JP2001311094A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid bleaching agent composition capable of excellently maintaining stability of an alkali metal hypochlorite and a hydrophobic substance even in the case of long-term storage of the liquid bleaching agent in a distribution process or at home, suitable useful for bleaching, mold removal, etc., for a hard surface of bathroom, kitchen, toilet, pipe, etc., and cloth, etc., due to exhibition of the effect of a hydrophobic substance, especially a hydrophobic functional substance in a use stage to the fullest extent. SOLUTION: This liquid bleaching agent composition is characterized in that the composition comprises (1) an alkali metal hypochlorite, (2) a hydrophobic substance and (3) a surfactant and the component (2) is emulsified by the component (3) and dispersed in the system as colloidal particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an alkali metal hypochlorite salt and a hydrophobic substance which are excellent in stability during storage and preservation. The present invention relates to a liquid bleach composition in which is effectively exhibited.

[0002]

2. Description of the Related Art
Bathroom, bathtub, kitchen tiles, joints,
Most of the dirt in places where water is frequently used, such as plastics, pottery, and drainage pipes, is due to mold-derived organic matter, and cannot be easily removed with ordinary detergents mainly containing surfactants. Therefore, in order to remove these stains, bleaching detergents based on alkali metal hypochlorite as a main base are frequently used.

At this time, an organic acid or a solvent is added to keep the colorant in the bleaching detergent stable, or a specific surfactant and a solvent are combined to keep the concentrated bleaching washing liquid stable. Formulation examples are disclosed (for example, see JP-A-61-2).
64098, JP-A-61-287996, JP-T-Hei07-07.
No. 500624). Further, there is disclosed a blending example in which a perfume component is solubilized with a specific surfactant and stabilized (for example, JP-A-62-32197).

Although these are certainly excellent in that they are stably present in the system, the alkali metal hypochlorite, which is the main base for bleaching and washing, is kept stable without decomposition over time. The point is not enough. In addition, the function is maintained during the distribution process and storage at home and when using liquid bleach,
Alternatively, there is no mention of a method of utilizing a functional substance that exhibits the maximum effect only after use.

Accordingly, an object of the present invention is to maintain the stability of the alkali metal hypochlorite and the hydrophobic substance, which are the bleaching base, when the liquid bleach is stored in the distribution process or at home. It is another object of the present invention to provide a liquid bleaching composition that is effective only when the effect of the hydrophobic functional substance is discharged or applied from a container.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they contain an alkali metal hypochlorite, a hydrophobic substance and a surfactant, and By adjusting the hydrophobic substance to be emulsified and dispersed as colloidal particles, the stability of the alkali metal hypochlorite, the hydrophobic substance, particularly the hydrophobic functional substance, is favorably maintained, The present inventors have found that a liquid bleach composition in which the effect of the functional substance is exerted for the first time in use can be obtained, and have completed the present invention.

That is, according to the present invention, it contains (1) an alkali metal hypochlorite, (2) a hydrophobic substance, and (3) a surfactant, and the component (2) is emulsified by the component (3). And a liquid bleaching composition which is dispersed in the system as colloidal particles. Further, the (2) hydrophobic substance is selected from the group consisting of (a) a hydrophobic solvent and / or (b) a bleach catalyst, a fungicide, an antibacterial agent, and a bactericide, and a mixture thereof. A liquid bleach composition that is a functional substance is provided.

[0008]

Embodiments of the present invention will be described below in more detail. As the alkali metal hypochlorite of the component (1) used in the present invention, sodium hypochlorite, potassium hypochlorite and the like can be mentioned, and sodium hypochlorite is particularly preferable. The content of the component (1) in the liquid bleach composition of the present invention is not particularly limited, but is usually within a range from 0.1 to 10% by mass, and preferably from 1 to 5% by mass. When the content of the component (1) is less than 0.1% by mass, the bleaching power is insufficient, and when it exceeds 10% by mass, the bleaching power is not particularly improved.

The hydrophobic substance of the component (2) used in the present invention is not particularly limited as long as it contributes to the improvement of the bleaching performance or the usability, and includes an organic solvent, a bleaching catalyst, a fungicide, Examples include antibacterial agents, bactericides, fragrances for reducing chlorine-like pungent odors, and pigments for clarifying the site of use.

The hydrophobic substance of the component (2) includes (a) a hydrophobic solvent for the purpose of improving the bleaching detergency and preventing the functional substance from being deteriorated by contact with water during storage. Is preferable. The hydrophobic solvent is not particularly limited, but when a polar parameter is used as a measure of hydrophobicity, for example, Dimroth
And Pyridinium-N-phenoxide betaine proposed by Reichart as an indicator
Solvents having a _T (30) value of 45 or less, preferably 40 or less are preferred. As a specific example, chloroform, 1,4
-Dioxane, ethyl acetate, diethyl ether, methylene chloride, benzene, tetrahydrofuran, and esters of various saturated fatty acids, methyl laurate, hexyl laurate, cetyl palmitate and the like.

[0011] The content of the component (a) in the liquid bleach composition of the present invention is not particularly limited, but is usually 0.1.
It is in the range of 1 to 50% by mass, preferably 1 to 20% by mass. When the content of the component (a) is less than 0.1% by mass,
It does not contribute to the improvement of the bleaching performance, and its stability decreases when a functional substance is used in combination. If it exceeds 50% by mass, the bleaching performance will be reduced.

Further, as the hydrophobic substance of the component (2),
(B) It preferably contains a hydrophobic functional substance selected from the group consisting of a bleach catalyst, a fungicide, an antibacterial agent, and a bactericide, and these are used alone or as a mixture.

As the hydrophobic bleaching catalyst, any catalyst can be used without particular limitation as long as it activates the bleaching power of the alkali metal hypochlorite and has low solubility in water. However, a hydrophobic chlorine-based catalyst in which at least one nitrogen atom is tertiary and which has a β-carbon is preferable. Specific examples include the following compounds, but are not limited thereto.

[0014] The hydrophobic fungicide, antibacterial and bactericide are not particularly limited, but have a low solubility in water having an action of controlling or inhibiting the growth and growth of microorganisms. Fungicides that have a bacteriostatic action to suppress the growth and proliferation of microorganisms and a bactericidal action to kill them can be mentioned.

Specifically, benzyl bromoacetate, α-bromocinnamaldehyde, tetrachloroisophthalonitrile as a halogen type, pentachlorophenyl laurate, p-chloro-m-xylenol, p-chloro-m-cresol as a phenol type 2- (carbomethoxyamino) -benzimidazole as an imidazole, 2- (4-thiocyanomethylthio) benzothiazole as a thiazole, 2,3,3 as a pyridine
5,6-tetrachloro-4- (methylsulfonyl)-
Examples of pyridine and amide compounds include dithio-2,2-bis (benzmethylamide), and other compounds such as N-dimethyl-N'-phenol-N '-(fluorodichloromethylthio) -sulfamide.

The content of the component (b) in the liquid bleach composition of the present invention is not particularly limited, but is usually 0.001 to 20% by mass, preferably 0.01 to 10% by mass. . When the content of the component (b) is less than 0.001% by mass, the function is extremely reduced, and when it exceeds 20% by mass, the stability of the alkali metal hypochlorite decreases.

The hydrophobic substance of the component (2) in the present invention preferably contains both a hydrophobic solvent as the component (a) and a hydrophobic functional substance as the component (b). Those comprising both are most preferred.

The surfactant of the component (3) used in the present invention is not particularly limited, and generally used surfactants such as anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants. Surfactants. For example, alkane sulfonate, fatty acid salt, alkyl sulfate salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate,
Polyoxyethylene alkylaryl sulfate,
Anionic surfactants such as polyoxyethylene alkyl phenyl ether sulfonate; nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl aryl ether; amphoteric such as sulfobetaine, carboxybetaine and alkyldimethylamine oxide Surfactant: One or more kinds of cationic surfactants such as alkyltrimethylammonium chloride can be appropriately blended.

Among the surfactants (3), particularly preferred are (a) an alkali metal salt of a fatty acid having 8 to 20 carbon atoms, and (b) a general formula R ¹ O (CH ₂ CH ₂ O) _m SO ₃ M
(R ¹ represents a linear or branched alkyl group having 8 to 20 carbon atoms, m is a number of 1 to 10 indicating an average addition mole number of ethylene oxide, and M is a cationic group) Polyoxyethylene alkyl sulfate salt,
(C) Formula R ² O (CH ₂ CH ₂ O) _n H (R ² is a linear or branched alkyl group having 8 to 20 carbon atoms, and n represents an average number of moles of ethylene oxide added. 3
(D) a polyoxyethylene alkyl ether represented by the general formula R ³ R ⁴ R ⁵ N → O (R ³
Is a linear or branched alkyl group having 8 to 20 carbon atoms, and R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to 3 carbon atoms. Amine oxide.

The content of the component (3) in the liquid bleaching composition of the present invention is not particularly limited, but is usually 0.1.
The range is from 01 to 30% by mass, preferably from 0.1 to 10% by mass. If the content of the component (3) is less than 0.01% by mass, the emulsifying power of the hydrophobic substance will be poor, and if it exceeds 30% by mass, precipitation and gelation will occur, which is not preferable.

In the present invention, in order to maintain the stability of the system, an aqueous solution of an alkali metal hypochlorite; a hydrophobic substance which does not always mix with water in the aqueous phase (W) irrespective of its chemical composition; An oil-in-water (O / W) emulsion in which (O) is dispersed is formed by the emulsifying power of a surfactant.

The size of the dispersed colloidal particles is not particularly limited, but the interface adsorbed as an oriented interface film at the interface between the two liquids so that the formed emulsion stably keeps the acid-separated state without coalescence. The activator is appropriately selected. The emulsifying method is not particularly limited, and examples thereof include a commonly used membrane emulsifying method and a method such as mechanical force using a homogenizer or a homomixer.

Hydrophobic substances such as solvents and functional substances are stably maintained in the emulsion formed in the system during the distribution process or during storage at home, and the liquid bleach is discharged from the discharge device during use, ie, from the discharge device. The emulsion breaks down due to shearing force when applied with a brush or the like or dilution into water, and the effect of a functional substance or the like is exhibited.

The pH of the liquid bleach composition of the present invention is not particularly limited, but is preferably 10 or more, more preferably 12 or more, for stabilizing the alkali metal hypochlorite. For this reason, an alkali agent is usually added, and examples of the alkali agent include caustic alkali and silicate. Sodium hydroxide, potassium hydroxide and the like are used as caustic alkalis, and sodium metasilicate and the like are used as silicates. Of these, sodium hydroxide is preferred. The content of the alkaline agent in the liquid bleach composition is usually in the range of 0.1 to 5% by mass, preferably 0.5 to 3% by mass. If the content is less than 0.1% by mass, the stability with the lapse of time is deteriorated.

[0025] Other optional components can be added to the liquid bleach composition of the present invention as needed. Specifically, as a builder for improving the cleaning performance, a component such as an aromatic sulfonate such as a toluene sulfonate or a xylene sulfonate can be blended as long as the effect of the present invention is not impaired.

The liquid bleach composition of the present invention can be adjusted by a usual method by adding a balanced amount of water to the above essential components and other optional components, but the viscosity of the composition is 25%. At 20 ° C. by a B-type viscometer is 20 to
It is desirable to be in the range of 300 mPa · s, especially 100 to 200 mPa · s. If the viscosity is too low, the adhesion retention property may be poor, and if it is too high, the usability may be poor.

The liquid bleach composition of the present invention can be used directly from a container or can be applied using a brush or the like.
It is preferable in terms of simplicity to use a discharge container equipped with a discharge device such as a trigger type sprayer, and such a discharge container is provided with a discharge device for discharging the above composition, Any discharge device having a sliding portion such as a piston / cylinder or a fitting portion for passing liquid through the pump housing can be used without any particular limitation.

As a specific example, the composition contained in the discharge container 1 as shown in FIG. 1, that is, the container body 2 is discharged by operating the piston 4 and the cylinder 5 by pulling the trigger 3. The discharge container 1 having a trigger type sprayer 6 to be driven and the discharge container having a pump sprayer or the like for discharging a composition contained in a container body through a dip tube by moving a pump head up and down as a discharge device are used. Is done.

In the present invention, when a discharge vessel having a discharge device such as a trigger type sprayer as described above is used, the composition is low in a high shear rate range when the composition is sprayed from the discharge device such as a trigger type sprayer. It is preferable that it has viscosity and has high viscosity in a low shear rate range (stationary) when it adheres to a wall surface or the like. Specifically, Ha at 25 ° C.
The viscosity measured with an ake RS-100 viscometer is 300
0.1 to 100 mPa in a high shear rate range of ⁰ sec ^-1
S, preferably ¹ to 50 mPa · s, more preferably 1 to 10 mPa · s, and 100 to ¹ × 10 ⁵ mPa · s, preferably 5 in the low shear rate region (stationary) of 0.5 sec ^−1. It is desirably from × 10 ² to 1 × 10 ⁵ mPa · s, more preferably from 1 × 10 ³ to 1 × 10 ⁵ mPa · s. If the viscosity in the high shear rate range of 3000 sec ^-1 is higher than the above value, the composition is difficult to spray from a discharge device such as a trigger sprayer, which is not preferable. Further, when the viscosity in the low shear rate region (stationary) of 0.5 sec ^-1 is lower than the above value, the adhesion retention property on the wall surface or the like is reduced, and when the viscosity is higher than the above value, the trigger sprayer described above is used. It becomes difficult to continuously pump up the composition from the dip tube in a discharge device such as the above.

[0030]

According to the present invention, even when the liquid bleach is stored for a long time in the distribution process or at home, the stability of the alkali metal hypochlorite and the hydrophobic substance is maintained well, and the hydrophobic property is maintained. Since the effect of the active substance, particularly the hydrophobic functional substance, is maximized in the use stage, that is, in the stage of discharging or applying from the container, the bathroom, kitchen, toilet,
It is suitably used for bleaching of cloths, hard surfaces such as water pipes, and mold removal.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The stability over time and the bleaching power in the examples were evaluated based on the following criteria.

<Aging stability: evaluation method of liquid properties> A transparent container (manufactured by Takemoto: JOY-120) made of polyethylene terephthalate was filled with 90 g of various liquid bleach compositions, and the container was covered with a lid. (Platinus PU-4SP, manufactured by Tabai Espec) for one month, and thereafter, changes in liquid properties were visually observed and judged according to the following evaluation criteria. Evaluation criteria: ○: No change △: Precipitate, sediment, and separation are slightly observed ×: Precipitate, sediment, and separation are severely observed

<Evaluation Method of Stability over Time; Hypochlorous Residue> In the same manner as the above evaluation method, the concentration of alkali metal hypochlorite in various liquid bleach compositions after storage for one month was determined by a fully automatic titrator ( Using Hiranuma Sangyo Co., Ltd .: TS-980), the sample reacted with potassium iodide and acetic acid was titrated with a sodium thiosulfate solution. This concentration was defined as the residual ratio of the alkali metal hypochlorite to the initial concentration, and was determined according to the following evaluation criteria. Evaluation criteria: ：: residual rate of alkali metal hypochlorite 60 to 100% △: residual rate of alkali metal hypochlorite 30 to 60% ×: residual rate of alkali metal hypochlorite 0 to 30 %

<Method of measuring bleaching power> Black mold (Clados)
porium cladosporioides was cultured and applied to unglazed tiles (SPAX made by INAX)
-1060) was used as a model plate. (L value of the model mold plate when the L value of the unglazed tile is calculated as 100) = 30-40. The model mold plate was placed horizontally, and 0.5 g of various liquid bleach compositions were gently dripped with a spatula, and a trigger type dispenser (YT87L-FM, manufactured by Yoshino Kogyosho) was used.
Stroke (spray amount on plate; about 0.5g) 10c
Each spraying operation was performed twice from a distance of m. These were left for 3 minutes and 15 minutes, washed with water and air-dried, and then the lightness (L value) was measured using a color difference meter (manufactured by MINOLTA; CR-200).

[0035]

EXAMPLE 1 Sodium hypochlorite 3%, coconut fatty acid sodium 0.4%, cocoamine oxide 0.5%, sodium alkylbenzene sulfonate 0.1%, sodium hydroxide 0.5%, liquid paraffin 5% , Tri-n-
Butylamine 0.05% and a water balance were mixed, and the mixed solution was passed through a membrane filter (manufactured by ADVANTEC) having a pore size of 1 μm by pressure filtration. After passing through the filter, the bleach solution is subjected to an optical microscope (manufactured by KEYENCE; VH
-Z450), an O / W emulsion having a diameter of 1 to 3 µm and uniformly dispersed was confirmed. The results obtained are shown in Table 1.

[0036]

Examples 2 to 5 Various liquid bleach compositions were prepared in the same manner as in Example 1 except that the solvent was changed from liquid paraffin to chloroform, ethyl acetate, benzene and methyl laurate. The results obtained are shown in Table 1.

[0037]

Example 6 3% sodium hypochlorite, 0.4% coconut fatty acid, 0.5% cocoamine oxide, 0.1% sodium alkylbenzenesulfonate, 0.5% sodium hydroxide, 10% squalane, A mixture of 0.05% tri-n-butylamine and water balance is mixed, and the mixed solution is mixed with a TK homomixer (TOKUSYU KIKAKOU).
(Manufactured by GYO) at 10,000 rpm. After the stirring, the bleach solution is subjected to an optical microscope (manufactured by KEYENCE);
VH-Z450), the diameter was 5 to 40 μm.
O / W emulsion was confirmed. Table 2 shows the obtained results.

[0038]

Examples 7 to 9 and Comparative Example 1 In the same manner as in Example 6, except that the functional substance was changed from tri-n-butylamine to the above-mentioned bleaching catalysts (2), (4) and (8), A liquid bleach composition was made. In addition, a sample which was subjected to the test in Example 6 without stirring the mixed solution (without emulsification) was used as Comparative Example 1. Table 2 shows the obtained results.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

Example 10 3% sodium hypochlorite, 0.4% coconut fatty acid, 0.5% cocoamine oxide,
0.1% sodium alkylbenzenesulfonate, 0.5% sodium hydroxide, 10% squalane, 0.01% α-bromocinnamaldehyde, water balance,
Transfer the mixed solution to a TK homomixer (TOKUSYU KIK).
(AKOUGYO) at 10,000 rpm. After the stirring, the bleach solution is subjected to an optical microscope (KEYENC).
E company; VH-Z450).
An OW emulsion of 40 μm was confirmed. This sample was used as a trigger dispenser (YT87L, manufactured by Yoshino Kogyosho).
-FM) to remove the mold from the bathroom
It took about two months longer for mold to grow on a sample containing no functional substance. In addition, the composition of the present invention had very good stability over time.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a main part of a discharge container provided with a discharge device.

[Explanation of symbols]

 1 Discharge container 2 Container body 3 Trigger 4 Piston 5 Cylinder

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takayasu Kuboen 1-3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4H003 AB03 AB19 AC15 BA12 DA05 DA08 DA12 DA13 EA21 EB09 EB43 ED04 ED04 ED09 ED27 EE08 FA44

Claims (2)

[Claims] (1) an alkali metal hypochlorite,
(2) a hydrophobic substance, (3) containing a surfactant, (2)
A liquid bleaching composition, wherein the components are emulsified by the component (3) and dispersed in the system as colloid particles. (2) The hydrophobic substance is selected from the group consisting of (a) a hydrophobic solvent and / or (b) a bleaching catalyst, a fungicide, an antibacterial agent, and a bactericide, and a mixture thereof. The liquid bleaching composition according to claim 1, which is a functional material having a lipophilic property.