JPH0631418B2 - 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 water-insoluble 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 strength increases the tendency to damage the object to be washed, and also has the drawback that the abrasive contained therein precipitates during storage. Further, in order to improve these drawbacks, if a composition in which importance is placed on dispersion stability is obtained by using a smectite or a clay having a double-chain structure type clay mineral or both as the main components, the clay will rise and the usability will be impaired, and at the same time it will occur. 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 initial purpose cannot be achieved. Also,
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 the coexisting surfactant, or the neutralized product itself Due to melting, the viscosity and thixotropy were remarkably lowered, and the composition tended to have extremely poor dispersion stability.

[Means for Solving Problems] Therefore, the cleaning properties such as polishing power, cleaning power, and foaming power are excellent, and the viscosity is low enough to be easily removed from the container, and the stability is maintained for a long time. There has been a demand for the development of an abrasive-containing detergent composition to be obtained. 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, it is mild to the skin and its viscosity is 2000 CP or less and it is very easy to take it out of the container, it can be used at high temperature as well as low temperature. 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 an aqueous composition comprising the following (a) to (f) and water, which is an aqueous composition comprising the following (a) to (f) and water: The ratio of the (a) component, the (b) component, and the (c) component in the inside is the point A [(a) 73: (b) 20: (c) 7] of triangular coordinates,
B [(a) 20: (b) 73: (c) 7], C [(a) 11: (b) 39: (c) 5
0] and D [(a) 39: (b) 11: (c) 50], and a cleaning agent composition containing an abrasive characterized in that PH is 4.0 to 6.5. It is provided.

(a) 1 selected from the group consisting of polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkane sulfonate
3 to 25% by weight of one or more anionic surfactants (b) Tertiary amine oxide 1 represented by general formula (I)
~ 10% by weight (In the formula, R ₁ is a linear or branched alkyl group having 12 to 14 carbon atoms and R ₂ and R ₃ are methyl groups or ethyl groups.) (C) Higher fatty acid alkanolamide 1 to 10% by weight ( d) 1 to 25% by weight of a water-insoluble abrasive having an average particle size of 5 to 100 μ and a Mohs hardness of 2 to 8 (e) 0.1 to 5% by weight of a nitrogen-free nonionic surfactant having an HLB of 6.0 to 19.5 % (F) 0.01 to 1.0% by weight of fatty acid represented by general formula (II) (R ₄ in the formula is a linear or branched alkyl group having 9 to 15 carbon atoms.) The anionic surfactant used as the component (a) is polyoxyethylene alkyl ether sulfate or alkylbenzene sulfonate. , Any one or more anionic surfactants selected from the group consisting of α-olefin sulfonates and alkane sulfonates can be used, but when viewed from the mild feeling to the hand skin, the following general formula is used. Polyoxyethylene alkyl ether sulfate represented by R ₅ O (CH ₂ CH ₂ O) _n SO ₃ M (In the formula, R ₅ 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, and M is an alkali metal, alkaline earth metal, ammonium group or alkanol-substituted ammonium group). 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, which is not preferable. A particularly preferred carbon number is in the range of 10 to 13. The ethylene oxide addition mole number n in the general formula is in the range of 0.5 to 7 on average in order to obtain a liquid crystal region that exists as a single liquid phase region that is stable over a wide temperature range or a region in which the amount of solubilization is increased. Preferably there is. If it deviates from this range, the dispersion stability of the abrasive tends to be impaired in the high temperature range of 35 ° C or higher or the low temperature range of -5 ° C or lower. Further, if it is less than 0.5, the irritation to the hand skin tends to increase. The particularly preferred ethylene oxide addition mole number 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, an alkaline earth metal such as magnesium or calcium, an ammonium residue, an alkanol-substituted ammonium residue such as a diethanol-substituted ammonium residue or a monoethanol-substituted ammonium residue. .

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 tertiary amine oxide used as the component (b) in the composition of the present invention is a tertiary amine oxide of mono-long-chain alkyl-di-short-chain alkylamine represented by the general formula (I), R ₁ in the formula is a linear or branched alkyl group having 12 to 14 carbon atoms. When the carbon number of R ₁ is less than 12, cleaning performance of the composition is low, and when it exceeds 14, stability with time is impaired, which is not preferable. R ₂ in the general formula and
R ₃ 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 one synthesized from alkanolamine and a fatty acid obtained from lauric acid or a glyceride of coconut oil, and as such, Examples thereof include lauroyl diethanolamide, cocoyl diethanolamide, coconut monoethanolamide and the like, and among them, particularly desirable is coconut oil fatty acid or diethanolamide of lauric acid. 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 5 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 5 μ, 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 1 to 25% by weight, and if the content is less than 1% by weight, the polishing power is insufficient. If it exceeds 5% by weight, the viscosity of the detergent composition increases, and the usability such as ease of taking out from the container is impaired, which is not preferable. The preferred content is in the range of 5 to 15% by weight.

The nonionic surfactant used as the component (e) in the composition of the present invention does not contain a nitrogen atom, and examples thereof include polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmi. Tate, polyoxyethylene sorbitan monooleate and other polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin monostearate and other polyoxyethylene glycerin fatty acid esters, polyoxyethylene linear or branched higher alcohol ethers, etc. There are 6.0-19.5. These may be used alone or in combination of two or more. The content of the nonionic surfactant in the composition of the present invention is in the range of 0.1 to 5.0% by weight, and if the content is less than 0.1% by weight, the viscosity of the cleaning composition will increase and the container It is not preferable because it impairs the feeling of use such as the ease of taking out the product, and when it exceeds 5.0% by weight, the suspension stability is not improved. The preferred content is 0.5 to 3.0% by weight.

As the fatty acid represented by the general formula (II) of the component (f) in the composition of the present invention, a linear fatty acid or a branched fatty acid such as lauric acid, myriphosphoric acid and palmitic acid can be used. The content of the fatty acid in the composition of the present invention is in the range of 0.01 to 1.0% by weight, the content of 0.0
If it is less than 1% by weight, the rinsing property will be poor, and if it exceeds 1.0% by weight, the viscosity will increase and the usability will be impaired.

Further, the pH of the composition in the present invention is 4.0 to 6.5,
If the pH is less than 4.0, it is not preferable because there is a problem with the finish such as irritation to the skin and water repellency after washing of glass dishes, and if the pH exceeds 6.5, the structural viscosity is lost and the dispersion stability is impaired. It 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 adjusted to have a viscosity that gives an appropriate feeling of use, for example, 800 to 2000 centipoise at room temperature.

Furthermore, (a) component and (b) component in the composition of the present invention and
The ratio of the component (c) is A [(a) 73: (b) 20: (c) 7], B [(a) 20: (b) 73 :( c)
7], C [(a) 11: (b) 39: (c) 50], and D [(a) 39:
By using within the range surrounded by (b) 11: (c) 50], a composition having more excellent dispersion stability can be obtained.

Further, the composition of the present invention, within the range of not losing the performance, other optional components used in ordinary liquid detergent compositions,
For example, polyhydric alcohols, hydrotropes such as short-chain alkylbenzene sulfonates, malic acid, oxycarboxylic acids such as citric acid, sulfuric acid, viscosity modifiers such as hydrochloric acid inorganic salts, or glycerin or sorbitol as a foam improver. , Fragrances, pigments, preservatives, fungicides, or other surfactants, texture-improving agents, polymeric substances such as cationized cellulose for the purpose of improving the finish of tableware, and proteins such as amphoteric substances keratin and collagen. Etc. 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 fat can be washed 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 kept 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 m1 of each composition was sampled in a 100 m1 glass bottle having an inner diameter of 40 mm and a height of 70 mm, and the appearance when stored for 3 months 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 container) Commercially available kitchen detergent container (600 m1) of each composition filled with 150 m1 The composition was fixed on a support table with an inclination of 45 °, and the weight of the composition that emerged from the container cap (caliber 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-easy to put out △… 3.0g or more but less than 7.0g-somewhat easy to put ×… less than 3.0g-difficult to put out Example 2 A composition shown in Table 2 was prepared and its 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 THE DRAWINGS FIG. 1 is a diagram showing the ratio of component (a), component (b) and component (c) of the present invention, wherein the numbers in the figure are the composition Nos. Of Tables 1 and 2. The range surrounded by points A, B, C, and D indicates components (a), (b),
The preferable range of the ratio of (c) is shown.

Claims (2)

[Claims] 1. An aqueous composition comprising the following (a) to (f) and water, wherein the ratio of the components (a), (b) and (c) in the composition is a triangle coordinate. Point A [(a) 73: (b) 20: (c) 7], B
[(A) 20: (b) 73: (c) 7], C [(a) 11: (b) 39: (c) 5]
0] and D [(a) 39: (b) 11: (c) 50] and having a pH of 4.0 to 6.5. (a) 1 selected from the group consisting of polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate and alkane sulfonate
3 to 25% by weight of one or more anionic surfactants (b) Tertiary amine oxide 1 represented by general formula (I)
~ 10% by weight (In the formula, R ₁ is a linear or branched alkyl group having 12 to 14 carbon atoms and R ₂ and R ₃ are methyl groups or ethyl groups.) (C) Higher fatty acid alkanolamide 1 to 10% by weight ( d) 1 to 25% by weight of a water-insoluble abrasive having an average particle size of 5 to 100 μ and a Mohs hardness of 2 to 8 (e) 0.1 to 5% by weight of a nitrogen-free nonionic surfactant having an HLB of 6.0 to 19.5 % (F) 0.01 to 1.0% by weight of fatty acid represented by general formula (II) (R ₄ in the formula is a linear or branched alkyl group having 9 to 15 carbon atoms.) 2. The detergent composition according to claim 1, wherein the component (a) is a polyoxyethylene alkyl ether sulfate represented by the general formula (III). R ₅ O (CH ₂ CH ₂ O) _n SO ₃ M (III) (In the formula, R ₅ 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)