JP2001316697A - Bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching agent composition which can give a good bleaching power in a short time because of excellent foaming ability when delivered from a delivery device, excellent delivery from a delivery device, and excellent capability of deposition and residence on a contaminated object on a vertical or inclined surface and which is therefore suitably used for a hard surface in a bathroom, a kitchen, a toilet and the like. SOLUTION: This bleaching agent composition contains (1) 0.1-10 mass % alkali metal hypochlorite, (2) 0.1-5 mass % alkalizing agent, and (3) 0.1-5 mass % amine oxide(s) represented by general formula I (wherein, R1 is an 8-22C linear or branched alkyl; and (n) and (m) are each the average number or ethylene oxide molecules added, not 0, and a number satisfying the relation of the formula: 2<=n+m<=15) and/or formula (II) (wherein, R2 is a 7-21C linear or branched alkyl; R3 and R4 are each a 1-3C linear or branched alkyl; and (n) is a number satisfying the relation of the formula: 2<=n<=5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching agent composition, and more particularly, to a bleaching agent which is excellent in spraying a bleaching agent on a vertical surface or an inclined surface using a discharge container provided with a discharge device. Shows foaming, adhesion retention, and bleaching performance,
The present invention relates to a bleaching composition which can be suitably used for hard surfaces such as bathrooms and kitchens.

[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.

[0003] At that time, in order to easily use the bleaching agent, a method of storing a bleaching agent in a discharge container provided with a discharging device such as a trigger type sprayer and spraying the bleaching agent using the discharging device has been adopted in many cases. . In addition, a surfactant is added to prevent mist scattering and the like, and a liquid is ejected in the form of a foam (see JP-A-63-72798 and JP-A-63-1654).
No. 95), a thickening method by salting out using a complex or the like of two or more surfactants to improve the adhesion retention property of a vertical surface or an inclined surface is disclosed (Japanese Patent Application Laid-Open No. 6-184594). No., JP-A-10-60491).

[0004] However, when the composition containing these surfactants is sprayed using a discharge device such as a trigger type sprayer, there is a disadvantage that the foaming properties are generally inferior. In order to improve this, it has been attempted to mix an amine oxide having a relatively high foaming property among the surfactants, but even a general-purpose amine oxide such as lauryl dimethyl amine oxide can be used. However, satisfactory foaming power was not obtained. In addition, since the hydrogen peroxide used as an oxidizing agent in the production stage using a tertiary amine as a starting material is mixed into the bleach as an excess, the amine oxide is hypochlorite, which is a bleaching base. The acid alkali metal salt has a serious disadvantage that it gradually decomposes and the bleaching power decreases.

[0005] Further, since the bleach containing these surfactants is a composition whose rheological properties show a Newtonian flow, the composition whose viscosity has been increased cannot be dissipated by a shear force for operating a discharge container. A normal ejection pattern cannot be obtained from the portion, and furthermore, there is a fatal problem that continuous spraying is not possible, or continuous spraying is possible, but the discharged composition is based on alkali metal hypochlorite. There was a problem that a satisfactory level of adhesion retention was not achieved because the viscosity was hardly observed in the high electrolyte solution.

Accordingly, an object of the present invention is to provide an excellent foaming property when a bleaching agent composition is discharged from a discharge device such as a trigger type sprayer by being housed in a container provided with a discharge device. In addition, by realizing a composition exhibiting a quasi-viscosity flow while using a surfactant alone, a good discharge pattern can be obtained from a discharge container, and after discharge, a vertical surface or an inclined surface can be cleaned. An object of the present invention is to provide a bleaching composition exhibiting excellent adhesion retention and bleaching performance.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by using an alkali metal hypochlorite, an alkali agent and a specific amine oxide, The present inventors have found that a bleaching composition having excellent foaming property, adhesion retention property and bleaching performance can be obtained, and thus completed the present invention. That is, according to the present invention, (1) an alkali metal hypochlorite salt; 0.1 to 10% by mass, (2) an alkali agent; 0.1 to 5% by mass, (3) the following general formula (I)
And / or an amine oxide represented by (II);
A bleach composition comprising 0.1 to 5% by mass is provided. (R ₁ is a linear or branched alkyl group having 8 to 22 carbon atoms, n and m are average addition moles of ethylene oxide, n and m are not 0, and 2 ≦ n + m
≤15) (R ₂ is a linear or branched alkyl group having 7 to 21 carbon atoms, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 3 carbon atoms, and n is 2 ≦ (represents a number n ≦ 5)

[0008] The present invention also provides the above bleaching composition, wherein the content of hydrogen peroxide in the amine oxide is 0.1% by mass or less based on the whole composition. Further, the above-mentioned bleach composition containing (4) an alkali metal salt of a fatty acid and / or (5) an alkylbenzene sulfonate as a surfactant is provided. Further, a bleach composition containing a discharge container, comprising a container body for storing the contents and a discharge device for discharging the contents stored in the container body, wherein the bleach composition at 25 ° C. Haake RS
The viscosity measured with a -100 viscometer is 100 to ¹ × 10 ⁵ mPa · s, 300 at a shear rate of 0.5 sec ^−1.
0.1 to 100 mPa · under a shear rate of ⁰ sec ^-1
s is provided.

[0009]

Embodiments of the present invention will be described below in 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 bleaching composition of the present invention is usually in the range of 0.1 to 10% by mass, preferably 1 to 5% by mass. When the content of the component (1) is less than 0.1% by mass, the bleaching power becomes insufficient.
Even if it exceeds 0% by mass, the bleaching power is not particularly improved.

The alkaline agent of the component (2) used in the present invention is not particularly limited, and examples thereof 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. (2) in the bleach composition of the present invention
The content of the component is usually in the range of 0.1 to 5% by mass, preferably 0.5 to 3% by mass. When the content of the component (2) is less than 0.1% by mass, the stability with time deteriorates,
If it exceeds 5% by mass, the effect on the skin and the mucous membrane of the eyes is considered, and the effect of the combination cannot be exhibited.

The amine oxide (3) used in the present invention is represented by the following general formulas (I) and / or (II). (R ₁ is a linear or branched alkyl group having 8 to 22 carbon atoms, n and m are average addition moles of ethylene oxide, n and m are not 0, and 2 ≦ n + m
≤15) (R ₂ is a linear or branched alkyl group having 7 to 21 carbon atoms, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 3 carbon atoms, and n is 2 ≦ (represents a number n ≦ 5)

In the above general formula, R ₁ has 8 to 2 carbon atoms.
Examples of the alkyl group 2 include an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and a mixture of alkyl groups derived from natural products and having different numbers of carbon atoms. Of these, a dodecyl group and an alkyl group derived from coconut oil are preferred. R ₂ has 7 to 7 carbon atoms.
It is an alkyl group having 21 and is preferably an alkyl group having 11 to 17 carbon atoms. The alkyl group may be linear or branched, and may be saturated or unsaturated. R ₃ and R ₄ have the same or different carbon numbers 1 to
The alkyl group is a methyl group, an ethyl group, a propyl group, and the like. Of these, a methyl group is preferable.

Specific examples of the amine oxide represented by the above general formula (I) include bishydroxyethyl dodecylamine oxide, bishydroxyethyl cocoalkylamine oxide, bishydroxyethyl myristylamine oxide, bishydroxyethylstearylamine oxide. And the like.

Specific examples of the amine oxide represented by the above general formula (II) include lauroylamidopropyldimethylamine oxide, palmitoylamidopropyldimethylamine oxide, stearoylamidopropyldimethylamine oxide, cocoylamidopropyldimethylamine oxide, Oleylamidopropyldimethylamine oxide, hardened tallow alkyloylamidopropyldimethylamine oxide, and the like.

The content of the component (3) in the bleaching composition of the present invention is usually 0.1 to 5% by mass, preferably 0.1 to 5% by mass.
It is in the range of 5 to 3% by mass. (3) The content of the component is 0.
When the amount is less than 1% by weight, the bubble force when sprayed using a discharge device such as a trigger type sprayer is deteriorated, and when it exceeds 5% by mass, the stability of the alkali metal hypochlorite over time is deteriorated.

The method for producing the amine oxides represented by the general formulas (I) and (II) is not particularly limited, and an aliphatic tertiary amine and an aqueous hydrogen peroxide solution may be reacted at 50 to 80 ° C. It is desirable that the amount of hydrogen peroxide brought into the agent composition be 0.1% by mass or less, preferably 0.05% by mass or less based on the whole composition. That is,
The tertiary amine oxide is used in an amount of about 1.1 times mol of hydrogen peroxide more than that of the aliphatic tertiary amine in order to increase the reaction efficiency when the aqueous hydrogen peroxide solution is added to the aliphatic tertiary amine. When added, the residual hydrogen peroxide reacts with the alkali metal hypochlorite, which is the bleaching base, and as a result, the effective chlorine content of the alkali metal hypochlorite decreases, and the bleaching power deteriorates Therefore, it is desirable to control the carry-in amount to 0.1% by mass or less based on the whole composition.

The tertiary amine used as a raw material includes bishydroxyethyldecylamine, bishydroxyethyldodecylamine, bishydroxyethylmyristylamine, bishydroxyethylpalmitylamine,
Examples include lauroylamidopropyldimethylamine, palmitoylamidopropyldimethylamine, and stearoylamidopropyldimethylamine. As the hydrogen peroxide to be reacted, an aqueous solution of 20 to 90% by mass is industrially available. % By mass is preferred.

In the present invention, other surfactants may be used in addition to the above-mentioned amine oxide. The surfactant is not particularly limited as long as it is used for general cleaning use, and an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a cationic surfactant, and the like can be used. Among these, it is preferable to mix (4) an alkali metal salt of a fatty acid and (5) an alkylbenzene sulfonate to improve the adhesion retention property. At least one of these may be blended,
It is preferable to use them in combination.

The alkali metal salt of a fatty acid as the component (4) is not particularly limited, but an alkali metal salt of a fatty acid having 8 to 20 carbon atoms and containing linear or branched unsaturation is preferable. Suitable alkali metal salts of fatty acids containing unsaturation include, for example, coconut fatty acids containing an average of about 12 carbons (derived from coconut oil) and tallow fatty acids containing an average of about 18 carbon atoms (derived from tallow fats). ), Sodium salts such as oleic acid and linoleic acid, and potassium salts. These alkali metal salts of unsaturated fatty acids may be used alone, for example, a mixture of unsaturated fatty acids such as oleic acid and linoleic acid and saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid. May be used as a sodium salt, a potassium salt and the like. The proportion of this unsaturated fatty acid in the mixture is preferably at least 2% by mass, particularly preferably at least 7% by mass. If the proportion occupied by the unsaturated fatty acid is too small, the viscosity of the system decreases, and as a result, the adhesion retention property deteriorates, which is not preferable.

The content of the component (4) in the bleaching composition of the present invention is in the range of 0.01 to 3% by mass, preferably 0.1 to 2% by mass of the whole composition. (4) When the content of the component is less than 0.01% by mass, the adhesion retention property is poor,
If it exceeds 3% by mass, the stability of the system is deteriorated.

The alkylbenzene sulfonate as the component (5) is not particularly limited, but the alkyl group substituted on the benzene ring has 8 to 20 carbon atoms, preferably 12 carbon atoms.
To 14, and a linear one is preferable. The content of the component (5) in the bleaching composition of the present invention is 0.01 to 0.5% by mass, preferably 0.0 to 0.5% by mass of the whole composition.
It is in the range of 5 to 0.3% by mass. (5) When the content of the component is less than 0.01% by mass, the adhesion retention property is poor, and
If the amount is more than mass%, the stability of the system deteriorates.

When these surfactants are dispersed in a high electrolyte solution mainly composed of an alkali metal hypochlorite,
In a stationary state or in a low shear rate region, the string-shaped micelles are entangled to increase the viscosity, and in a high shear rate region discharged from the nozzle of the discharge container, the flow is untangled or the string-shaped micelles are formed. Are arranged in parallel, the viscosity is considered to be extremely reduced. The composition discharged to the object to be washed, such as a vertical surface or an inclined surface, is considered to be formed again with a random entanglement when returning to the low shear rate region, which is in the attached state, and to the standing state, and the viscosity is reduced again. The thixotropy of the quasi-viscous flow increases.

In the present invention, it is preferable that the composition has the above structural viscosity. For this reason, the composition has a low viscosity in a high shear rate range when spraying from a discharge device such as a trigger type sprayer. It has a viscosity and needs to have a high viscosity in a low shear rate region (stationary) when it adheres to a wall surface or the like. That is, Haake RS-10 at 25 ° C.
The viscosity measured with a 0 viscometer is 0.1 to 100 mpa · s, preferably ^{1 in} a high shear rate region of 3000 sec ^−1.
５０50 mPa · s, more preferably 1 to 10 mPa · s
In the low shear rate region (stationary) of 0.5 sec ⁻¹ , 100 to ¹ × 10 ⁵ mPa · s, preferably 5 × 10 ²
１1 × 10 ⁵ mPa · s, more preferably 1 × 10 ³
It needs to be 1 × 10 ⁵ mPa · s. 3000se
If the viscosity in the high shear rate range of c ^-1 is higher than the above value, it is not preferable because the composition is difficult to spray from a discharge device such as a trigger type sprayer. Also, 0.5s
When the viscosity in the low shear rate region (stationary) of ec ^-1 is lower than the above value, the adhesion retention property on a wall surface or the like decreases, and when the viscosity is higher than the above value, a discharge device such as a trigger type sprayer described below. It becomes difficult to continuously pump up the composition from the dip tube.

The composition of the present invention contains components (1) to (3) as essential components, and further contains components (4) and (5) as necessary. It is also possible to mix optional components such as aromatic sulfonates such as sulfonates and xylene sulfonates, solvents, dyes, and fragrances. The mixing amount of these optional components can be a usual amount as long as the effects of the present invention are not impaired. The bleach composition of the present invention can be prepared by a conventional method by adding a balanced amount of water to the above essential components and the other optional components.

The discharge container of the present invention is provided with a discharge device for discharging the above-described composition, and the discharge device is fitted with a sliding portion such as a piston / cylinder or a liquid passage to a pump housing. If it has a part, it will be used without a restriction | limiting in particular.

As a specific example, the composition contained in the discharge container 1 as shown in FIG.
The discharge container 1 provided with the trigger type sprayer 6 for discharging by operating the piston 4 and the cylinder 5 by pulling the trigger 3 and the composition stored in the container body by moving the pump head up and down through the dip tube. A discharge container provided with a discharge device such as a pump sprayer for discharging is used.

[0027]

According to the present invention, since the bleaching agent contained in a discharge container provided with a discharge device such as a trigger type sprayer has excellent foaming power when discharged from the discharge device,
The mist can be prevented from scattering or bouncing. In addition, since the composition has excellent thixotropy even though it is a surfactant system, it is excellent in dischargeability from the discharge device and adhesion retention property of the discharge liquid sprayed on the dirty object on the vertical surface or inclined surface, Very good bleaching power can be obtained in a short time. Therefore,
The bleach of the present invention does not need to be re-applied to the same place many times, so that waste is not wasted. Therefore, it is suitably used for hard surfaces such as bathrooms, kitchens, and toilets.

[0028]

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.

[0029]

[Production Example 1] Bishydroxyethyl dodecylamine 27
3 g (1.0 mol) and 589 g of ion-exchanged water were charged into a reaction vessel equipped with a thermometer, a stirrer, a cooling tube, and a dropping funnel, and heated while stirring, and kept at 60 to 70 ° C.
102 g of a 35% aqueous hydrogen peroxide solution (1.
(0.5 mol) was dropped, and the mixture was aged for 3 hours to complete the reaction. Unreacted amine was extracted from the reaction mixture with hexane to obtain 30% by mass of amion oxide.

[0030]

Production Examples 2 to 4 Similarly to Production Example 1, 107 g of a 35% aqueous hydrogen peroxide solution (1.1 mol, ion-exchanged water 464)
g), 117 g (1.2 mol, ion exchange water 454)
g), 126 g (1.3 mol, 445 g of ion-exchanged water)
Was used to obtain 30% by mass of amion oxide, amion oxide, and amion oxide.

[0031]

Production Example 5 Amion oxide was obtained in the same manner as in Production Example 1 using bishydroxyethyl cocoalkylamine.

[0032]

Production Example 6 299 g (1.0 mol) of lauroylamidopropyldimethylamine synthesized from lauric acid and N, N-dimethyl-1,3 propanediamine and 646 g of ion-exchanged water were charged into a reaction vessel and heated with stirring. And
After maintaining the temperature at 80 ° C., 107 g (1.1 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise over 3 hours, and the mixture was aged for 5 hours to complete the reaction. Unreacted amine was extracted from the reaction mixture with hexane to obtain 30% by mass of amion oxide.

[0033]

EXAMPLE I Various bleaching compositions having the compositions shown in Tables 1 and 2 were prepared, and the foaming power and the bleaching power were evaluated based on the following criteria. Tables 1 and 2 show the obtained results.

<Measurement of Foaming Force> Using a trigger type dispenser (YT87L-FM, manufactured by Yoshino Kogyosho Co., Ltd.) adjusted so that the sample is sprayed in a steady state, the distance was 20 cm.
Spray panel (30 × 3)
(0 cm; ABS) was sprayed with two strokes of each of the bleaching compositions on the central portion, and the foaming power at that time was sensory evaluated by five panelists according to the following evaluation criteria.

Evaluation criteria: ：: good foaming at spraying △: slightly foaming at spraying ×: no foaming at spraying

<Bleaching power; horizontal measuring method> Black mold (Cla)
dosporium cladosporioide
s) was cultivated and applied, and an unglazed tile (SPAXC-1060, manufactured by INAX) was used as a model plate (L value of model mold plate when L value of unglazed tile was calculated as 100 = 30-4
0). The model mold plate was placed horizontally, and about 0.5 g of each bleaching composition was dropped at the center of the plate. Three
After leaving to stand for minutes, washing with water and air-drying, the lightness (L value) was measured using a colorimeter (CR-200, manufactured by MINOLTA).

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

EXAMPLE II Various bleaching compositions having the compositions shown in Tables 3 and 4 were prepared and evaluated for viscosity, dischargeability, adhesion retention rate and bleaching power based on the following criteria. The obtained results are shown in Tables 3 and 4.

<Measurement of Viscosity> HAAKE FISON
S company viscometer (Rheo Stress RS-10)
Using 0), the viscosity of each bleaching detergent was measured. C35 / 4 ° is used for the cone plate, and the sample volume is about 0.5 mL.
And then, the shear rate 0~3000sec ^-1 / 10 min, 3
The measurement was performed at 000 to ⁰ sec ⁻¹ / 10 minutes, and the viscosity was 3000 sec ⁻¹ at the time of the forward trip and 0.0.
A viscosity of 5 sec ^-1 / was determined.

<Evaluation Method of Discharge Property> A trigger type sprayer (YT87L-FM, manufactured by Yoshino Kogyo Co., Ltd.) was filled with various compositions, and the total was added to the center of a spray panel vertically set from a position at a distance of 20 cm. The user stroked 10 times.
In order to eliminate the influence of the initial empty space and the like, the dischargeability when the stroke was performed 5 to 10 times was sensory evaluated by five panelists according to the following evaluation criteria.

Evaluation criteria: ：: Stroke can be performed without resistance, and the agent can be discharged uniformly. Δ: Some resistance to stroke, making continuous spraying difficult. X: There is considerable resistance to the stroke and continuous spraying is not possible.

<Measurement Method of Adhesion Retention Ratio> Similar to the evaluation of dischargeability, various bleaching detergents are sprayed for two strokes, and one minute later, the weight of the panel is measured. This test was performed three times, and the adhesion retention rate was calculated by the following equation.

(Equation 1)

<Bleaching power; vertical measuring method> Bleaching power: A model mold plate adjusted in the same manner as the horizontal measuring method was placed vertically, and a trigger-type dispenser (YT8 manufactured by Yoshino Kogyosho Co., Ltd.)
7L-FM), and sprayed various bleach compositions onto the center of a 1-stroke (about 0.8 g) plate from a distance of 10 cm. After leaving for 3 minutes, washing with water and air-drying, a colorimeter (CR-200, manufactured by MINOLTA)
Was used to measure the lightness (L value).

[0045]

[Table 3]

[0046]

[Table 4]

[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

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C11D 3/395 C11D 3/395 (72) Inventor Fujio Wakui 1-7-3 Honjo, Sumida-ku, Tokyo Lion stock In-company (72) Inventor Akihiro Sato 1-12-8 Ryogoku, Sumida-ku, Tokyo Muneka Wabiru Lion Akzo Co., Ltd.

Claims (4)

[Claims] (1) alkali metal hypochlorite;
0.1 to 5% by mass; (3) an amine oxide represented by the following general formula (I) and / or (II): 0.1 to 5% by mass; A bleaching composition characterized by containing: (R ₁ is a linear or branched alkyl group having 8 to 22 carbon atoms, n and m are average addition moles of ethylene oxide, n and m are not 0, and 2 ≦ n + m
≤15) (R ₂ is a linear or branched alkyl group having 7 to 21 carbon atoms, R ₃ and R ₄ are linear or branched alkyl groups having 1 to 3 carbon atoms, and n is 2 ≦ (represents a number n ≦ 5) 2. The bleaching composition according to claim 1, wherein the content of hydrogen peroxide in the amine oxide is 0.1% by mass or less based on the whole composition. 3. An alkali metal salt of (4) a fatty acid,
The bleach composition according to claim 1, further comprising (5) an alkylbenzene sulfonate. 4. A bleaching composition in a discharge container comprising a container main body for storing contents and a discharge device for discharging the contents stored in the container main body, wherein the bleaching composition contains The viscosity measured with a Haake RS-100 viscometer at 25 ° C. is 10 at a shear rate of 0.5 sec ^−1.
The bleaching agent composition according to claim 1, wherein the bleaching agent composition has a shear rate of 0.1 to 100 mPa · s under a shearing rate of 0 to 1 × 10 ⁵ mPa · s and 3000 sec ⁻¹ .