JPH0631406B2 - Abrasive-containing cleaning composition - Google Patents

Description

The present invention relates to a stable suspension type liquid detergent composition, more specifically, it has excellent detergency and abrading power, and is particularly mild to the skin of hands. The present invention also relates to a liquid detergent composition containing an abrasive, which is excellent in dispersion stability.

[Conventional technology]

Liquid detergents for kitchen use such as washing vegetables and dishes have hitherto been mainly composed of compositions utilizing only the detergency of a surfactant. This type of cleaning agent has excellent cleaning power for washing vegetables and liquid oil, semi-solid oil, etc., but for example, food, solid oil, baked oil denatured or semi-solidified by cooking food or leaving it The cleaning power against such as is relatively weak, and a granular, powdery or liquid polishing cleanser is usually used as a cleaning aid for cleaning dishes and cooking utensils to which these are adhered.

[Problems to be solved by the invention]

On the other hand, recently, various liquid detergent compositions containing a non-aqueous abrasive have been proposed. These cleaning agents are preferably those having both a normal cleaning power for removing non-sticky dirt and a polishing power for removing sticky dirt. Increasing the content of the abrasive in order to improve the power increases the tendency to damage the object to be washed, and
There is a drawback that the abrasive contained in it precipitates during storage. In addition, if a composition that emphasizes dispersion stability is made with a smectite or a clay having a double-chain structure type clay mineral or both as the main components to improve these drawbacks, the viscosity will increase and the use feeling will be impaired at the same time. The foaming power and detergency are unavoidable. Alternatively, when the clay mineral is not sufficiently sheared, only a composition having extremely poor dispersion stability can be obtained, and the intended purpose cannot be achieved. Further, when a fatty acid salt is used as a thickening / dispersion stabilizer, the dispersion stability at room temperature is improved, but at high temperatures, this neutralized product is solubilized by a coexisting surfactant, or Since it itself melts, the viscosity and thixotropy are remarkably lowered, and the composition tends to have extremely poor dispersion stability.

[Means for solving problems]

For this reason, the development of an abrasive-containing detergent composition that has excellent cleaning properties such as polishing power, cleaning power, and foaming power, yet has a low viscosity that makes it easy to take it out of a container and that can maintain stability for a long time Was requested. The inventors of the present invention have conducted extensive studies in order to meet such demands, and the following components are contained in water in a specific ratio range, and the pH thereof is 4.0 to 6.5.
Although it has excellent cleaning power, foaming power and polishing power, is mild to the skin and has a viscosity of 2000 cp or less and is very easy to remove from the container, it can be used at high temperatures as well as low temperatures. It was found that even the excellent dispersion stability of the abrasive was exhibited, and the present invention was completed based on this finding.

In the present invention, the reason why the composition of the present invention has excellent dispersion stability despite its low viscosity is that the detergent composition of the present invention has an anionic surfactant and an amine oxide in a weakly acidic region. Form a strong aggregate, which increases the solubilization region, has a suitable structural viscosity, and is a thermally stable one-phase region over a wide temperature range of -15 ° C to + 70 ° C. It is considered that this is because the existing smectic liquid crystal region is formed.

That is, the present invention is selected from the group consisting of (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkane sulfonate 1
One or more anionic surfactants 3 to 25% by weight (b) mono-linear alkyl tertiary amine oxide 1 to 10% by weight (c) higher fatty acid alkanolamide 1 to 10% by weight (d) average A water-based composition comprising 4 to 25% by weight of a water-insoluble abrasive having a particle size of 1 to 100 µ and a Mohs hardness of 2 to 8, and a ratio of components (a), (b) and (c). , Point A with triangular coordinates [(a) 73: (b) 20: (c)
7], E [(a) 55: (b) 38: (c) 7], F [(a) 55: (b) 2
5: (c) 20], G [(a) 50: (b) 25: (c) 25] and H [(a) 5
0: (b) 14: (c) 36] and a pH of the composition is 4.0 to 6.5.

The anionic surfactant used as the component (a) is one or more selected from the group consisting of polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkane sulfonate. Although any of the anionic surfactants can be used, the polyoxyethylene alkyl ether sulfate represented by the following general formula R ₁ O (CH ₂ CH ₂ O) _n SO ₃ M ( In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 9 to 15 carbon atoms, n is a real number of 0.5 to 7 on average, M is an alkali metal, alkaline earth metal, ammonium group or alkanol A substituted ammonium group) is preferred. If the carbon number is less than 9, the cleaning performance is low,
On the other hand, when it is 16 or more, not only is the rinsing property remarkably lowered, but also the abrasive of the composition tends to precipitate and the stability over time tends to be impaired, such being undesirable. A particularly preferred carbon number is in the range of 10 to 13. Further, the ethylene oxide addition mole number n in the general formula is preferably in the range of 0.5 to 7 on average in order to obtain a region where a stable liquid crystal phase exists or a region where the amount of solubilization is increased over a wide temperature range. . If it deviates from this range, high temperature of 35 ℃ or more
Since the liquid crystal phase is less likely to exist in a low temperature region of 5 ° C. or less, the dispersion stability of the abrasive tends to be impaired. Further, if it is less than 0.5, the irritation to the hand skin tends to increase. Particularly preferred number of moles of ethylene oxide added
n is in the range of 2.0 to 5.5. Further, M in the formula is an alkali metal such as potassium or sodium, or an alkaline earth metal such as magnesium or calcium, an ammonium residue,
Alkanol-substituted ammonium residues such as diethanol-substituted ammonium residues and monoethanol-substituted ammonium residues.

The content of the component (a) in the present invention is in the range of 3 to 25% by weight, and if the content is less than 3% by weight, the detergency /
The foaming power is insufficient, and when it exceeds 25% by weight, the stability of the composition is deteriorated. The preferred content is in the range of 8 to 12% by weight.

The mono-linear alkyl tertiary amine oxide used as the component (b) in the composition of the present invention has the following general formula: (In the formula, R ₂ is a straight-chain or branched alkyl group having 12 to 14 carbon atoms and R ₃ and R ₄ are methyl groups or ethyl groups). Oxide is preferred. When the carbon number of R ₂ is less than 12, the cleaning performance of the composition is low, and when it exceeds 14, the stability over time is impaired, which is not preferable. In addition, R ₃ and R ₄ in the general formula
Is a methyl group or an ethyl group, which may be the same or different from each other. This tertiary amine oxide needs to be contained in the detergent composition in a proportion of 1 to 10% by weight, and if the content deviates from the above range,
In combination with the component (a), the detergency is lowered or the stability is impaired.

The higher fatty acid alkanolamide used as the component (c) in the composition of the present invention is synthesized from alkanolamine and one or a mixture of two or more saturated or unsaturated fatty acids having 10 to 18 carbon atoms. Preferred are, for example, lauroyl diethanolamide, cocoyl diethanolamide, cocoyl monoethanolamide and the like. Among them, particularly desirable are coconut oil fatty acid or lauric acid diethanolamide. The content of these higher fatty acid alkanolamides is in the range of 1 to 10% by weight.

The water-insoluble abrasive used as the component (d) in the composition of the present invention has an average particle size of 1 to 100 μm and a Mohs hardness of 2 to 8. If the Mohs hardness is less than 2, the polishing force is too small to provide sufficient polishing properties, and if it exceeds 8 the tendency to damage the object to be washed becomes unsuitable. Examples of suitable abrasives are agate, quartz, silica, alumina, diatomaceous earth, perlite, feldspar, aluminosilicate, aluminum hydroxide, emery, dolomite, magnesium oxide, titanium oxide, silicon carbide, polystyrene, polyacrylate, nylon. Examples thereof include plastic powder, natural crushed products such as sand, and the like.
These may be used alone or in combination of two or more. If the particle size of this abrasive is less than 1 μ, the dispersion stability will be good, but the polishing power will be extremely low, and if it is too large, it will cause damage to a substrate such as stainless steel or glass, which is not preferable. In the composition of the present invention, the content of the water-insoluble abrasive is in the range of 4 to 25% by weight, and if the content is less than 4% by weight, the polishing power is insufficient. If it exceeds 5% by weight, the viscosity of the detergent composition may increase and the usability such as the ease of taking it out of the container may be impaired. The preferred content is in the range of 5 to 15% by weight.

The ratios of the components (a) to (b) and (c) in the composition of the present invention are shown by the triangular coordinate point A [(a) 7 shown in FIG. 1 of the accompanying drawings.
3: (b) 20: (c) 7], E [(a) 55: (b) 38: (c) 7], F
[(A) 55: (b) 25: (c) 20], G [(a) 50: (b) 25: (c) 25]
And H [(a) 50: (b) 14: (c) 36], and if it deviates from this range, the dispersion stability of the abrasive tends to be impaired. This can be easily explained based on the component ratios and viscosities of the above components and the phase diagram. FIG. 1 shows the scope of the present invention. The outer pentagon has components (a) and (b).
The ratio of the component and the component (c) is within the range satisfying the above claims. Figures 2 and 3 show 20 ℃ and pH4.
In 0 to 6.5, the ratio of (a) component, (b) component and (c) component and the stable solubilized region is a phase with an increased phase or moderate structural viscosity, and is a thermally stable region with time, That is, it is a state diagram showing a region where a smectic liquid crystal phase existing as a stable one-phase region over a wide temperature range of -15 ° C to + 70 ° C is obtained and a diagram showing a relationship with viscosity. In FIG. 2, a stable solubilized region has an increased phase or a region showing a time- and thermally-stable smectic liquid crystal phase having an appropriate structural viscosity (I in the figure).
And area indicated by LC) and an appropriate viscosity in Fig. 3
The overlapping portion of the area indicating (800 to 2000 cp) is the area within the characteristic range of the present invention in FIG. II in FIG. 2 is a liquid-liquid two-phase system, and the numbers in FIG. 3 are viscosities (cp / 20 ° C.). That is, if a composition having a higher ratio of the component (a) is tried to obtain only a composition having a lower viscosity and a feeling of use, the dispersion medium itself becomes thermodynamically unstable, resulting in a composition that impairs dispersion stability. And, focusing only on dispersion stability
If the composition of the components (b) and (c) is high, the composition will have a too high viscosity and will impair the feeling of use, and the composition will also have a poor super-foaming power.

According to the present invention, a composition which is particularly excellent in terms of rinsing property after washing and finishing property within the range surrounded by the pentagon of FIG. 1 can be obtained.

Further, the pH of the composition in the present invention is 4.0 to 6.5, irritation to the skin when this pH is less than 4.0, and problems with the finish such as water repellency after cleaning glass dishes and cleaning composition This is not preferable because the viscosity increases and the usability such as the ease of ejection from the container is impaired. Further, if the pH exceeds 6.5, the structural viscosity is lost and the dispersion stability is impaired, which is not preferable. From the viewpoint of dispersion stability, low irritation to the skin, and rinsability, the pH is preferably 5.0 to 6.5.

The composition of the present invention is liquefied with water as a medium, and is prepared to have a viscosity giving an appropriate feeling of use, for example, 800 to 2000 cp at room temperature.

Further, the composition of the present invention includes a short-chain fatty acid carboxylic acid having 1 to 6 carbon atoms, an oxyacid or an acid salt thereof, an acidic amino acid or an acid salt thereof, an aromatic carboxylic acid, nicotinic acid, kainic acid, sorbic acid, By blending one or more organic acids selected from the group consisting of benzenesulfonic acid, toluenesulfonic acid and pyrrolidonecarboxylic acid or a salt thereof, a more stable and low viscosity composition can be obtained. Tartaric acid,
Oxycarboxylic acids such as malic acid, citric acid and the like are particularly preferred. The blending amount is suitably 0.05 to 10% by weight, particularly 0.5 to 5% by weight.

Further, the composition of the present invention, within a range that does not impair the intended performance, other optional components used in a normal liquid detergent composition, for example, a hydrotrope agent such as polyhydric alcohol, sulfuric acid, or the like, Viscosity modifiers such as inorganic salts of hydrochloric acid, alkenyl succinic acid, glycerin, sorbitol as foam quality improvers, fragrances, dyes, antiseptic, antifungal agents, or other surfactants and cationized celluloses as touch enhancers. A polymer substance or the like can be added as desired.

〔The invention's effect〕

The cleaning composition of the present invention is not only extremely easy to use, such as easy to remove from the container, but also eliminates various drawbacks of conventionally known cleaning agents of this type, has excellent cleaning power and rinsability, It is a cleaning composition containing an abrasive having a high practical value, which has polishing power and dispersion stability and is mildly irritating to the skin.

〔Example〕

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

Example 1 The compositions shown in Table 1 were prepared, and the detergency, foaming power, viscosity, storage stability and ease of removal from the container of each composition were investigated. The various performances of the cleaning composition in each example were measured and evaluated as follows.

<Test method> (Detergency) 0.1% by weight of Sudan III (red pigment) as an indicator in beef tallow
Add 5g of this to a magnetic dish (25cm in diameter) and rub it with a sponge soaked with detergent and water.
It is indicated by the number of washed dishes until no more beef tallow is removed from the dishes.

(Foaming Power) The foaming power is measured when 0.1% by weight of commercially available butter is added as a soil component to a detergent solution having a detergent concentration of 0.5% by weight.
The measuring method is as follows. The above detergent solution containing butter is placed in a glass cylinder having a diameter of 5 cm, and the mixture is rotatively stirred for 5 minutes, and the foam height after stopping is measured.

(Viscosity) Each composition was placed in a viscosity beaker maintained at 20 ° C, and a B-type viscometer (rotor No. 3 was used.
4; measurement is performed using a rotation speed of 60 rpm).

(Storage stability) 100 ml of each composition was sampled in a 100 ml glass bottle having an inner diameter of 40 mm and a height of 70 mm, and the appearance when stored for 1 month after sealing was visually observed. The judgment criteria at this time are as follows.

○: Not separated (stable) △: Slightly separated ×: Completely separated (easy to remove from the container) A container (600 ml) of commercially available kitchen detergent of each composition was filled with 150 ml, and an angle of 45 Fix it on a support with an inclination of °,
The weight of the composition that emerged from the container cap (bore diameter 3.0 mm) when a lead weight with a load of 2 kg was placed was measured. The criteria for judgment at this time are as follows.

○: 7.0g or more easily produced △: 3.0g or more, but less than 7.0g Slightly easy to produce ×… less than 3.0g difficult to produce Example 2 The composition shown in Table 2 was prepared and the detergency, foaming power, viscosity, storage stability and ease of ejection from the container were examined. At this time, 30 housewives actually used it at home and evaluated it as follows for the ease of taking it out from the container.

(Evaluation method) +2 ... Very easy to output +1 ... Easy to output 0 ... Neither can be said -1 ... Slightly difficult to output -2 ... Difficult to output

[Brief description of drawings]

FIG. 1 is a diagram showing the ratios of the components (a), (b) and (c) of the present invention, and the numbers in the figure show the composition Nos. In Tables 1 and 2. Fig. 2 shows the phase equilibrium diagram of the ternary system of (a), (b) and (c), and Fig. 3 shows the equilibrium diagram of the ternary system of (a), (b) and (c) at 20 ° C. A viscosity curve diagram is shown.

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Claims (3)

[Claims] (A) One or more anionic surface active agents selected from the group consisting of (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkane sulfonate. Agent 3
-25 wt% (b) Mono-linear alkyl tertiary amine oxide 1-10 wt% (c) Higher fatty acid alkanolamide 1-10 wt% (d) Average particle size 1-100μ and Mohs hardness 2-8 An aqueous composition comprising 4 to 25% by weight of a water-insoluble abrasive and water, wherein the ratios of components (a), (b) and (c) are points A ((a) 73 :( b) 20: (c)
7], E [(a) 55: (b) 38: (c) 7], F [(a) 55: (b) 2
5: (c) 20], G [(a) 50: (b) 25: (c) 25] and H [(a) 5
0: (b) 14: (c) 36], and the pH of the composition is 4.0 to 6.5. 2. The cleaning composition according to claim 1, wherein the component (a) is a polyoxyethylene alkyl ether sulfate represented by the general formula (I). R ₁ O (CH ₂ CH ₂ O) _n SO ₃ M (I) (In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 9 to 15 carbon atoms, and n is 0.5 to 0.5 on average. A real number of 7, M is an alkali metal, alkaline earth metal, ammonium group or alkanol-substituted ammonium group) 3. (e) a short-chain aliphatic carboxylic acid having 1 to 6 carbon atoms, an oxyacid or an acid salt thereof, an acidic amino acid or an acid salt thereof, an aromatic carboxylic acid, nicotinic acid, kainic acid, sorbic acid, The cleaning composition according to claim 1, which comprises 0.05 to 10% by weight of one or more organic acids selected from benzenesulfonic acid, toluenesulfonic acid and pyrrolidonecarboxylic acid or salts thereof.