. A compound of the following general formula (II) or (III): [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 claim 1 or 2, comprising a bleaching activator represented by the formula: