JP4877919B2 - Chlorine bleach composition - Google Patents

Description

  The present invention relates to a chlorine bleach composition.

Conventionally, many bleaching compositions mainly composed of alkali metal hypochlorite are known, and are caused by dirt, particularly mold, attached to hard surfaces such as bathrooms, bathtubs, kitchens, toilets, and water pipes. Widely used for the purpose of removing dirt. In order to exhibit excellent bleaching performance when applied to any surface, the bleaching composition as described above is not limited to a horizontal plane, but a variety of vertical surfaces, inclined surfaces, etc. There is a demand for retention of adhesion to the target dirt. In addition, when using a bleaching composition in a bathroom or the like, it can be applied efficiently over a wide range, or it can be applied intensively to the target dirt, so that it is a trigger. A sprayer of the type is often used, and it is necessary to satisfy the compatibility at the same time when such a container is used. In order to meet such demands, attempts have been made to improve the adhesion and retention of the composition by various methods. For example, Patent Document 1 discloses a detergent product having improved adhesion retention by imparting viscosity to a composition. Patent Document 2 discloses that a relatively high-viscosity cleaning agent having thixotropic properties is sprayed into a foam having an appropriate roughness using a sprayer, so that even if the object is a mesh structure, the mesh passes through the mesh. There has been disclosed a cleaning agent and a cleaning agent product that adheres so as to uniformly cover the surface of an object without any problems and can exhibit excellent adhesion retention. Patent Document 3 discloses a bleaching composition having a specific polymer and excellent in storage stability.
JP 2003-41300 A JP 2003-253297 A JP 7-305099 A

  Although the detergent product described in Patent Document 1 has increased adhesion retention of the composition, it does not form bubbles even when sprayed with a trigger sprayer, and is inferior in comfort and visibility. The cleaning agent and the cleaning product described in Patent Document 2 increase the adhesion and retention of the cleaning agent, but have poor usability such as visibility due to coarse bubbles. The bleaching composition described in Patent Document 3 is excellent in the storage stability of alkali metal hypochlorite, but there is no description of the state when sprayed with a trigger sprayer, which is suitable for such applications. There is no specific suggestion of means that can provide characteristic bubbles.

  That is, there is a demand for a chlorine-based bleach composition that is excellent in ease of use, such as visibility of bubbles discharged during spraying by a sprayer such as a trigger and adhesion and retention on a target surface.

The present invention comprises (a) an alkali metal hypochlorite salt (hereinafter referred to as component (a)), (b) an alkali metal hydroxide (hereinafter referred to as component (b)), (c) a surfactant [ (Hereinafter referred to as “component (c)”), and (d) a chlorine bleach composition containing a compound of the following general formula (1) [hereinafter referred to as “component (d)”].
XO (AO) _p Y (1)
(In the formula, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, p represents an average added mole number in the number of 10 to 100, and X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkanoyl group. Y represents —SO ₃ H, —CH ₂ COOH or an alkali metal salt thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the chlorine-type bleach composition excellent in usability, such as the visibility obtained by the foam discharged at the time of spraying with a sprayer, such as a trigger, the adhesion retention property to a target surface, etc. is obtained.

  Examples of the alkali metal hypochlorite (a) include sodium hypochlorite and potassium hypochlorite, with sodium hypochlorite being particularly preferred. Sodium hypochlorite is mixed with sodium hypochlorite and equimolar sodium chloride in production, but sodium hypochlorite containing a large amount of sodium chloride may impair storage stability. It is preferable to use one with reduced sodium. Specifically, sodium chloride is 10 to 60 mol%, preferably 10 to 40 mol%, based on sodium hypochlorite. Such sodium hypochlorite with reduced sodium chloride is commercially available as low dietary sodium hypochlorite. The content of the component (a) in the chlorine bleach composition of the present invention is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, and 1.0 to 3%. 0.0 mass% is particularly preferable. When the content of the component (a) is 0.1% by mass or more, sufficient bleaching power is obtained, and when it is 5.0% by mass or less, good stability of the alkali metal hypochlorite is obtained.

  The component (b) alkali metal hydroxide represents a combination of an alkali metal ion and a hydroxy ion present in the chlorine-based bleach composition, that is, a free alkali, and in the case of a combination with another counter ion. Not subject to this. Examples of the component (b) include sodium hydroxide and potassium hydroxide, and sodium hydroxide is particularly preferable. In the present invention, the amount of component (b) in the composition is measured by the method described in ASTM D 2022-89. That is, in this method, the amount of free alkali in the bleaching agent is measured as sodium hydroxide (NaOH). Also in the present invention, the amount of free alkali in the composition obtained by this method is determined in the composition. (B) The amount of the component. The chlorine bleach composition of the present invention contains the component (b) as a component that improves the stability of the alkali metal hypochlorite, and the content thereof is 0.1 to 1.0 mass. % Is preferable, 0.2 to 0.8 mass% is more preferable, and 0.3 to 0.7 mass% is particularly preferable. When the content of component (b) is 0.1% by mass or more, good alkali metal hypochlorite stability is obtained, and when 1.0% by mass or less, good stability is obtained.

As the surfactant of the component (c) in the chlorine-based bleach composition of the present invention, surfactants usually used in chlorine-based bleach compositions can be used, among which the following general formula (2), It is preferable to blend one or more selected from the compounds represented by (3), (4), (5), and (6).
R ₁ R ₂ R ₃ N → O (2)
R ₄ SO ₃ M (3)
R ₅ O (AO) _q SO ₃ M (4)
R ₆ COOM (5)
R ₇ O (AO) _r R ₈ COOM (6)
Wherein R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, R ² and R ³ are linear or branched alkyl groups having 1 to ³ carbon atoms, and R ⁴ is 6 to 6 carbon atoms. 22 linear or branched alkyl groups, or alkylaryl groups in which a linear or branched alkyl group having 6 to 22 carbon atoms is bonded to the benzene ring, R ⁵ , R ⁶ and R ⁷ are each 6 to 6 carbon atoms. 22 represents a linear or branched alkyl group having 22. A represents one or more linear or branched alkylene groups having 2 to 4 carbon atoms, and R ⁸ represents an alkylene group having 1 to 4 carbon atoms. Q and r each represent an average number of added moles in a number of 0 to 100, and M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom.

  Among these, it is preferable to blend one or more compounds represented by the general formulas (2), (3), (4), and (5). The compound represented by the general formula (2) and the general formula ( 3), (4), a combination with the compound represented by (5), or a combination of the compound represented by the general formula (4) and the compound represented by the general formula (3), (5) preferable.

Each compound will be described in detail. The general formula (2) represents an alkylamine oxide, and R ₁ is an alkyl having 8 to 18 carbon atoms from the viewpoint of foaming properties during spraying and stability of the composition. Group is preferable, and an alkyl group having 10 to 16 carbon atoms is preferable, and an alkyl group having 12 to 16 carbon atoms is particularly preferable. R ₂ and R ₃ are preferably methyl groups from the viewpoint of the stability of the composition.

The general formula (3) represents an alkane sulfonate and an alkylbenzene sulfonate, and R ₄ is preferably an alkyl group having 8 to 18 carbon atoms from the viewpoint of foamability and composition stability. An alkyl group having 8 to 16 is preferable, and an alkyl group having 10 to 14 carbon atoms is particularly preferable. In the case of alkane sulfonate, the carbon atom of the alkyl group to which the sulfonic acid group is bonded may be any of primary, secondary, and tertiary carbon atoms, or a combination thereof. Alkyl benzene sulfonate generally has a linear alkyl group. Alkylbenzene sulfonate exhibits the low temperature stability of the composition and the effect of suppressing white turbidity at the time of blending. Alkylbenzene sulfonates exhibit sufficient foaming properties even when used alone, but are more preferably used in combination with other surfactants.

The general formula (4) represents an alkyl sulfate ester salt or a polyoxyalkylene alkyl ether sulfate ester salt, and R ₅ is preferably an alkyl group having 8 to 18 carbon atoms from the viewpoint of foamability and composition stability. A C10-16 alkyl group is preferable, and a C10-14 alkyl group is particularly preferable. q is preferably a number of 0 to 10 and particularly preferably 0 to 5 from the viewpoint of foamability and stability of the composition.

General formula (5) shows a fatty acid or a salt thereof, and R ₆ is preferably an alkyl group having 8 to 18 carbon atoms from the viewpoint of foamability and stability of the composition. From the standpoint of foamability and adhesion, R ₆ is preferably a single alkyl group having 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms. It is preferable to use a mixed alkyl group containing at least 60% (mass ratio) of 12 to 14 alkyl groups and having a distribution of 8 to 18 carbon atoms.

The general formula (6) represents an alkyl carboxymethyl ester salt or a polyoxyalkylene alkyl carboxymethyl ester salt, and R ₇ is preferably an alkyl group having 8 to 18 carbon atoms from the viewpoint of foamability, and among them, an alkyl group having 8 to 14 carbon atoms. An alkyl group is preferable, and an alkyl group having 8 to 10 carbon atoms is particularly preferable. When used in combination with other surfactants, particularly fatty acid salts, R ₇ is preferably an alkyl group having 8 to 18 carbon atoms, particularly an alkyl group having 10 to 16 carbon atoms, from the viewpoint of the stability of the composition. In particular, an alkyl group having 12 to 14 carbon atoms is preferred. r is preferably a number of 1 to 20, and particularly preferably 3 to 15, in terms of foamability and stability of the composition.

  Among such compounds, combinations of dodecyldimethylamine oxide and sodium dodecane sulfonate, sodium dodecyl sulfate, sodium polyoxyethylene (q = 4) sodium dodecyl ether sulfate, sodium dodecanoate, tetradecyldimethylamine oxide and the like , Sodium dodecanesulfonate, sodium decyl sulfate, sodium polyoxyethylene (q = 4) sodium dodecyl ether sulfate, sodium dodecanoate, sodium coconut fatty acid, or sodium polyoxyethylene (q = 4) dodecyl ether sulfate And a combination of sodium dodecanesulfonate, sodium decanoate, sodium dodecanoate, and the like. Among them, in terms of adhesion and foaming properties, a combination of dodecyldimethylamine oxide and sodium dodecyl sulfate, sodium dodecanoate, tetradecyldimethylamine oxide, sodium dodecanesulfonate, sodium decyl sulfate, sodium dodecanoate, A combination of coconut fatty acid sodium and the like is more preferable, and a combination of tetradecyldimethylamine oxide, sodium decyl sulfate ester, sodium dodecanoate, and sodium coconut fatty acid is most preferable. Further, by adding sodium dodecylbenzenesulfonate or sodium decylbenzenesulfonate to the combination of these surfactants, it is possible to improve the low-temperature stability of the composition and the suppression of white turbidity at the time of blending.

  As content of (c) component in a composition, 0.1-3.0 mass% is preferable, 0.2-2.0 mass% is more preferable, 0.3-1.5 mass% is especially preferable. preferable. When the content of the component (c) is 0.1% by mass or more, good foaming properties are obtained, and when it is 3.0% by mass or less, the stability of the composition is good. Among the components (c), the alkylbenzene sulfonate is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.4% by mass, and most preferably 0.05 to 0% in the composition. It is blended at a concentration of 3% by mass. This is the concentration when counted as a sodium salt. When the alkylbenzene sulfonate content is 0.01% by mass or more, low-temperature stability can be further improved, and when it is 0.5% by mass or less, white turbidity at the time of blending can be suppressed.

The component (d) is a compound represented by the following general formula (1).
XO (AO) _p Y (1)
(In the formula, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, p represents an average added mole number in the number of 10 to 100, and X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkanoyl group. Y represents —SO ₃ H, —CH ₂ COOH or an alkali metal salt thereof.

Specifically, as component (d), A preferably has 2 carbon atoms from the viewpoint of foamability and adhesion. p is preferably from 10 to 100, more preferably from 10 to 70, particularly preferably from 20 to 40, from the viewpoint of foamability and adhesion. X is preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or an alkanoyl group having 2 to 3 carbon atoms, and more preferably a methyl group. Y represents —SO ₃ H, —CH ₂ COOH or an alkali metal salt thereof, and —SO ₃ H or an alkali metal salt thereof is preferable because of excellent stability of hypochlorite. The content of the component (d) in the composition is preferably 0.05 to 3.0% by mass, more preferably 0.05 to 2.0% by mass, and particularly preferably 0.1 to 1.0% by mass. preferable. The content of the component (d) is 0.05% by mass or more in terms of foamability, and is 3.0% by mass or less from the viewpoint of stability.

  The chlorine-based bleach composition of the present invention comprises (e) a hydrotrope having a benzene ring as a component for further improving the foaming power and foam density when sprayed with a low temperature stability or a trigger sprayer. It is preferable to contain. (E) By containing a hydrotrope such as xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzoic acid or alkali metal salts thereof as component (e), the low temperature stability and foaming ability can be further improved. . Among these, metaxylene sulfonic acid or a sodium salt thereof is particularly preferable. The content of the component (e) in the chlorine bleach composition of the present invention is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.0% by mass, and 0.3 to 1 0.0 mass% is particularly preferable. (E) When the content of the component is 0.1% by mass or more, the effect of further improving the foaming force and adhesion when sprayed with a sprayer such as low temperature stability or a trigger becomes large, and is 3.0% by mass or less. Thus, good stability of alkali metal hypochlorite can be obtained.

  The chlorine bleach composition of the present invention can contain a fragrance. As examples of perfume ingredients that can be blended into hypochlorite systems, reference can be made to JP-A-50-74581 and JP-A-62-205200. Perfume may be used. Although a fragrance | flavor is normally contained in 0.001-0.5 mass% in a composition, since there exists a possibility of impairing stability, a caution is required for a compounding component and content.

  The balance of the chlorine-based bleach composition of the present invention is water, and ion-exchanged water or distilled water from which metal ions and the like existing in a trace amount are removed is preferable in terms of storage stability. The water content is preferably 80 to 98% by mass, more preferably 90 to 98% by mass in the composition from the viewpoint of storage stability. Moreover, it is preferable from the point of storage stability and the bleaching effect to adjust pH at 20 degreeC of a composition to 12.5-13.5.

  The chlorine-based bleach composition of the present invention is preferably a composition imparted with viscosity from the viewpoint of adhesion and retention on various target surfaces such as a vertical surface and an inclined surface. Viscosity (B-type viscometer, measurement condition: 20 ° C. Rotor No. 1, 60 rpm, the value 60 seconds after the start of rotation is the viscosity) is preferably 5 to 100 mPa · s, more preferably 5 to 50 mPa · s, and particularly preferably 5 to 30 mPa · s.

As a method of using the chlorine-based bleach composition of the present invention, a form of a bleach in a container formed by filling a spray container from the viewpoint of simplicity and foamability is preferable. As a sprayer, a trigger type spray capable of foaming and spraying a chlorine-based bleach composition containing the components (a) to (d) and the component (e) and water, specifically, one operation. A trigger having a mechanism for discharging 0.5 to 2 mL of the composition and forming bubbles is preferable. Moreover, when using the chlorine-type bleach composition of this invention, it is preferable to spray in the ratio of 5-15g with respect to 1 m < ² > of target objects.

  A chlorine bleach composition shown in Table 1 was prepared, and the viscosity was measured, the foam specific volume was measured, and the foam adhesion retention was evaluated by the following methods. The results are shown in Table 1.

<Measurement of viscosity>
Using the B-type viscometer (manufactured by TOKIMEC), the temperature of the composition was set to 20 ° C., rotor No. 1 was used, and the number of rotations was 60 rpm, and the measurement was performed under the conditions 60 seconds after the rotation started.

<Measurement of foam specific volume>
Using a trigger sprayer of mold remover High Strong (manufactured by Kao Corporation) with the chlorine-based bleach composition shown in Table 1, the volume (mL) of foam produced when sprayed 10 times into a 200 mL graduated cylinder is read. In addition, the spray amount (g) at that time is measured using a balance capable of measuring to the unit of 10 mg, and calculated by the formula of foam specific volume (mL / g) = foam volume (mL) / spray amount (g). did. The larger the value, the better the effect and visibility.

<Evaluation of adhesion and retention of foam>
The chlorine-based bleach composition shown in Table 1 is separated by 10 cm along the tile joint of the bathroom wall with 10 cm x 10 cm earthenware tiles using a trigger sprayer of mold remover Strong Strong (manufactured by Kao Corporation). Then, spraying was performed four times horizontally within a range of a width of 10 cm, and the area from the position where the bubbles adhered to the position where the bubbles dropped after 1 minute was calculated. It shows that adhesion retention is so high that a numerical value is small. In addition, although the difference by numerical expression is small, the difference by visual observation is clear.

-Sodium hypochlorite: Sodium hypochlorite, manufactured by Nankai Chemical Industry Co., Ltd.-Sodium hydroxide: 48% liquid caustic soda, manufactured by Nankai Chemical Industry Co., Ltd. (The values in the table are the amount of free sodium hydroxide. Is shown.)
Tetradecyldimethylamine oxide: A sample synthesized from Farmin DM4098 myristylamine (manufactured by Kao Corporation) and hydrogen peroxide (manufactured by Nippon Peroxide).
Fatty acid Na: sodium salt of Lunac L-70 (a mixture of fatty acids having a compositional mass ratio of capric acid 10, lauric acid 76, myristic acid 14), manufactured by Kao Corporation. Alkylbenzenesulfonic acid Na: Neoperex G-25 , Manufactured by Kao Corporation. Compound 1: A sample of ethylene oxide added to methanol and further reacted with sulfuric anhydride. The average added mole number of ethylene oxide was 23, and the terminal of ethylene oxide was completely a sulfate group.
Compound 2: A sample obtained by adding ethylene oxide to methanol and further reacting with sulfuric anhydride. The average added mole number of ethylene oxide was 54, and the terminal of ethylene oxide was completely a sulfate group.

Claims (7)

(A) alkali metal hypochlorite [hereinafter referred to as component (a)] , (b) alkali metal hydroxide (hereinafter referred to as component (b)) , (c) surfactant [hereinafter referred to as (c) ) Component] , (d) a chlorine bleach composition containing a compound of the following general formula (1) [hereinafter referred to as component (d)] .
XO (AO) _p Y (1)
(In the formula, AO is an alkyleneoxy group having 2 to 4 carbon atoms, p is an average added mole number in the number of 10 to 100, and X is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or 2 to 3 carbon atoms. the .Y showing an alkanoyl group indicates a -SO ₃ H, -CH ₂ COOH or alkali metal salt thereof.) The component (c) surfactant is one or more selected from compounds represented by the following general formulas (2), (3), (4), (5), and (6). The chlorine bleach composition according to 1.
R ₁ R ₂ R ₃ N → O (2)
R ₄ SO ₃ M (3)
R ₅ O (AO) _q SO ₃ M (4)
R ₆ COOM (5)
R ₇ O (AO) _r R ₈ COOM (6)
Wherein R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, R ² and R ³ are linear or branched alkyl groups having 1 to ³ carbon atoms, and R ⁴ is 6 to 6 carbon atoms. 22 linear or branched alkyl groups, or alkylaryl groups in which a linear or branched alkyl group having 6 to 22 carbon atoms is bonded to the benzene ring, R ⁵ , R ⁶ and R ⁷ are each 6 to 6 carbon atoms. 22 represents a linear or branched alkyl group having 22. A represents one or more linear or branched alkylene groups having 2 to 4 carbon atoms, and R ⁸ represents an alkylene group having 1 to 4 carbon atoms. Q and r each represent an average number of added moles in a number of 0 to 100, and M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. The component (c) is a combination of a compound represented by the general formula (2) and a compound selected from the compounds represented by the general formulas (3), (4) and (5), or the general formula ( The chlorine bleach composition according to claim 2, which is a combination of the compound represented by 4) and a compound selected from the compounds represented by the general formulas (3) and (5). The chlorine bleach composition according to any one of claims 1 to 3, comprising 0.1 to 3.0% by mass of the component (c). The chlorine-based bleach composition according to any one of claims 1 to 4, comprising 0.05 to 3.0% by mass of component (d). The chlorine bleach according to any one of claims 1 to 5, wherein the component (a) is sodium hypochlorite, and the content of sodium chloride is 10 to 60 mol% with respect to sodium hypochlorite. Composition. (E) The chlorine bleach composition according to any one of claims 1 to 6, comprising a hydrotrope having a benzene ring.