JPH0959676A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid bleaching agent composition excellent in storage stability and having high bleaching power. SOLUTION: This composition contains 0.5-10wt.% hydrogen peroxide, 0.1-30wt.% of one or more nonionic surfactants and 0.1-10wt.% bleaching activator comprising a nitrilated quaternary ammonium salt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid bleaching composition containing a specific bleaching activator, more specifically, a liquid bleaching composition having excellent storage stability and high bleaching power. Regarding

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents, but chlorine-based bleaching agents are limited in the fibers that can be used. Oxygen-based bleaching agents, which do not have these drawbacks, have recently become extremely popular because they cannot be used and have a characteristic odor. Among these oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid oxygen-based bleaching agent. However, these oxygen-based bleaches have 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. Furthermore, JP-A-4-228000
No. 4-253947 or 2-13
No. 2196 discloses a bleach activator having a high bleaching performance, which comprises a quaternary ammonium salt having a nitrile group.

By the way, these bleach activators are unstable in an aqueous solution and are generally used for powder bleaching agents, but their use for liquid bleaching compositions has also been studied. 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. Further, JP-A-7-70593 discloses a fluid aqueous liquid detergent composition containing a substantially water-insoluble organic peroxy acid. Furthermore, the present inventors have disclosed in JP-A-6-207196 and JP-A-7-82591 a liquid bleaching agent composition in which a specific surfactant and a bleaching activator are combined.

However, these liquid bleaching compositions use an ester compound as a bleaching activator, and it is difficult to apply them to the bleaching activator composed of the above quaternary ammonium salt having a nitrile group. .

Accordingly, it is an object of the present invention to provide a liquid bleaching composition having a high bleaching power which is excellent in storage stability and which contains a bleaching activator comprising a quaternary ammonium salt having a nitrile group. It is in.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have combined a specific surfactant with a bleach activator composed of a quaternary ammonium salt having a nitrile group. As a result, they have found that the above problems can be solved, and have completed the present invention.

That is, the present invention provides (a) 0.5% hydrogen peroxide.
To 10% by weight, (b) 0.1 to 30% by weight of one or more nonionic surfactants, and (c) a nitrile group 4
A liquid bleaching composition comprising 0.1 to 10% by weight of a bleaching activator comprising a primary ammonium salt.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. [Component (a)] In the present invention, hydrogen peroxide is used as the component (a).

[Component (b)] In the present invention, one or more nonionic surfactants are used as component (b). As the nonionic surfactant blended as the component (b), the compound represented by the general formula (3) is preferable.

R ¹² -B- (AO) _m -Y (3) [wherein R ¹² is a linear or branched C 6-22, preferably 8-18, more preferably 10-18 alkyl. Represents a group or an alkenyl group, or represents an aryl group which may be substituted by a linear or branched alkyl group having 1 to 18 carbon atoms, of which the alkyl group is preferable. B represents an -O- group or a -COO- group, preferably an -O- group. A represents a linear or branched alkylene group having 2 to 3 carbon atoms, and m A's may be the same or different. Y is H or 1 to 3 carbon atoms
Is an alkyl group. m is a number of 3 to 50, preferably 3 to 20, more preferably 4 to 15, which represents the average number of moles of alkylene oxide added. ] In the general formula (3), AO
Represents ethylene oxide or propylene oxide,
These may be added to the block type or may be added to the random type. Specific examples of the compound represented by the general formula (3) include the following compounds.

C ₁₀ H ₂₁ O (C ₂ H ₄ O) _m -HC ₁₂ H ₂₅ O (C ₂ H ₄ O) _m -HC ₁₄ H ₂₉ O (C ₂ H ₄ O) _m -HC ₁₆ H ₃₃ O (C ₂ H ₄ O) _m -HC ₁₈ H ₃₇ O (C ₂ H ₄ O) _m -HC ₂₀ H ₄₁ O (C ₂ H ₄ O) _m -HC ₁₀ H ₂₁ O (C ₃ H ₆ O) _m -HC ₁₂ H ₂₅ O (C ₃ H ₆ O) _m -HC ₁₄ H ₂₉ O (C ₃ H ₆ O) _m -HC ₁₆ H ₃₃ O (C ₃ H ₆ O) _m -HC ₁₈ H ₃₇ O (C ₃ H ₆ O) _m -HC ₂₀ H ₄₁ O (C ₃ H ₆ O) _m -HC ₉ H ₁₉ COO (C ₂ H ₄ O) _m -HC ₁₁ H ₂₃ COO (C ₂ H ₄ O) _m -HC ₁₃ H ₂₇ COO (C ₂ H ₄ O) _m -HC ₁₅ H ₃₁ COO (C ₂ H ₄ O) _m -HC ₁₇ H ₃₅ COO (C ₂ H ₄ O) _m -HC ₁₉ H ₃₉ COO (C ₂ H ₄ O) _m -HC ₁₀ H ₂₁ O (C ₂ H ₄ O) _m -CH ₃ C ₁₂ H ₂₅ O (C ₂ H ₄ O) _m -CH ₃ C ₁₄ H ₂₉ O (C ₂ H ₄ O) _m -CH ₃ C ₁₆ H ₃₃ O (C ₂ H ₄ O) _m -CH ₃ C ₁₈ H ₃₇ O (C ₂ H ₄ O) _m -CH ₃ C ₂₀ H ₄₁ O (C ₂ H ₄ O) _m -CH ₃ C ₉ H ₁₉ COO (C ₂ H ₄ O) _m -CH ₃ C ₁₁ H ₂₃ COO (C ₂ H ₄ O) _m -CH ₃ C ₁₃ H ₂₇ COO (C ₂ H ₄ O) _m -CH ₃ C ₁₅ H ₃₁ COO (C ₂ H ₄ O) _m -CH ₃ C ₁₇ H ₃₅ COO (C ₂ H ₄ O) _m -CH ₃ C ₁₉ H ₃₉ COO (C ₂ H ₄ O) _m -CH ₃ 〔(c ) Component] In the present invention, as the component (c), a quaternary ammonium having a nitrile group is used. A bleach activator consisting of a salt of water is used. Preferable examples of the bleach activator include quaternary ammonium salts represented by the general formula (1) or the general formula (2).

[0013]

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[In the formula, R ¹ , R ⁷ and R ¹⁰ are the same or different and each represents a linear or branched alkylene group having 1 to 3 carbon atoms, and R ² , R ³ , R ⁵ and R ⁶ are Identical or different, having 1 to 1 carbon atoms
3 is an alkyl group or a hydroxyalkyl group, preferably an alkyl group. R ⁴ may have an aryl group as a substituent and may be branched and has 1 carbon atom.
To alkylene groups or arylene groups, preferably linear alkylene groups having 1 to 9 carbon atoms, and more preferably linear alkylene groups having 1 to 3 carbon atoms. Also, R ⁸ ,
At least one of R ⁹ and R ¹¹ is a linear or branched alkyl group having 4 to 18 carbon atoms, preferably 4 to 12 carbon atoms,
Alternatively, it is an aryl group which may be substituted with an alkyl group having 1 to 18 carbon atoms, and the rest is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. X represents an organic or inorganic anion. The quaternary ammonium salt represented by the general formula (1) can be obtained, for example, by the general formula (4)

[0015]

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(Wherein R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the above meanings) and a diamine and chloroacetonitrile, chloropropionitrile or the like are reacted. be able to. Further, the quaternary ammonium salt represented by the general formula (2) has the general formula (5)

[0017]

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(In the formula, R ⁹ , R ¹⁰ and R ¹¹ have the above-mentioned meanings), and a tertiary amine represented by the general formula (6) R ⁸ —X (6) (wherein R ⁸ And X have the above-mentioned meanings) and can be produced by reacting a compound represented by

The following compounds can be mentioned as specific examples of the bleach activator of the component (c).

[0020]

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[0021]

[Chemical 6]

[Liquid bleach composition] The liquid bleach composition of the present invention contains 0.5 to 10% by weight of component (a), preferably 1 to
10% by weight, more preferably 1 to 6% by weight, (b) component
0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, component (c) is 0.1 to 10% by weight, preferably 0.5 to 10% by weight, more preferably 1.0 to 10% by weight.
It can be blended. 0.5% by weight of component (a)
If it is less than 10% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 10% by weight, the storage stability of hydrogen peroxide is significantly reduced. If the blending amount of the component (b) is less than 0.1% by weight, the storage stability of the bleaching activator will be insufficient, and if it exceeds 30% by weight, the viscosity will increase and handling will be difficult. When the content of the component (c) is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and when it exceeds 10% by weight, the viscosity of the composition increases and it becomes difficult to handle.

[Arbitrary Ingredient] In the present invention, the above (b)
It is preferable to use an anionic surfactant together with the nonionic surfactant as a component. Examples of the anionic surfactant include alkylbenzene sulfonic acids having 8 to 22 carbon atoms or salts thereof, alkyl or alkenyl ether sulfates or salts thereof, polyoxyethylene alkyl or alkenyl ether sulfates or salts thereof, alkyl or alkenyl sulfates, or Salts thereof, α-olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acids or salts thereof, N-acyl amino acid type surfactants, alkyl or alkenyl ether carboxylic acids or salts thereof, polyoxyethylene alkyl or alkenyl ethers Examples thereof include carboxylic acids or salts thereof, amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. Of these, fatty acids or salts thereof, alkylbenzene sulfonic acids or salts thereof, polyoxyethylene alkyl or alkenyl ether sulfates, or polyoxyethylene alkyl ether carboxylic acids or salts thereof are particularly preferable. These anionic surfactants are preferably incorporated in the composition of the present invention in an amount of 0.1 to 30% by weight.

A sequestering agent may be added as an optional component to the composition of the present invention. The following compounds may be mentioned as specific examples of the sequestering agent. (1) Phosphoric acid compounds such as phytic acid or their alkali metal salts or alkanolamine salts (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-
Diphosphonic acid, phosphonic acid such as methanehydroxyphosphonic acid, or their alkali metal salts or alkanolamine salts (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or their alkali metal salts or alkanolamine salts (4) Aspartic acid, glutamic acid, amino acids such as glycine or their alkali metal salts or alkanolamine salts (5) nitrilotriacetic acid, Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencoric acid or their alkali metal salts or alkanolamine salts (6) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid , Oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, and other organic acids, or their alkali metal salts or alkanolamine salts (7) Alkali metal salts of aluminosilicate represented by zeolite A or alkanolamine salts (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 At least one selected from the group consisting of (2), (5), (6) and (7) is preferable, and at least one selected from the group consisting of (2) above is more preferable.
The amount of such a sequestering agent is 0.0005 to 5% by weight, preferably 0.01 to 1% by weight, based on the liquid bleaching composition of the present invention.

[0025]

INDUSTRIAL APPLICABILITY In the present invention, excellent storage stability,
Moreover, it is possible to provide a liquid bleaching composition having a high bleaching power.

[0026]

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

Examples 1 to 5 and Comparative Examples 1 to 3 (a) H ₂ O ₂ as a component, and the following compound (b-1) as a component (b)
~ (B-2), the following compounds as the component (c) (c-1) ~ (c-2),
A liquid bleaching agent composition was prepared by using (d-1) to (d-3) as an anionic surfactant and (e-1) as a sequestering agent, each having the composition shown in Table 1. Bleaching performance and storage stability of the obtained liquid bleaching agent composition were determined by the following methods, and the results are shown in Table 1. The composition shown in Table 1 was adjusted to pH 2.0 with 1/10 N sulfuric acid.

(B) Component C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₀ -H (b-1) C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -H (b-2) (c) component

[0029]

[Chemical 7]

Anionic surfactant C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ -CH ₂ COOH (d-1) alkyl (C ₁₂ ) sodium benzenesulfonate (d-2) lauric acid (d-3) ) Sequestering agent

[0031]

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<Method of measuring bleaching performance> Tap water at 20 ° C. and a commercially available powder detergent were dissolved in a 2 liter beaker to a concentration of 0.0833%, and the liquid bleaching composition shown in Table 1 was initially mixed. 40 or those stored at 40 ° C for 3 months
Dissolved in ml. Five pieces of black tea-contaminated cloths prepared as described below were added and immersed at 20 ° C. for 30 minutes. Then, it was rinsed with tap water, dried, and the bleaching rate was calculated by the following formula. Bleaching rate of tea-contaminated cloth

[0033]

[Equation 1]

The reflectance is NDR-101 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with DP using a 460 nm filter. <Preparation method of black tea cloth> Nitto black tea (yellow package) 80
After being boiled with 3 liters of ion-exchanged water for about 15 minutes, it was rubbed with desizing-exposed cotton, and a cotton cloth # 2003 was dipped in this solution and boiled for about 15 minutes. Remove from heat as it is, about 2
After leaving it for about an hour, it was naturally dried, washed with water until the washing liquid was not colored, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used for the experiment.

<Storage stability> The concentration of the bleach activator in the liquid bleach composition after storage at 40 ° C. for 3 months was measured by high performance liquid chromatography, and the residual ratio of the bleach activator was calculated by the following formula. It was

[0036]

[Equation 2]

[0037]

[Table 1]

Front Page Continuation (72) Inventor Shigumi Tsuchiya 1334 Minato Minato, Wakayama City, Wakayama Kao Research Institute

Claims (6)

[Claims] 1. (a) 0.5 to 10% by weight of hydrogen peroxide, (b)
0.1 to 30% by weight of one or more nonionic surfactants, and 0.1 to 10% by weight of (c) a bleaching activator comprising a quaternary ammonium salt having a nitrile group. A liquid bleach composition. 2. An anionic surfactant is further added in an amount of 0.1 to 30.
The liquid bleaching composition according to claim 1, wherein the liquid bleaching composition is contained by weight%. 3. The bleach activator of the component (c) has the general formula (1)
Alternatively, the liquid bleaching composition according to claim 1 or 2, which is a quaternary ammonium salt represented by the general formula (2). Embedded image [In the formula, R ¹ , R ^7, and R ¹⁰ are the same or different, and represent a linear or branched alkylene group having 1 to 3 carbon atoms, R ² , R ³ ,
R ⁵ and R ⁶ are the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ⁴ represents an alkylene group having 1 to 9 carbon atoms or an arylene group which may have an aryl group as a substituent and may be branched. At least one of R ⁸ , R ⁹ and R ¹¹ is a linear or branched alkyl group having 4 to 18 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 18 carbon atoms. And the rest is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. X represents an organic or inorganic anion. ] 4. The liquid bleach composition according to claim 1, wherein the nonionic surfactant as the component (b) is a compound represented by the general formula (3). R ¹² -B- (AO) _m -Y (3) [wherein R ¹² represents a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or a linear or branched carbon atom] The aryl groups which may be substituted with the alkyl groups of the numbers 1 to 18 are shown. B represents an -O- group or a -COO- group. A
Represents a linear or branched alkylene group having 2 to 3 carbon atoms, and m A's may be the same or different. Y represents H or an alkyl group having 1 to 3 carbon atoms. m is a number of 3 to 50 indicating the average number of moles of alkylene oxide added. ] 5. The anionic surfactant is fatty acid soap,
The liquid bleach composition according to any one of claims 2 to 4, which is at least one selected from alkylbenzene sulfonate, polyoxyethylene alkyl or alkenyl ether sulfate, and polyoxyethylene alkyl ether carboxylate. 6. The liquid bleaching composition according to claim 1, which further contains 0.0005 to 5% by weight of a sequestering agent.