JPH09188896A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liq. bleaching agent compsn. which exhibits a satisfactorily high bleaching power to hydrophilic and hydrophobic stains, is excellent in storage stability, and does not become cloudy even at low temps. SOLUTION: This compsn. contains hydrogen peroxide, a surfactant, and at least one bleaching activator represented by the general formula (wherein R1 is 1-19C alkyl, etc.; M is H or a cation; and n is 2-10). The compsn. may further contain an arom. carboxylic acid compd. having at least one hydroxyl group.

Description

Detailed Description of the Invention

[0001]

The present invention relates to liquid bleach compositions. More specifically, the present invention relates to a liquid bleaching composition which exhibits high bleaching performance on lipophilic stains and hydrophilic stains and has excellent storage stability, and a liquid bleaching agent composition which does not become cloudy even when stored at low temperatures.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents. However, chlorine-based bleaching agents cannot be used for colors and patterns because of the limited fibers that can be used. In addition, oxygen-based bleaching agents such as sodium percarbonate, sodium perborate or hydrogen peroxide, which do not have these drawbacks, have recently been remarkably popular because they have a unique odor. Of these oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, hydrogen peroxide is used as a liquid oxygen-based bleaching agent, and liquid oxygen-based bleaching agents are used directly on clothing. It is especially preferred because it is easy to apply.

However, since these oxygen-based bleaching agents have lower bleaching power than chlorine-based bleaching agents, there is a demand for improvement thereof. In order to make up for these drawbacks, it has been practiced to use an oxygen bleaching agent in combination with a bleaching activator to enhance the bleaching power. Tetraacetylethylenediamine, acetoxybenzenesulfonates, tetraacetylglycolyl, glucose pentaacetate and the like are typically used as such a bleach activator, but these bleach activators are not used in an aqueous solution. Because of its stability, it is commonly used in powder bleaches.

Further, in recent years, studies have been made on the use of bleach activators for liquid bleaching agents. For example, JP-A-61-2308
Japanese Patent Publication No. 97 discloses a composition in which a solid bleaching activator is dispersed in an acidic aqueous solution containing hydrogen peroxide, which has excellent storage stability and exhibits activity at low temperatures. However, in this composition, since the bleaching activator is in a dispersed state, the bleaching activator precipitates and separates during storage, which significantly impairs the appearance of the product. Further, this composition gradually decomposes when the bleach activator is stored in an aqueous solution,
There was a problem that a satisfactory bleaching power could not be obtained during use. Further, WO9411475 discloses a liquid bleach composition in which two kinds of nonionic surfactants are solubilized and stabilized with triethyl acetylcitrate which is a bleach activator. Further, JP-A-7-3293 discloses a liquid bleach composition in which an alkanoyloxybenzene sulfonate, which is a bleach activator, is solubilized in a nonionic surfactant and stabilized.

Furthermore, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 6-207196,
JP-A-7-82591 and JP-A-7-82592 disclose liquid bleaching compositions in which a specific surfactant and a bleaching activator are combined. Further, JP-A-62-230897 discloses a liquid bleaching composition in which particles of a bleaching activator which produces an organic peracid are dispersed in an acidic aqueous solution containing hydrogen peroxide.

However, the bleach activators used for these produce an organic peracid having a lipophilic group such as an alkyl group, and thus show high bleaching power for lipophilic stains, but hydrophilic stains. On the other hand, since it has a small affinity with the organic peracid, it has a drawback that it is not effective. Further, in order to have a bleaching effect on hydrophilic stains, it is effective to add a bleaching activator that produces a hydrophilic organic peracid such as peracetic acid. It has been difficult to stabilize a bleach activator that produces peracid in an aqueous hydrogen peroxide solution.

Further, the storage stability of the bleach activator is not sufficiently satisfactory, and there is a problem that it gradually decomposes during storage and a satisfactory bleaching power cannot be obtained at the time of use. As a result, crystals of alkanoyloxybenzene sulfonate are deposited, and there is a problem that the appearance of the product is significantly impaired.

Therefore, an object of the present invention is to provide a liquid bleach composition having a high bleaching power which is satisfactory for hydrophilic and lipophilic stains and which is extremely excellent in storage stability. Another object of the present invention is to provide a liquid bleach composition having good low-temperature stability that does not become cloudy even when stored at low temperatures.

[0009]

As a result of intensive studies to solve the above problems, the present inventors have found that by combining hydrogen peroxide, a surfactant and a specific bleaching activator, hydrophilicity and A liquid bleaching composition having a high bleaching power for lipophilic stains and excellent storage stability is obtained, and by adding a specific aromatic carboxylic acid to this composition, it becomes cloudy even when stored at a low temperature. It was found that a liquid bleach composition which does not exist was obtained, and the present invention was completed.

That is, the present invention provides the following (a), (b) and
The present invention provides a liquid bleaching composition containing the component (c). (a) Hydrogen peroxide (b) Surfactant (c) One or more bleach activators represented by the general formula (1)

[0011]

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[Wherein R ₁ is substituted with an alkyl group or an alkenyl group having a total of 1 to 19 carbon atoms which may be interrupted by an ester group, an amide group or an ether group, or an alkyl group having a carbon number of 1 to 12] Represents an optionally substituted aryl group. M is
H 2 or an organic or inorganic cation. n is 2-10
Indicates the number of Further, the present invention, in addition to the components (a), (b) and (c),
Further, the present invention provides a liquid bleaching composition containing an aromatic carboxylic acid having at least one hydroxyl group in the molecule as the component (d).

In addition to the above-mentioned components (a), (b) and (c), or the above-mentioned components (a), (b), (c) and (d), the present invention further comprises The present invention provides a liquid bleach composition containing a bleach activator represented by

[0014]

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[In the formula, R ₁ and M have the above-mentioned meanings. ]

[0016]

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

[Component (b)] In the present invention, a surfactant is used as the component (b). Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants described in detail below, and even if any one of these is used alone. Alternatively, any two or more may be used in combination.

Examples of the anionic surfactant used in the present invention include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate ester salt, α-olefin sulfonate, saturated or unsaturated fatty acid salt, N-acyl. Amino acid type surfactants, alkyl or alkenyl ether carboxylates,
Examples thereof include amino acid type surfactants, alkyl or alkenyl phosphate ester salts and the like. In the present invention, these anionic surfactants preferably have an average carbon number of 8 to 22, more preferably an average carbon number of 8 to 2
2, especially 8 to 14 alkylbenzene sulfonates, and saturated fatty acid salts having an average carbon number of 8 to 22, especially 8 to 18, and more particularly 8 to 14.

Examples of the cationic surfactant used in the present invention include quaternary ammonium salts and the like.
Examples of the quaternary ammonium salt include compounds represented by the following general formula (4).

[0020]

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[In the formula, at least one of R _{3 to} R ₆ is an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and the rest are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. Furthermore, Z ^- represents an anion of an organic or inorganic. Specific examples of the quaternary ammonium salt represented by the general formula (4) include compounds represented by the following general formulas (4-1) and (4-2).

[0022]

[Chemical 6]

[Wherein, h is a number of 6 to 20, preferably 6 to 18, R ⁷ is an alkyl group of 1 to 3 or a hydroxyalkyl group, preferably an alkyl group of 1 to 3 carbon atoms, Z ⁻ is a halogen anion, an alkyl sulfate anion or a fatty acid anion. ]

[0024]

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[In the formula, g and d are each a number of 6 to 20, preferably 6 to 18, and R ⁷ and Z ^- have the above-mentioned meanings. Among the compounds represented by the above general formulas (4-1) and (4-2), particularly dioctyldimethylammonium salt, didecyldimethylammonium salt, didodecyldimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt Particularly preferred is hexadecyltrimethylammonium salt.

Examples of the nonionic surfactant used in the present invention include polyoxyethylene alkyl ethers; polyoxyethylene alkenyl ethers; polyoxyethylene alkylphenyl ethers; higher fatty acid alkanolamides; higher fatty acid alkanolamides. Alkylene oxide adduct of sucrose fatty acid ester;
Examples thereof include alkyl glucooxides, and the compounds represented by the following general formula (3) are preferable.

R ₂ -X- (AO) _m -Y (3) [In the formula, R ₂ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or an alkyl group having 1 to 18 carbon atoms. Represents an aryl group which may be substituted with a group, and X is -O-
Or -COO-. A represents an alkylene group having 1 to 5 carbon atoms, and m A's may be the same or different.
m represents an average value of 2 to 50. Y represents H or an alkyl group having 1 to 6 carbon atoms. In the general formula (3), R ₂ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or 1 carbon atom.
The aryl group which may be substituted with an alkyl group having 18 to 18 carbon atoms is shown, among which 6 to 22 carbon atoms, more preferably 6 to 18, and especially 8 to 14 carbon atoms.
Alkyl groups, especially linear alkyl groups are preferred. X is -O
-Or -COO- is shown, but -O- is preferable. A represents an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 3 and particularly preferably an ethylene group or a propylene group. m is an average value of 2 to 50, but 2 to 30 and 2
-20, especially 3-15 are preferred. Y is H or has 1 to 6 carbon atoms
Are preferred, but H 2 or an alkyl group having 1 to 3 carbon atoms is preferable, and H 2 or a methyl group is particularly preferable.

In the general formula (3), the alkylene oxide group represented by -AO- may be polymerized in a block type or a random type. Table 1 shows specific examples of these nonionic surfactants.

[0029]

[Table 1]

Examples of the amphoteric surfactant used in the present invention include amine oxide, sulfobetaine, carbobetaine and the like.

In the present invention, as the component (b) surfactant,
At least one selected from these anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants is used. Among these, nonionic surfactants are particularly preferred, and the nonionic surfactants shown below are particularly preferred. Surfactants are preferred.

[0032] _{C 8 H 17 - (OC 2} H 4) a -OH C 10 H 21 - (OC 2 H 4) a -OH C 12 H 25 - (OC 2 H 4) a -OH C 14 H 29 - _{(OC 2 H 4) a -OH} C 16 H 33 - (OC 2 H 4) a -OH C 18 H 37 - (OC 2 H 4) a -OH C 8 H 17 - (OC 2 H 4) a - _{OCH 3 C 10 H 21 - (} OC 2 H 4) a -OCH 3 C 12 H 25 - (OC 2 H 4) a -OCH 3 C 14 H 29 - (OC 2 H 4) a -OCH 3 C 16 H _{33 - (OC 2 H 4)} a -OCH 3 C 18 H 37 - (OC 2 H 4) a -OCH 3 C 7 H 15 CO- (OC 2 H 4) a -OH C 9 H 19 CO- (OC ₂ H ₄ ) _a -OH C ₁₁ H ₂₃ CO- (OC ₂ H ₄ ) _a -OH C ₁₃ H ₂₇ CO- (OC ₂ H ₄ ) _a -OH C ₁₅ H ₃₁ CO- (OC ₂ H ₄ ) _a -OH C ₁₇ H ₃₅ CO- (OC ₂ H ₄ ) _a -OH C ₇ H ₁₅ CO- (OC ₂ H ₄ ) _a -OCH ₃ C ₉ H ₁₉ CO- (OC ₂ H ₄ ) _a -OCH ₃ C ₁₁ H ₂₃ CO- (OC ₂ H ₄ ) _a -OCH ₃ C ₁₃ H ₂₇ CO- (OC ₂ H ₄ ) _a -OCH ₃ C ₁₅ H ₃₁ CO- (OC ₂ H ₄ ) _a -OCH ₃ C ₁₇ H _{35 CO- (OC 2 H 4)} a -OCH 3 where a is a number of 2 to 20.

[Component (c)] In the present invention, as the component (c),
The bleaching activator represented by the above general formula (1) is used.
In the general formula (1), R ₁ is substituted with an alkyl group or alkenyl group having 1 to 19 carbon atoms, which may be interrupted by an ester group, an amide group, or an ether group, or an alkyl group having 1 to 12 carbon atoms. Shows an aryl group which may be, preferably an alkyl group or an alkenyl group having 1 to 19 carbon atoms, or an aryl group optionally substituted by an alkyl group having 1 to 12 carbon atoms, particularly 5 to 19 carbon atoms, Further, an alkyl group or an alkenyl group of 5 to 11 is preferable, and an alkyl group is particularly preferable. Here, the total carbon number refers to the carbon number calculated including the groups interrupted by an ester group, an amide group or an ether group.

Further, M represents H 2 or an organic or inorganic cation, but H 2, an alkali metal or an alkaline earth metal is preferable, and H 2 is particularly preferable. Further, n represents a number of 2 to 10, preferably a number of 2 to 5.

Examples of the bleach activator represented by the general formula (1) include compounds represented by the following general formulas (1-1) to (1-8), among which (1-1) And the compounds represented by (1-5) are preferable, and the para-form represented by (1-1) is particularly preferable.

[0036]

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(Wherein i is 1 to 19, preferably 5
-19, more preferably 5-11, particularly preferably 7-11, j is 1-17, preferably 3-17, k is 1-18,
Preferably a number of 4-18, n is 2-10, preferably 2-5
Indicates the number of The component (c) of the present invention may be a single bleach activator consisting of a compound of the general formula (1) in which n is only one, or a mixture of two or more bleach activators consisting of compounds of different n. May be In the case of a mixture of two or more bleaching activators consisting of compounds in which n is different, a preferable composition is 0.1 to 99% by weight of n = 2, preferably 20 to 99% by weight, and 0.1 of n = 3. ~ 99% by weight, preferably 1-80
% By weight, n = 4 0 to 60% by weight, preferably 0 to
30% by weight, n = 5, 0-40% by weight, preferably 0
10% by weight.

These bleach activators can be synthesized by mixing the corresponding fatty acid chloride with p-hydroxybenzoic acid or salicylic acid in a specific ratio such as toluene, acetone, acetonitrile, dimethylformamide, dimethylacetamide or xylene. It can be synthesized by using an ordinary esterification reaction using a water solvent or without a solvent. In the esterification reaction of such a fatty acid chloride with p-hydroxybenzoic acid or salicylic acid, an acid chloride exchange reaction occurs to obtain a mixture of n = 1 to 10. In addition, p-hydroxybenzoic acid or salicylic acid is previously reacted with an acid chlorinating agent such as phosphorus trichloride or thionyl chloride at a specific ratio to obtain an esterification condensate, and then the esterification condensate is usually used. It can also be synthesized by dehydration esterification using the above fatty acid or esterification using fatty acid chloride.

The bleach activator synthesized by these methods is
By changing the molar ratio of fatty acid chloride or fatty acid to p-hydroxybenzoic acid or salicylic acid, p
The degree of condensation n of hydroxybenzoic acid or salicylic acid can be changed. Further, when produced by such a synthetic method, a mixture composed of compounds having different condensation degrees n is obtained, and such a mixture may be used as it is as the component (c) of the present invention, or may be recovered from the mixture. A single bleach activator may be used as the component (c) by extracting only compounds having the same degree of condensation n by purification such as crystallization or distillation.

When synthesized by the above synthesis method, unreacted p-
In addition to hydroxybenzoic acid and salicylic acid, a condensate of p-hydroxybenzoic acid or salicylic acid that has not been esterified with a fatty acid may be contained as an impurity. Such a condensate also reacts with hydrogen peroxide to produce organic peroxide. Since an acid can be generated, there is no particular problem even if it is contained in the component (c) to some extent. However, since such a condensate has low storage stability in a liquid bleach composition, in order to reduce the amount of such a condensate and improve the storage stability of the liquid bleach composition, it is preferably 30% by weight. Less than 10% by weight, more preferably less than 10% by weight.

In the present invention, basically, the bleaching activator represented by the above general formula (1) is used as the component (c), but the bleaching activator represented by the above general formula (2) is further added. May be included.

When the bleaching activator used in the present invention is a mixture of the bleaching activator represented by the general formula (1) and the bleaching activator represented by the general formula (2), The blending ratio of the bleaching activator of the formula (1) and the bleaching activator of the general formula (2) is (1) / (2) = 1 / 1000-1000 / 1, preferably 1 / 100- 100/1 is more preferable, especially 1/50 to
100/1 is preferred.

[Component (d)] In the present invention, in order to obtain a liquid bleach composition which does not become cloudy even when stored at low temperature,
Aromatic carboxylic acids having at least one hydroxyl group in the molecule are used as the component (d).

As the aromatic carboxylic acid having at least one hydroxyl group in the molecule, salicylic acid,
Examples thereof include p-hydroxybenzoic acid and m-hydroxybenzoic acid, with salicylic acid and p-hydroxybenzoic acid being preferred.

[Liquid Bleaching Agent Composition] The liquid bleaching agent composition of the present invention contains the above-mentioned components (a) to (c) as essential components, and the content of each component is as follows: 0.5-20% by weight, preferably 0.5-10% by weight, more preferably 1-6
% By weight, and the component (b) is 0.1 to 50% by weight, preferably
0.5 to 30% by weight, more preferably 1 to 20% by weight,
The component (c) is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight. like this
The contents of the components (a) to (c) are defined on the basis of the following reasons, but when the following reasons are not taken into consideration, the blending amount of each component in the present invention is the above blending amount. It is not bound by quantity.

Component (a): 0.5% by weight or more is preferable in order to make the bleaching performance of the liquid bleaching composition sufficient.
Further, in order to sufficiently maintain the stability of hydrogen peroxide in the liquid bleaching composition, it is preferably 20% by weight or less. Component (b): 0.1% by weight or more is preferable in order to make the stability of the bleach activator in the liquid bleach composition sufficient, and the liquid bleach composition is easy to handle because the increase in viscosity is suppressed. 50% by weight or less is preferable to obtain the product. (c) Component: In order to obtain a liquid bleaching composition capable of obtaining sufficient bleaching performance, the content is preferably 0.05% by weight or more, and a liquid bleaching agent composition which suppresses an increase in viscosity and is easy to handle To achieve this, it is desirable that the amount be 20% by weight or less.

When the component (d) is contained in addition to the above components (a) to (c), the content of the component (d) is 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, more preferably Is 0.1
~ 0.5% by weight. (d) Content of component 0.001% by weight
By the above, it is possible to prevent the crystals of the bleaching activator from precipitating at a low temperature, and to obtain a liquid bleaching agent composition having a transparent appearance without clouding. The storage stability of the bleach activator can be kept good.

Further, the liquid bleach composition of the present invention comprises e)
A sequestering agent can be added as a component. Examples of the sequestering agent include (1) a phosphoric acid compound such as phytic acid or an alkali metal salt or an alkanolamine salt thereof (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, Ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-
Triphosphonic acid, ethane-1,2-dicarboxy-1,2-
Phosphonic acid such as diphosphonic acid, methanehydroxyphosphonic acid or an alkali metal salt or alkanolamine salt thereof (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or alkali metal salts or alkanolamine salts thereof (4) aspartic acid, glutamic acid, amino acids such as glycine or alkali metal salts or alkanolamine salts thereof (5) nitrilotriacetic acid, Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and dienecoric acid, or their alkali metal salts or alkanolamine salts (6) Glycolic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid Acid, malic acid, oxydisuccinic acid,
Gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, α-hydroxypropionic acid, α-hydroxyisobutyric acid, and other organic acids or their alkali metal salts or alkanolamine salts (7) Alkaline aluminosilicate represented by zeolite A Metal salt or alkanolamine salt (8) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or polyethylenepolyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt.

Among these, the above (2), (5), (6) and
At least one selected from the group consisting of (7) is preferable, and at least one selected from the group consisting of (2) and (6) above is more preferable.

The amount of such a sequestering agent is from 0.0005 to 5% by weight, preferably from the liquid bleaching composition of the present invention.
0.01 to 1% by weight is desirable.

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. In addition, as a stabilizer for peroxides or hydrogen peroxide adducts, known magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium salts such as magnesium hydroxide, and silicates such as sodium silicate are used. be able to. Further, if necessary, a redeposition inhibitor such as carboxymethylcellulose, polyvinylpyrrolidone, or polyethylene glycol can be added.

The liquid bleach composition of the present invention basically comprises the above-mentioned components (a), (b) and (c), components (a), (b), (c) and (d) and (a). ), (b), (c) and (e) components, or (a), (b), (c),
Although the components (d) and (e) are dissolved or dispersed in water, the hydrotrope is used for the purpose of improving the stability and freeze-restoration of the liquid at low temperature and preventing the liquid separation at high temperature. It does not matter if an agent is added. As such a hydrotrope, in general, toluene sulfonate,
Examples thereof include short-chain alkylbenzene sulfonates represented by xylene sulfonate, alcohols represented by ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin and the like, 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.

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

Further, the liquid bleaching composition of the present invention may contain a substance known as an anti-fading agent. 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. When the anti-browning agent is added, the addition amount thereof is preferably 0.001 to 1.0% by weight in the composition of the present invention.

In the liquid bleach composition of the present invention, Tinopal CBS [Ciba Geigy (Cib Geigy (Cib
a-Geigy), Chinopearl SWN [Ciba-Geigy] and color index fluorescent whitening agents 28, 40, 6
A fluorescent whitening agent such as 1,71 may be added in an amount of 0 to 5% by weight.

Further, the liquid bleaching composition of the present invention may contain a thickener 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, polyacrylates, acrylic acid-maleic acid copolymer, carboxymethylcellulose derivatives, methylcellulose, synthetic polymers such as hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum, kelzan, montmorillonite, veegum Water-swellable clay minerals are used. The addition amount of these thickeners is preferably 0 to 20% by weight in the composition of the present invention.

Further, the liquid bleaching composition of the present invention further comprises colorants such as dyes and pigments, fragrances, silicones, germicides, ultraviolet absorbers, inorganic electrolytes (eg NaCl,
Na ₂ SO ₄ , CaCl ₂ ) and other various trace additives in appropriate amounts (each 0
To about 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acidic solution is particularly preferable.

In the composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) may be added, if necessary, in order to improve the bleaching performance.

The pH of the liquid bleach composition of the present invention is preferably 6 or less, more preferably 3.5 or less. In order to adjust the pH, use an inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as toluenesulfonic acid or benzenesulfonic acid, or use the above-described metal-sequestering agent or anionic surfactant in an acid form. Or, if necessary, by using a caustic such as sodium hydroxide or potassium hydroxide.

The liquid bleaching composition of the present invention can also be used as a mixture with a conventionally known clothes detergent.

[0061]

EXAMPLES The present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited to these examples.

Synthesis Example 1: Synthesis of the following compound (c-1)

[0063]

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Glass 1 with a capacity of 1 liter equipped with a cooling tube, a thermometer, a dropping funnel and a mechanical stirrer
A one-necked flask was charged with 300 ml of toluene and 1 mol of p-hydroxybenzoic acid, and the temperature was raised to 100 ° C. Thereafter, 1.5 mol of octanoyl chloride was added dropwise from the dropping funnel over about 30 minutes, and aged at 100 ° C. for about 5 hours. After cooling, the reaction mixture was allowed to stand overnight at -10 ° C. The precipitated crystals were collected by filtration, washed with hexane several times and then dried to obtain compound (c-1). 57% yield, compound by high performance liquid chromatography (hereinafter abbreviated as HPLC)
It was confirmed that (c-1) had the following composition.

P = 1 ... 24.7 wt% p = 2 ... 62.8 wt% p = 3 ... 5.5 wt% Others …… 7.0 wt% (where p is the value of p in the above formula (c-1)) Synthetic Example 2: Synthesis of the following compound (c-2)

[0066]

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The compound (c-1) synthesized in Synthesis Example 1 was recrystallized several times with hexane to obtain a compound (c-2). It was confirmed by HPLC that the compound (c-2) had the following composition.

Q = 2 96.2% q = 3 0.3% Solvent 3.5% (where q is the value of q in the above formula (c-2)) Synthesis Example 3: Compound below Synthesis of (c-3)

[0069]

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Glass 1 with a capacity of 1 liter equipped with a cooling tube, a thermometer, a dropping funnel and a mechanical stirrer
To a one-necked flask, 300 ml of toluene and 1 mol of salicylic acid were charged, and the temperature was raised to 50 ° C. Thereafter, 0.5 mol of thionyl chloride was added dropwise from the dropping funnel over about 30 minutes, and the mixture was aged at 50 ° C. for about 2 hours. Thereafter, the solvent was distilled off to obtain a white powder. The whole powder was charged again into a 4-liter glass flask with a capacity of 1 liter equipped with a cooling tube, a thermometer, a dropping funnel and a mechanical stirrer, and 500 ml of toluene.
Was added and the temperature was raised to 100 ° C. 0.8 mol of lauroyl chloride was added dropwise from the dropping funnel over about 30 minutes, and the mixture was heated at 100 ° C for about 5 minutes.
Aged for hours. After cooling, the mixture was allowed to stand at -10 ° C for 24 hours, and the precipitated crystals were collected by filtration. It was washed with hexane several times and dried to obtain a compound (c-3). Yield 43%, compound (c
It was confirmed that -3) had the following composition.

R = 2 …… 26.4% r = 3 …… 61.1% r = 4 …… 6.3% r = 5 …… 1.2% Others …… 5.0% (where r is in the above formula (c-3)) The value of r is shown.) Synthesis example 4: Synthesis of the following compound (c-4)

[0072]

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The compound (c-3) synthesized in Synthesis Example 3 was recrystallized several times with hexane to obtain a compound (c-4). It was confirmed by HPLC that (c-4) had the following composition.

S = 2 ... 0.3% s = 3 ... 93.7% s = 4 ... 0.5% solvent ... 5.5% (where s represents the value of s in the above formula (c-4)) Examples 1 to 6 and Comparative Examples 1 to 6 Hydrogen peroxide as the component (a) and the following (b-1) as the component (b)
(b-5), (c) component synthesized in the above synthesis example (c-1) ~
A liquid bleach composition having the compositions shown in Tables 2 and 3 using the following (e-1) as the components (c-4) and (e) and the following (c'-1) as the other bleach activator. Was prepared, and its storage stability and bleaching performance were measured by the following methods. The results are shown in Tables 2 and 3. The bleaching agent compositions were adjusted to pH 2.5 with 0.1N sulfuric acid aqueous solution.

[0075]

Embedded image

<Evaluation Method of Storage Stability> In each of the Examples and Comparative Examples, after storing the liquid bleaching composition under the conditions shown in Table 2 or Table 3, the organic peracid in the composition was formed. The amount of the bleach activator was measured by HPLC, and the effective bleach activator residual rate was calculated by the following formula.

[0077]

[Equation 1]

<Method of measuring bleaching performance> A 2 liter aqueous solution containing 0.0833% of a commercially available aqueous detergent solution (pH = 10.2) was used, and the bleaching agent composition shown in each Example and Comparative Example was stored before being stored. 2 and 40 ml each of which was stored under the conditions shown in Table 3 were added respectively, and 5 pieces of black tea-contaminated cloth (hydrophilic stain) and 5 pieces of curry-contaminated cloth (lipophilic stain) prepared as follows were prepared.
Immerse for a minute. Thereafter, it was rinsed with tap water, dried, and the bleaching ratio was calculated by the following equation.

[0079]

[Equation 2]

The reflectance is NDR-101D manufactured by Nippon Denshoku Industries Co., Ltd.
Measured using P at 460 nm filter.

Preparation method of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes, then rubbed with de-squeezed bleached cotton, and soaked cotton cloth # 2003 in this liquid. Boiled for about 15 minutes. It was removed from the heat as it was and left for about 2 hours, then taken out, naturally dried, washed with water until the washing liquid became colorless, dehydrated, pressed, and then subjected to an experiment as a 10 × 10 cm test piece.

Method for Preparing Curry-Contaminated Cloth After removing the solid content of the house food retort curry (curry marche) with a mesh, the obtained solution was heated to boiling. Cotton gold cloth # 2003 was dipped in this solution and boiled for about 15 minutes. After removing from the fire and leaving it to room temperature,
The cloth was pulled out, the excess curry solution was removed with a spatula, and air-dried. Then, it was pressed and used as a 10 × 10 cm test piece in the experiment.

[0083]

[Table 2]

[0084]

[Table 3]

Examples 7 to 12 and Comparative Examples 7 to 11 Hydrogen peroxide as the component (a) and the following (b-6) as the component (b)
(b-8), (c) synthesized in the above synthesis example as the component (c-1) ~
(c-4), (d-1) and (d-2) as the (d) component, and (e-2) to (e-4) below as the (e) component are used. A liquid bleach composition having the composition shown below was prepared, and its storage stability, low temperature stability and bleaching performance were measured by the following methods. The results are shown in Tables 4 and 5. These bleach compositions are
The pH was adjusted to 2.5 with 0.5N sulfuric acid aqueous solution.

(B) Component C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₈ -OH (b-6) C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₁₀ -OH (b-7) C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₁₃ -OH (b-8) (d) Component p-hydroxybenzoic acid (d-1) salicylic acid (d-2)

[0087]

Embedded image

<Evaluation Method of Storage Stability> Evaluation was carried out by the same method as in Examples 1 to 6. <Low-temperature stability> The liquid bleaching composition was placed in a 50 cc transparent glass container with a lid, and after storing at 0 ° C for 20 days, the liquid feeling was visually observed.

<Method of measuring bleaching performance> To a 2 liter aqueous solution containing 0.0833% of a commercially available aqueous detergent solution (pH = 10.2), 40 ml of the liquid bleaching agent composition shown in Table 4 and Table 5 was added. Each of the black tea-contaminated cloths prepared in the same manner as in Nos. 6 and 5 and the curry-contaminated cloths prepared as described below was immersed for 5 minutes each. After sufficiently rinsing with tap water and drying, the bleaching rate was calculated by the same formula as in Examples 1-6.

Preparation of Curry Contaminated Cloth Bonsai curry manufactured by Otsuka Pharmaceutical Co., Ltd. was heated at 80 ° C. for 30 minutes, filtered through a colander, and the cotton wire cloth # 2003 was dipped in the liquid from which solid matter was removed, and heated for about 15 minutes. . After leaving it for about 2 hours,
The cloth was taken out from the liquid, the excess liquid was removed, and the product was naturally dried. After pressing, the test piece was used as a 10 cm × 10 cm test piece.

[0091]

[Table 4]

[0092]

[Table 5]

[0093]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid bleaching composition which has a high bleaching effect on both lipophilic stains and hydrophilic stains and is also excellent in storage stability.
Moreover, according to this invention, the liquid bleaching agent composition which does not become cloudy even if it stores at low temperature can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Muneo Aoyagi 1334 Minato, Wakayama City, Wakayama Pref.

Claims (16)

[Claims] 1. A liquid bleaching composition comprising the following components (a), (b) and (c): (a) Hydrogen peroxide (b) Surfactant (c) One or more bleach activators represented by the general formula (1) (In the formula, R ₁ may be substituted with an alkyl group or an alkenyl group having 1 to 19 carbon atoms which may be interrupted by an ester group, an amide group or an ether group, or an alkyl group having 1 to 12 carbon atoms. It represents a good aryl group. M represents H 2 or an organic or inorganic cation. n shows the number of 2-10. ] 2. The content of component (a) is 0.5 to 20% by weight, and (b)
The content of the component is 0.1 to 50% by weight, and the content of the component (c) is 0.
The liquid bleach composition according to claim 1, which is from 05 to 20% by weight. 3. The liquid bleaching composition according to claim 1, which further comprises, as the component (d), an aromatic carboxylic acid having at least one hydroxyl group in the molecule. 4. The liquid bleaching composition according to claim 3, wherein the content of the component (d) is 0.001 to 1% by weight. 5. The liquid bleaching composition according to claim 1, further comprising a bleaching activator represented by the following general formula (2). Embedded image [In the formula, R ₁ and M have the above-mentioned meanings. ] 6. The blending ratio of the bleaching activator represented by the general formula (1) and the bleaching activator represented by the general formula (2) is (1)
/ (2) (weight ratio) = 1/1000 to 1000/1. The liquid bleaching composition according to claim 5. 7. The R ₁ is an alkyl group or an alkenyl group having 1 to 19 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 12 carbon atoms. The liquid bleaching composition according to. 8. The liquid bleaching composition according to claim 1, wherein R ₁ is an alkyl group or an alkenyl group having 5 to 19 carbon atoms. 9. The liquid bleaching composition according to claim 1, wherein M is H, an alkali metal or an alkaline earth metal. 10. The liquid bleaching composition according to any one of claims 1 to 9, wherein n is a number of 2 to 5. 11. The liquid bleaching composition according to claim 1, wherein the surfactant as the component (b) is a nonionic surfactant. 12. The nonionic surfactant has the following general formula:
The liquid bleaching composition according to claim 11, which is a nonionic surfactant represented by (3). R ₂ -X- (AO) _m -Y (3) [In the formula, R ₂ is substituted with a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or an alkyl group having 1 to 18 carbon atoms. Represents an optionally substituted aryl group, and X is -O-
Or -COO-. A represents an alkylene group having 1 to 5 carbon atoms, and m A's may be the same or different.
m represents an average value of 2 to 50. Y represents H or an alkyl group having 1 to 6 carbon atoms. ] 13. In the general formula (3), R ₂ has 6 to 6 carbon atoms.
20 is a straight-chain alkyl group, X is -O-, A is an alkylene group having 2 to 3 carbon atoms, m is a number of 2 to 20, Y is H or 1 to 3 carbon atoms. The liquid bleaching composition according to claim 12, which is an alkyl group. 14. The liquid bleaching composition according to any one of claims 3 to 13, wherein the component (d) is salicylic acid or p-hydroxybenzoic acid. 15. The liquid bleaching composition according to claim 1, which contains a sequestering agent as the component (e). 16. The liquid bleaching composition according to claim 15, wherein the content of the sequestering agent is 0.0005 to 5% by weight.