JPH11256190A - Bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching agent composition capable of suppressing the fading of a clothing with a colored pattern due to bleaching and cleaning using city water. SOLUTION: This bleaching agent composition comprises (a) an inorganic peroxide to generate hydrogen peroxide in an aqueous solution and (b) an aromatic compound which contains one or more groups having >=0.5 Taltσ* as substituent groups and one or more hydrophilic groups in the molecule in which the total of Taltσ* in the substituent groups is 2-5. Taltσ* is defined by Lange's Handbook of Chemistry, 13 th addition 3-133 to 3-139 pages, John A. Dean McGraw-Hill Book Company. Preferably, the composition further contains 1-50 wt.% of a surfactant and 0.0005-5 wt.% of a metal ion sequestering agent.

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 capable of suppressing the discoloration or fading of colored clothes due to chlorine in tap water when the colored clothes are repeatedly washed.

[0002]

2. Description of the Related Art In many cases, dyed textiles such as clothing are discolored or faded when repeatedly washed with tap water. This is because chlorine, which is contained in tap water at about 0.1 to 0.5 ppm, acts on a dye that colors textiles. Therefore, by repeating washing, the degree of discoloration or fading increases.

[0003] Various chlorine scavengers have been proposed to solve such problems. For example, JP-A-8-5
Japanese Patent No. 3698 discloses a low molecular weight polyethyleneimine as a chlorine scavenger.
No. 45 discloses ammonium sulfate as a chlorine scavenger, and JP-A-60-44599 discloses:
Ammonium compounds, amide compounds and imide compounds are disclosed as chlorine scavengers.

[0004] However, such a chlorine-based scavenger impairs the stability of hydrogen peroxide, a bleaching active species, when used in combination with an oxygen-based bleaching agent, which is widely used as a bleaching detergent for clothing such as colored products. There is a problem.

[0005] Accordingly, the present invention provides a bleaching detergent which, when repeatedly bleached and washed with tap water, can continuously exhibit excellent bleaching washing power and can suppress discoloration or fading of colored clothing due to chlorine in tap water. The purpose is to do.

[0006]

Means for Solving the Problems The present inventors have found that, in an aromatic compound having a substituent, one or more substituents Ta
By setting ftσ ^* to a predetermined value and further making at least one substituent a hydrophilic group, irrespective of the properties of the bleaching agent, it does not impair the bleaching power during storage and use, and has a high chlorine trapping capacity. The present inventors have found that the present invention exhibits the property and completed the present invention.

That is, the present invention provides (a) an inorganic peroxide that generates hydrogen peroxide in an aqueous solution and (b) a molecule in the molecule.
A bleaching composition comprising an aromatic compound having one or more substituents having Taftσ ^* of 0.5 or more, and having a total Taftσ ^* of 2 to 5 in all the substituents. Is what you do.

[0008] The bleach composition of the present invention can be a liquid or powdery composition. In the present invention, “Taftσ ^* ” is “LANGE'S HANDBO”.
OKOF CHEMISTRY, 13th edition, 3-133
Pp. 3-139, JOHNA. DEAN McGra
w-Hill Book Company ". This “Taftσ ^* ” describes Hammett's rule that quantitatively discusses the effect of a substituent on the reaction of an organic compound. W. It is a substituent constant when extended to an aliphatic ortho substituent by Taft et al., And is a value determined by the type of the substituent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic peroxide which generates hydrogen peroxide in an aqueous solution (a) used in the present invention includes, in addition to hydrogen peroxide, percarbonates, perborates, perphosphates and the like. Inorganic peroxide salts can be mentioned. The choice of the component (a) is determined depending on whether the bleaching composition is liquid or powder. That is, hydrogen peroxide is used in the case of liquid, and inorganic peroxide other than hydrogen peroxide is used in the case of powder.

The content of the component (a) is preferably from 0.5 to 10.0% by weight, particularly preferably from 1.0 to 6.0% by weight, in order to impart a sufficient bleaching detergency. .

The component (b) used in the present invention is a component that acts as a chlorine scavenger in tap water at the time of bleaching and washing.

Taf in the aromatic compound of the component (b)
As a substituent having tσ ^* of 0.5 or more, NO ₂ , CN, O
H, OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ , OC ₆ H
₅ , COCH ₃ , COOH, COOCH ₃ , COOC
It may be mentioned those selected from ₂ H _5, Cl and SH. As for the substituent having Taftσ ^* of 0.5 or more, the same or different one may be bonded to two or more substituents, and Taftσ ^* is preferably from 1.0 to 4.0.

The hydrophilic group in the aromatic compound as the component (b) is SO ₃ M or COOM [where M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. ] Can be mentioned. M is preferably an alkali metal atom such as a hydrogen atom, a sodium atom, and a potassium atom.

The total of Taftσ ^* of all the substituents (including the hydrophilic group) in the aromatic compound (b) is 2 to 5, preferably 2 to 3, in order to enhance the chlorine scavenging property.
5

As the aromatic compound of the component (b), the following general formula (I):

[0016]

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[Wherein one of X and Y is NO ₂ , CN, O
H or OCH ₃ , and the other represents SO ₃ M or COOM (where M has the same meaning as described above), and the above substitution is performed so that the sum of Taftσ ^* in all the substituents becomes 2 to 5. Shows a group selected from the group of groups. ] Can be mentioned. As the aromatic compound of the component (b) represented by the general formula (I), the following general formula (I)
I):

[0018]

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[Wherein, the meanings of X and Y are the same as above. ] Is preferable.

The aromatic compounds represented by the general formula (II) include those represented by the following formulas.

[0021]

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When the aromatic compound as the component (b) is unstable to oxidation, the aromatic compound is granulated using a binder such as a fatty acid, polyethylene glycol, or an inorganic salt in order to enhance the stability in the composition. Alternatively, after a more stable derivative, it can be blended.

The content of the component (b) is preferably from 0.001 to 10% by weight, particularly preferably from 0.01 to 5.0% by weight in order to impart sufficient chlorine scavenging properties.

The bleaching composition of the present invention may further contain a surfactant. As the surfactant, at least one selected from an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant can be 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 ethers. Carboxylic acid salts, α-sulfofatty acid salts, α-sulfofatty acid esters, etc .; examples of nonionic surfactants include polyoxyethylene, polyoxypropylene or a copolymer thereof, polyoxyethylene alkyl or alkenyl ether. , Polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, etc .; Examples of the activating agent include amine oxide, sulfobetaine, carbobetaine, and the like;
Examples of the cationic surfactant include quaternary ammonium salts and the like. Among these, alkyl (C10-20) benzenesulfonates, alkyl (C10-20) or alkenyl (C10-20) sulfates, alkyl (C10-20) or alkenyl (C1
0-20) ether sulfates, polyoxyethylene alkyl or alkenyl ethers (ethylene oxide added mole number 4 to 30, alkyl or alkenyl group having 1 carbon atom)
0-20), and quaternary ammonium salts having at least one alkyl group having 10 to 20 carbon atoms are particularly preferred.

The amount of the surfactant is preferably 0.1
To 40% by weight, particularly preferably 0.1 to 30% by weight.

The bleaching composition of the present invention may further contain a sequestering agent. Examples of the sequestering agent include those described in JP-A-9-188896, column 14, line 44 to column 15, line 36, and examples thereof include the following.

(1) ethane-1,1-diphosphonic acid, ethane-
1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2- Phosphonic acids such as diphosphonic acid and methanehydroxyphosphonic acid, and alkali metal salts or alkanolamine salts thereof; (2) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylimino Aminopolyacetic acids such as diacetate, triethylenetetraminehexaacetic acid, diencoric acid and the like or alkali metal salts or alkanolamine salts thereof; (3) diglycolic acid, oxysuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid Acid, malic acid, gluconic acid, carboxymethyl succinic acid, mosquito Organic acids such as boxymethyltartaric acid or alkali metal salts or alkanolamine salts thereof; (4) alkali metal salts or alkanolamine salts of aluminosilicic acid represented by zeolite A; One or more selected ones are preferred.

The compounding amount of the sequestering agent is preferably from 0.0005 to 5% by weight, particularly preferably from 0.005 to 5% by weight.
1 to 1% by weight.

The bleach composition of the present invention may further contain a builder. Examples of the builder include water-soluble inorganic builders such as sulfate, carbonate, bicarbonate, silicate and phosphate. The amount of the builder is preferably 0.1 to 40% by weight.

The bleaching composition of the present invention may further contain a stabilizer for hydrogen peroxide. Examples of the stabilizer include magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium salts such as magnesium hydroxide, silicates such as sodium silicate, phosphoric acid, barbituric acid, uric acid, Acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, DL-tocopherol, gallic acid derivatives, butylated hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT), etc. Can be mentioned. The compounding amount of the stabilizer is preferably from 0 to 5% by weight, particularly preferably from 0.01 to 3% by weight.

The bleaching composition of the present invention may further contain a redeposition inhibitor. Examples of the anti-redeposition agent include carboxymethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol and the like. The compounding amount of the anti-redeposition agent is preferably 0.1 to 5.
0% by weight.

The bleaching composition of the present invention may further contain a discoloration preventing agent. As the anti-fading agent, phenylalanine, histidine, lysine, tyrosine, methionine and the like, or salts thereof, amino or imide compounds such as hydroxyiminodiacetic acid, acrylonitrile or acrylonitrile having a quaternary ammonium group can be copolymerized. And copolymers of one or more of these monomers. Although amino acids have optical isomers, optical isomers do not contribute to achieving the object of the present invention. Therefore, a chemically synthesized amino acid can be used as a discoloration inhibitor.
The compounding amount of the discoloration preventing agent is preferably 0.1 to 5% by weight.
It is.

The bleach composition of the present invention may further contain a fluorescent whitening agent. Examples of the fluorescent whitening agent include Tinopal CBS (manufactured by Ciba Geigy), Tinopal SWN (manufactured by Ciba Geigy), and color index fluorescent whitening agents 28, 40, and 5.
1, 71 and the like. The compounding amount of the optical brightener is preferably 0 to 5% by weight.

The bleach composition of the present invention may further contain a hydrotrope for the purpose of stabilizing the composition at low temperatures and improving freeze-recoverability and preventing liquid separation at high temperatures. Examples of the hydrotrope include short-chain alkylbenzene sulfonates such as toluene sulfonate and xylene sulfonate, ethanol, ethylene glycol, propylene glycol,
Alcohols represented by hexylene glycol, glycerin and the like can be mentioned. The blending amount of the hydrotrope is preferably 0 to 30% by weight.

The bleaching composition of the present invention may further contain about 0 to 2% by weight of a coloring agent such as a dye or a pigment, a silicone, a bactericide, an ultraviolet absorber and the like. The dye is preferably an acid dye having hydrogen peroxide resistance in an acidic solution. Further, the liquid bleach composition used in the present invention may contain enzymes such as cellulase, amylase, protease and lipase in order to improve the bleaching detergency.

The bleaching composition of the present invention may further contain a thickener in order to increase the viscosity of the liquid composition and improve the usability. Examples of the thickener include polyacrylates, acrylic acid / maleic acid copolymers, carboxymethylcellulose derivatives, methylcellulose, synthetic polymers such as hydroxymethylcellulose, chitansan gum, guar gum, natural polymers such as kelzan,
Water-swellable clay minerals such as montmorillonite and veegum can be mentioned. Also, by combining an amphoteric surfactant and an anionic surfactant as described in JP-A-1-319600, viscoelastic rheological properties can be imparted. The compounding amount of the thickener is such that the viscosity of the composition can be maintained in a desired range.

The bleaching composition of the present invention may further contain an alkali agent such as JIS No. 2 sodium silicate and an inorganic salt such as sodium sulfate in the case of a powdery composition.

When the bleaching composition of the present invention is a liquid composition, the pH of the composition itself is preferably 6 or less, particularly preferably 3 or less. In the case of a powdery composition, the pH when dissolved in water at the time of use is preferably 6 or more, particularly preferably 8 or more.

When the bleach composition of the present invention is in a liquid state, it is applied directly to clothing or dipped in clothing. In addition, it can be used in the same bath with a commercially available detergent. In the case of a powder, it can be used by dissolving it in tap water in advance and then used in the same manner as in the case of a liquid. Alternatively, it can be directly attached to an object to be treated and then added with water. In such a method of use, the amount of the component (b) is 1 to 1000 with respect to the amount of chlorine in tap water.
It is preferable to use it in an equivalent amount,
It is particularly preferable to use it in an equivalent amount.
It is more preferable to use it so that it becomes 00 equivalent.
Here, when the amount of the component (b) is 1 to 1,000 equivalents, a sufficient effect of suppressing discoloration or fading can be imparted, and it is economical.

[0041]

Examples 1 to 10 and Comparative Examples 1 to 5 The following (b-1) to (b-6) were used as hydrogen peroxide and an aromatic compound serving as a chlorine scavenger, and the following (c) was used as a surfactant. -1) to (c-4), and a liquid bleaching agent composition shown in Table 1 (% by weight) was obtained using the following (d-1) as a sequestering agent. In addition, (b'-
1) and (b'-2) were used as comparative examples.

[0042]

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[0043] c-1: alkyl (C12) benzene sulfonate c-2: N-tetradecyl -N, N-dimethyl -N- ethylammonium sulfate _{c-3: C 12 H 25} O (C 2 H 4 O) 8 Hc-4: fatty acid soap (sodium laurate) d-1: 1-hydroxyethylidene-1,1-diphosphonic acid (manufactured by Nippon Monsanto Co., trade name Diquest 201)
0).

These liquid bleach compositions were tested for the stability of hydrogen peroxide and the effect of inhibiting discoloration by the following methods. Table 1 shows the results.

(Stability of Hydrogen Peroxide) The liquid bleach composition was stored at 40 ° C. for 3 months, and then titrated with a 1 / 10N potassium permanganate standard solution to obtain an effective oxygen concentration. The residual ratio of hydrogen peroxide was determined, and the stability was evaluated.

[0046]

(Equation 1)

(Discoloration Inhibiting Effect) As a test cloth, a naphthol dye (dipping agent: Naphthol AS, developer: Fast Red GBa)
se), a cotton cloth (10 × 10 cm) dyed with the above was prepared. Effective chlorine concentration 0.01% by weight (approx.
Five test cloths were immersed for 30 minutes in a solution obtained by adding 20 g of the bleaching composition shown in Table 1 to 2 L of an aqueous chlorine solution (double the chlorine concentration). Thereafter, it was rinsed with tap water and dried. This operation was repeated 20 times, and the degree of discoloration (discoloration) was evaluated based on the discoloration prevention rate (%) obtained from the following equation. In addition, as a control, the same test was performed using only a chlorine aqueous solution to which no bleaching agent composition was added. The reflectance is Nippon Denshoku Industries
The measurement was performed using NDR-101DP manufactured by K.K. using a 460 nm filter. If the reflectance after bleach treatment is higher than the reflectance of the control, it is displayed as a negative value.

[0048]

(Equation 2)

[0049]

[Table 1]

As is clear from Table 1, the aromatic compound (b) used as the chlorine scavenger did not impair the bleaching power and exhibited an excellent discoloration preventing effect due to the chlorine scavenging property.

Examples 11 to 20, Comparative Examples 6 to 10 Sodium percarbonate, (b-1) to (b-6) of Table 1 as aromatic compounds serving as chlorine scavengers, and (b) of Table 1 as surfactants c-1) to (c-4), powder bleaching compositions shown in Table 2 (% by weight) using (d-1) of Table 1 and other components shown in Table 2 as sequestering agents I got something.
The stability of sodium percarbonate was tested for these powdered bleach compositions by the following method.
The discoloration inhibiting effect was tested in the same manner as in Example 1. Table 2 shows the results
Shown in

(Stability of sodium percarbonate) The powder bleach composition was stored at 40 ° C. and 80% relative humidity for 3 months.
Then, a 5% by weight aqueous solution was titrated with a 1 / 10N potassium permanganate standard solution to determine the effective oxygen concentration.
The remaining rate of sodium percarbonate was determined according to the above equation, and the stability was evaluated.

[0053]

[Table 2]

As is clear from Table 2, the aromatic compound (b) used as the chlorine scavenger did not impair the bleaching power, and exhibited an excellent discoloration preventing effect due to the chlorine scavenging property.

[0055]

According to the bleaching composition of the present invention, the aromatic compound (b) acts as a chlorine scavenger,
Both liquid and powder forms exhibit excellent bleaching detergency for textiles such as clothing and have the effect of inhibiting discoloration or fading when repeatedly washed with tap water. .

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Akira Ishikawa 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Institute (72) Inventor Muneo Aoyagi 1334 Minato, Wakayama City Wakayama Prefecture Kao Corporation Research Institute (72) Inventor Satoshi Suzuki 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Center

Claims (7)

[Claims] (1) an inorganic peroxide that generates hydrogen peroxide in an aqueous solution and (b) Taftσ ^* in the molecule ^.
Has one or more substituents having 0.5 or more, and an aromatic compound having a total Taftσ ^* of 2 to 5 in all the substituents. 2. The bleaching composition according to claim 1, wherein at least one of the substituents of component (b) is water-soluble. 3. Ta in the aromatic compound of the component (b)
When the substituent having ftσ ^* of 0.5 or more is NO ₂ , CN, OH,
OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ , OC ₆ H ₅ ,
COCH ₃ , COOH, COOCH ₃ , COOC ₂ H ₅ , C
3. The bleaching composition according to claim 1, which is 1 or SH. 4. The method according to claim 1, wherein the hydrophilic group in the aromatic compound as the component (b) is SO ₃ M or COOM [where M is a hydrogen atom,
Indicates an alkali metal atom or an alkaline earth metal atom. ]
The bleaching composition according to claim 1, 2 or 3, which is represented by the formula: 5. The aromatic compound of the component (b) has the following general formula (I): [Wherein one of X and Y is NO ₂ , CN, OH or OCH
₃ and the other represents SO ₃ M or COOM (where M has the same meaning as described above), and further from the above substituent group such that the sum of Taftσ ^* in all the substituents is 2 to 5. Indicates the selected group. The bleaching composition according to any one of claims 1 to 4, which is represented by the formula: 6. The bleaching composition according to claim 1, further comprising 1 to 50% by weight of a surfactant. 7. The method further comprises adding 0.0005 to the sequestering agent.
The bleaching composition according to any one of claims 1 to 5, comprising from 5 to 5% by weight.