JPH10245595A - Liquid bleach composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid bleach composition being one containing a batty acid ester of hydroxybenzenecarboxylic acid as the bleaching activator and being capable of giving efficient bleaching effect even when the content of the activator is small. SOLUTION: This composition contains 0.1-10wt.% hydrogen peroxide, 0.01-2.0wt.% bleaching activator represented by the formula [wherein R<1> is a 5-9C alkyl; and M is H, an alkali metal or an alkaline earth metal], 0.01-50wt.% nonionic surfactant and 0.05-2.0wt.% chelating agent having a calcium chelating constant (pkCa) of 4 or above and satisfying the requirements: the ratio bleaching activator/chelating agent is 1 or larger by mole, the ratio hydrogen peroxide/chelating agent is 150 or below by mole, and the ratio hydrogen peroxide/bleaching activator is 10-80 by mole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleaching composition, and more particularly, to a liquid bleaching composition which efficiently produces an organic peracid in an actual washing situation and has a high bleaching power. It is.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaching agents are limited in the fibers that can be used, and cannot be used for colors and patterns. Oxygen bleaching agents that do not have these disadvantages have recently become very popular because of their unique odor. Among these oxygen bleaching agents, sodium percarbonate and sodium perborate are used as powdered oxygen bleaching agents, and hydrogen peroxide is used as a liquid oxygen bleaching agent. However, these oxygen-based bleaches have a lower bleaching power than chlorine-based bleaches, and their improvement is required.

[0003] In order to compensate for these drawbacks, it has been practiced to increase the bleaching power by using a bleach activator in combination. Representative examples of such a bleaching activator include tetraacetylethylenediamine, acetoxybenzenesulfonates, tetraacetylglycolyl, glucose pentaacetate and the like. However, these bleach activators react with hydroperanions in a washing bath to produce peracetic acid, and have a high effect on hydrophilic stains, but have no effect on lipophilic stains. have.

As bleaching activators which have improved this disadvantage, the present inventors have disclosed JP-A-63-233969 and JP-A-63-31566.
As disclosed in JP-A-64-68347 and JP-A-1-190654, the reaction with hydrogen peroxide causes
It has been found that a compound that produces an organic peracid having a quaternary ammonium group is excellent. An example of a bleach activator having an anionic group in which a lipophilic group is introduced into a molecule is disclosed in
-12520, JP-A-8-143894, JP-A-8-143
143896 JP, JP-A-8-1443898, JP-A-7-82
No. 592.

Among these bleaching activators, the present inventors disclosed in Japanese Patent Application Laid-Open No. 7-82592 that storage stability was improved by solubilizing a fatty acid ester of p-hydroxybenzenecarboxylic acid in a nonionic surfactant. It discloses that a liquid bleach composition having excellent and high bleaching effect can be obtained. However, when the liquid bleaching composition contains a nonionic surfactant in an amount of 5% by weight or more, the bleaching effect can be efficiently obtained if the bleaching activator is added in an amount of 0.5% by weight or more. There is a problem that the blending amount of the bleaching activator is limited because the effect is reduced. Therefore, it has been desired to obtain a high bleaching effect even if the content of the bleaching activator is small.

Accordingly, an object of the present invention is to provide a liquid bleaching composition using a fatty acid ester of hydroxybenzenecarboxylic acid as a bleaching activator, whereby an efficient bleaching effect can be obtained even if the content of the bleaching activator is small. It is to provide a liquid bleach composition.

[0007]

The present inventors have found that the bleaching composition disclosed in the above-mentioned JP-A-7-82592 has a problem, that is, a fatty acid ester of hydroxybenzenecarboxylic acid is used as a bleaching activator. In the liquid bleach composition, the bleaching effect is remarkably reduced when the content of the bleaching activator is small, and to solve the problem that the desired bleaching effect cannot be obtained. The fatty acid ester has a carboxylic acid group and combines with the hardness component in tap water, and it is thought that organic peracid may not be generated efficiently, and as a result of earnestly examining a method of efficiently generating organic peracid, A chelating agent having a calcium chelate constant (pkCa) of 4 or more, and a chelate of a fatty acid ester of hydrogen peroxide and hydroxybenzenecarboxylic acid By limiting the compounding ratio with the agent within a specific range, an organic peracid is efficiently generated,
The inventors have found that bleaching can be performed effectively, and have completed the present invention.

That is, the present invention relates to a method for preparing a compound of the formula (I)

[0009]

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[In the formula, R ¹ represents a linear or branched alkyl group having 5 to 9 carbon atoms, and M represents H or an alkali metal or an alkaline earth metal. A bleach activator (hereinafter abbreviated as bleach activator (I)) 0.01 to 2.0% by weight, a nonionic surfactant 0.01 to 50% by weight and a chelating agent 0.05 to 2.0% by weight, A liquid bleaching composition characterized in that the chelating agent has a calcium chelating constant (pkCa) of 4 or more, and that the mixing ratio of hydrogen peroxide, bleach activator (I) and chelating agent satisfies the following formula: Is provided.

Bleach activator (I) / chelator (molar ratio) = 1 or more Hydrogen peroxide / chelator (molar ratio) = 150 or less Hydrogen peroxide / bleach activator (I) (molar ratio) = 10 ~ 80

[0012]

Embodiments of the present invention will be described below in detail.

[0013] The content of hydrogen peroxide in the bleach composition of the present invention is 0.1 to 10% by weight, preferably 1 to 5% by weight. If the content of hydrogen peroxide is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 10% by weight, storage stability decreases.

The bleach activator (I) used in the present invention is preferably a compound represented by formula (I-1).

[0015]

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[Wherein, R ¹ and M have the same meanings as above. In the general formulas (I) and (I-1), R ¹ represents a straight-chain or branched-chain alkyl group having 5 to 9 carbon atoms, preferably a straight-chain alkyl group having 7 to 9 carbon atoms. M 1 represents H 2, or an alkali metal such as Na or K, or an alkaline earth metal such as Ca or Ba, preferably H 2 or Na, and particularly preferably H 2.

The content of the bleach activator (I) in the bleaching composition of the present invention is 0.01 to 2.0% by weight, preferably 0.01 to 2.0% by weight.
0.5% by weight. 0.01% by weight bleach activator
If the amount is less than the above, sufficient bleaching performance cannot be obtained, and if the amount exceeds 2.0% by weight, the object of the present invention cannot be achieved.

Specific examples of the nonionic surfactant used in the present invention include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl Glycoside, fatty acid glycerin monoester and the like can be mentioned. Among these, nonionic surfactants shown in the following (1) and (2) are particularly preferable.

(1) a polyoxyethylene alkyl ether having an alkyl group having an average of 10 to 22 carbon atoms and having 1 to 30 mol of ethylene oxide added thereto; (2) a polyoxyethylene alkyl ether having an alkyl group having an average carbon number of 9 to 12; The content of the nonionic surfactant in the bleach composition of the present invention is 0.01 to 50% by weight, preferably 1 to 30% by weight, more preferably 5 to 25% by weight. ~ 30% by weight. If the content of the nonionic surfactant is less than 0.01% by weight, the bleaching activator (I) cannot be solubilized. If the content exceeds 50% by weight, the viscosity becomes high and handling becomes difficult.

The chelating agent used in the present invention has a calcium chelate constant (pkCa) of 4 or more. If the calcium chelate constant (pkCa) is less than 4, an organic peracid can be efficiently produced. Can not.

Here, the calcium chelate constant (pkC
a) is a calcium ion electrode and a chelating agent 0.1
It is a value measured using a 0.1% -NH ₄ Cl-NH ₄ OH buffer solution at pH 10, 25 ° C., at a weight% solution.

Specific examples of the chelating agent used in the present invention include ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminoacetic acid-based chelating agents such as hydroxyethyliminodiacetic acid or salts thereof; 1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1 Phosphonic acid-based chelating agents such as 1,2-diphosphonic acid and methanehydroxyphosphonic acid;
Examples include polycarboxylic acid-based chelating agents such as acrylic acid-maleic acid copolymers; and polyphosphoric acid-based chelating agents such as tripolyphosphoric acid. Among them, phosphonic acid chelating agents are particularly excellent.

The content of the chelating agent in the bleaching composition of the present invention is 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight.
It is. If the content of the chelating agent is less than 0.05% by weight, the rate of organic peracid generation becomes low during washing, so that bleaching power cannot be obtained efficiently. If it exceeds 2.0% by weight, it is uneconomical. Inconveniences such as cloudiness of the composition at low temperatures occur.

In the bleaching composition of the present invention, the mixing ratio of hydrogen peroxide, bleaching activator (I) and chelating agent is as follows:
The molar ratio of the bleaching activator (I) to the chelating agent is 1 or more, preferably 1 to 5, more preferably 1 to 2 for the bleaching activator (I) / chelating agent. The molar ratio of hydrogen peroxide / chelating agent is 150 or less, preferably 30 to 150, more preferably 50 to 120, and the molar ratio of hydrogen peroxide to bleach activator (I) is hydrogen peroxide / bleach activator. Agent (I) = 10-80, preferably 20-80.

The bleaching activator (I) / chelating agent molar ratio is less than 1 or the hydrogen peroxide / chelating agent molar ratio is less than 1.
If the ratio exceeds 150 or the molar ratio of hydrogen peroxide / bleaching activator (I) is out of the range of 10 to 80, the production rate of organic peracid decreases due to the effect of hardness components in tap water, and bleaching occurs. When the amount of the activator is large, the bleaching effect can be obtained because of the absolute amount of the organic peracid even if the production rate is low, but it is hard to say that it is effective. The bleaching effect cannot be obtained effectively.

In the bleaching composition of the present invention, at least one of an anionic surfactant and a cationic surfactant can be blended as required in addition to the nonionic surfactant. As the anionic surfactant used in the present invention, 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 Examples thereof include carboxylate salts, α-sulfofatty acid salts, and α-sulfofatty acid esters. Examples of the cationic surfactant include quaternary ammonium salts.

Among these anionic or cationic surfactants, in particular, alkyl (C ₁₀ -C ₂₀ ) benzenesulfonates, alkyl or alkenyl (C ₁₀ -C ₂₀ ) sulfates, alkyl or alkenyl (C ₁₀ -C ₂₀₎ ) Ether sulfates and quaternary ammonium salts having at least one alkyl group having 10 to 20 carbon atoms are particularly preferred. Also,
The content of these anionic or cationic surfactants,
The content is preferably 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, in the liquid bleach composition of the present invention.

The liquid bleaching composition of the present invention may contain known components which are usually added in addition to the above components. For example, water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates and phosphates can be used as builders. As a stabilizer for hydrogen peroxide, known magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicates such as sodium silicate can be used. Further, if necessary, a redeposition inhibitor such as carboxymethylcellulose, polyvinylpyrrolidone, or polyethylene glycol can be added.

The liquid bleaching composition of the present invention may also contain a hydrotrope for the purpose of stabilizing the liquid at low temperatures and improving freeze-recoverability and preventing liquid separation at high temperatures. No problem. As such a hydrotrope, generally, a short-chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin, etc. Representative examples include alcohols and polyhydric alcohols. The hydrotrope can be added in an amount of about 0 to 30% by weight in the liquid bleach composition of the present invention.

The liquid bleach composition of the present invention may further contain various compounds. For example,
Phosphoric acid, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline, phenacetin and the like, and DL-α-tocopherol, gallic acid derivatives, butyl known as hydrogen peroxide stabilizers Hydroxyanisole (BHA), 2,6-
Di-tert-butyl-4-methylphenol (BHT) and the like can be added. The amount of these stabilizers depends on the concentration of hydrogen peroxide, but it is usually about 0 to 5% by weight, preferably 0.01 to 3% by weight, in the composition of the present invention.

Further, the liquid bleach composition of the present invention may contain a substance known as a discoloration inhibitor. Such substances include phenylalanine, histidine,
Lysine, tyrosine, amino acids such as methionine and amino acid salts, and amino or imide compounds such as hydroxyiminodiacetic acid, and acrylonitrile and one or two or more monomers copolymerizable with acrylonitrile having a quaternary ammonium group And copolymers. Although amino acids have optical isomers, optical isomers do not participate in the effects of the present invention. Therefore, it is also possible to use chemically synthesized amino acids. In addition, the liquid bleach composition of the present invention contains Tinopearl (T) as a fluorescent whitening agent to increase the bleaching effect on white fiber.
inopal) CBS (manufactured by Ciba-Geigy),
A fluorescent whitening agent such as Tinopearl SWN (manufactured by Ciba Geigy) or a color index fluorescent whitening agent 28, 40, 61, 71 may be added in an amount of 0 to 5% by weight.

Further, a thickener can be added to the liquid bleaching composition of the present invention in an amount of 0 to 20% by weight for the purpose of increasing the viscosity of the composition and improving the usability. As the thickener, generally, a carboxymethylcellulose derivative,
Synthetic polymers such as methylcellulose and hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum and kelzan, and water-swellable clay minerals such as montmorillonite and veegum are used.

Further, the liquid bleaching composition of the present invention further comprises a coloring agent such as a dye or a pigment, a fragrance, a bactericide, an ultraviolet absorber, and an inorganic electrolyte (eg, NaCl, Na ₂ SO ₄ , CaCl ₂ ).
, Etc., can be added in appropriate amounts (each about 0 to about 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acidic solution is particularly preferable. Further, in the composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be blended as needed in order to improve the bleaching performance.

The pH of the liquid bleaching composition of the present invention is desirably 6 or less, preferably 3.5 or less, from the viewpoint of storage stability of hydrogen peroxide. In order to adjust the pH, an inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as toluenesulfonic acid or benzenesulfonic acid is used, or the above-described anionic surfactant is added in the form of an acid. It is preferable to use caustic such as sodium hydroxide or potassium hydroxide as necessary.

The liquid bleach composition of the present invention is applied directly to clothing and left for 10 to 30 minutes, and then washed or washed with an aqueous solution in which the liquid bleach composition of the present invention is previously dissolved in tap water. Can be immersed and bleached. Further, the liquid bleach composition of the present invention can be used by mixing with a conventionally known clothing detergent.

[0036]

According to the present invention, it is possible to provide a liquid bleaching composition which efficiently produces an organic peracid in an actual washing situation and has a high bleaching power.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 8 and Comparative Examples 1 to 6 The following components (b-1) to (b-
3), the following components (c-1) and (c-
2), LAS-S as an anionic or cationic surfactant
(Alkyl (C ₁₂ ) benzenesulfonic acid) and N-tetradecyl-N, N-dimethyl-N-ethylammonium ethyl sulfate (abbreviated as TDMEAS), Diquest 2 manufactured by Monsanto Japan as a chelating agent according to the present invention.
010CS (abbreviation D2010CS; pkCa = 7.1), ethylenediaminetetraacetate sodium salt (abbreviation EDTA / 4N
a; pkCa = 12.0) and sodium nitrilotriacetic acid (abbreviated as NTA · 3Na; pkCa = 6.6), and sodium gluconate (pkCa = 2.8) and sodium citrate (pkCa = 3.2) as comparative chelating agents. A liquid bleach composition having the composition shown in Table 2 was prepared. These were adjusted to pH 2.5 with an aqueous solution of N / 10 sulfuric acid or N / 10 NaOH.

[0039]

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Polyoxyethylene lauryl ether (EO = 8 mol) (c-1) Polyoxyethylene capryl ether (EO = 12 mol) (c-2) The organic peracid generation rate of the obtained composition was determined by the following method. And the bleaching performance was measured. The results are shown in Tables 1 and 2.

<Measurement of bleaching performance> Tables 1 and 2 were added to a 2 liter aqueous solution containing 0.0833% of a commercially available detergent solution (pH = 10.2).
Was added, and 5 pieces of black tea-stained cloth (hydrophilic soil) and 5 pieces of curry-stained cloth (lipophilic soil) prepared as described below were immersed for 15 minutes. Then, it was rinsed with tap water, dried, and the bleaching ratio was calculated by the following equation.

[0042]

(Equation 1)

The reflectance was NDR-10 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with DP using a 460 nm filter.

Preparation of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled with 3 liters of ion-exchanged water for about 15 minutes, filtered with bleached cotton after desizing, and cotton gold cloth # 2003 was immersed in this liquid. Boil for about 15 minutes. The sample was taken out of the fire and left for about 2 hours, then taken out and air-dried, washed with water until the washing liquid did not color, dehydrated, pressed, and subjected to an experiment as a 10 × 10 cm test piece.

Preparation of Curry-Contaminated Cloth After removing the solid content of house food retort curry (curry Marche) with a mesh, the resulting liquid was heated to boiling. Cotton gold cloth # 2003 was dipped in this solution and boiled for about 15 minutes. After being removed from the heat and left at room temperature for about 2 hours, the cloth was taken out, excess curry liquid adhering to the cloth was removed with a spatula, and the cloth was air-dried. Then, it was pressed and used as a 10 × 10 cm test piece in the experiment.

<Measurement of Peracid Generation Rate> Diameter 10 mm, length 30 mm
Was placed in a 1-liter glass beaker containing a cylindrical stirrer piece, and stirred at 100 rpm at 100 rpm. The bleaching compositions shown in Tables 1 and 2 were added all at once, and after a predetermined time shown in Tables 1 and 2, 0.3% was added.
10% aqueous catalase aqueous solution, and stirred for 1 minute,
The concentration of the generated organic peracid was measured by an iodine titration method to determine the peracid generation rate.

[0047]

[Table 1]

[0048]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3: 395 3:39) (72) Inventor Muneo Aoyagi 1334 Minato 1334 Wakayama-shi, Wakayama Prefecture Kao Corporation

Claims (6)

[Claims] 1. Hydrogen peroxide 0.1 to 10% by weight, represented by the general formula (I): ## STR1 ## [In the formula, R ¹ represents a linear or branched alkyl group having 5 to 9 carbon atoms, and M represents H or an alkali metal or an alkaline earth metal. (Hereinafter abbreviated as bleach activator (I)) 0.01 to 2.0% by weight, a nonionic surfactant 0.01 to 50% by weight, and a chelating agent 0.05 to 2.0%.
% By weight, the chelating agent has a calcium chelating constant (pkCa) of 4 or more, and the mixing ratio of hydrogen peroxide, bleach activator (I) and chelating agent satisfies the following formula: Liquid bleach composition. Bleach activator (I) / chelator (molar ratio) = 1 or more Hydrogen peroxide / chelator (molar ratio) = 150 or less Hydrogen peroxide / bleach activator (I) (molar ratio) = 10-80 2. The liquid bleaching composition according to claim 1, wherein the mixing ratio of hydrogen peroxide, bleach activator (I) and chelating agent satisfies the following formula. Bleach activator (I) / chelator (molar ratio) = 1-5 Hydrogen peroxide / chelator (molar ratio) = 30-150 Hydrogen peroxide / bleach activator (I) (molar ratio) = 20- 80 3. The liquid bleaching composition according to claim 1, wherein the mixing ratio of hydrogen peroxide, bleach activator (I) and chelating agent satisfies the following formula. Bleaching activator (I) / chelating agent (molar ratio) = 1 to 2 Hydrogen peroxide / chelating agent (molar ratio) = 50 to 120 Hydrogen peroxide / bleaching activator (I) (molar ratio) = 20 to 80 4. The content of hydrogen peroxide is 1 to 5% by weight, the content of bleach activator (I) is 0.01 to 0.5% by weight, and the content of nonionic surfactant is 1 to 30% by weight. %, And the content of the chelating agent is 0.1 to 1.0% by weight. The liquid bleach composition according to any one of claims 1 to 3. 5. The liquid bleach composition according to claim 1, wherein the chelating agent is a phosphonic acid chelating agent. 6. The composition according to claim 1, further comprising at least one kind of an anionic surfactant or a cationic surfactant.
A liquid bleaching composition according to any one of the preceding claims.