JPH0441717B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a stable suspension liquid detergent composition, more specifically, it has excellent cleaning power and polishing power,
The present invention relates to a liquid detergent composition containing an abrasive that has an excellent feel on the hands and skin after use and has excellent dispersion stability. [Prior Art] Conventionally, liquid detergents for kitchens such as vegetable and dishwashing have been mainly composed of compositions that utilize only the detergency of surfactants. This type of cleaning agent has excellent cleaning power for cleaning vegetables, liquid oil, semi-solid oil, etc., but it can also be used to clean foods that have been denatured or semi-solid due to food cooking or being left unused, solid oil, and baking oil. The cleaning power of these substances is relatively weak, and granular, powdered, or liquid polishing cleansers are usually used as cleaning aids to clean tableware and cooking utensils that have been contaminated with these substances. [Problems to be Solved by the Invention] On the other hand, various liquid cleaning compositions containing water-insoluble abrasives have recently been proposed. These cleaning agents are preferable because they have both normal cleaning power for removing non-adhesive stains and abrasive power for removing adherent stains. Increasing the content of abrasive to improve the strength increases the tendency to damage the items to be washed, and has the disadvantage that the abrasive contained therein settles out during storage. In addition, in order to improve these drawbacks, creating a composition that emphasizes dispersion stability by using a clay whose main component is smectite, a multi-chain structure type clay mineral, or both, increases viscosity and impairs the feel of use. At the same time, foaming power and cleaning power are inevitably reduced. Alternatively, if sufficient shear is not applied at the time of blending the clay mineral, a composition with extremely poor dispersion stability will be obtained, failing to achieve the initial objective. In addition, dispersion stability at room temperature is improved when fatty acid salts are used as thickeners and dispersion stabilizers, but at high temperatures, this neutralized product is solubilized by coexisting surfactants, Because the compound itself melts, the viscosity and thixotropy decrease significantly,
This tended to result in a composition with extremely poor dispersion stability. [Means for solving the problem] For this purpose, an abrasive-containing cleaning composition that has excellent cleaning properties such as polishing power, cleaning power, and foaming power, and can maintain stability for a long period of time is developed. development was requested. The inventors of the present invention have conducted intensive research in order to meet these demands. As a result, we have found that a product containing the following ingredients as essential ingredients and whose pH has been adjusted to 4.0 to 6.5 has excellent cleaning power and foaming. It has strong and abrasive power, has an excellent feel on the skin after use, and has a low viscosity.
It was discovered that the abrasive exhibits excellent dispersion stability not only at low temperatures but also at high temperatures, even though it is very easy to remove from the container at 2000 cp or less, and based on this knowledge, the present invention was completed. In the present invention, the reason why the composition has excellent dispersion stability despite its low viscosity is that the cleaning 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 area, and has an appropriate structural viscosity, making it a single phase that is thermally stable over time and over a wide temperature range of -15℃ to +70℃. This is thought to be due to the formation of a smectic liquid crystal region that exists as a region. That is, the present invention provides (a) one or more anionic surfactants selected from the group consisting of polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and alkanesulfonates; 3 to 25% by weight (b) Monolinear alkyl tertiary amine oxide 1 to 25% by weight
10% by weight (c) 1-10% by weight of higher fatty acid alkanolamide (d) 0.1-10% by weight of polyalkylene oxide adduct of polyhydric alcohol and/or its sulfate ester salt (e) Mohs with an average particle size of 1-100μ It contains 1 to 25% by weight of a water-insoluble abrasive having a hardness of 2 to 8, and the proportions of components (a), (b), and (c) are triangular coordinate point 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:(b)11:(c)50] and has a PH of 4.0 to 6.5. The anionic surfactant used as component (a) is one or more selected from the group consisting of polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and alkanesulfonates. Any anionic surfactant can be used, but polyoxyethylene alkyl ether sulfate R ₁ O (CH ₂ CH ₂ O) _o SO ₃ M ( In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 9 to 15 carbon atoms, and n is an average of
A real number from 0.5 to 7, M being an alkali metal, an alkaline earth metal, an ammonium group or an alkanol-substituted ammonium group) is preferred. If the carbonic acid number is less than 9, the cleaning performance will be low, and if it is more than 16, not only will the rinsing performance be markedly reduced, but the abrasive in the composition will tend to precipitate and the stability over time will tend to be impaired, so this is preferable. do not have. The particularly preferred number of carbon atoms is in the range of 10 to 13. In addition, the number n of moles of ethylene oxide added in the general formula should be within the average range of 0.5 to 7 in order to obtain a region where a stable liquid crystal phase exists over a wide temperature range or a region where the amount of solubilization is increased. is preferred. Outside this range, the liquid crystal phase becomes difficult to exist at high temperatures above 35°C or low temperatures below -5°C, and the dispersion stability of the abrasive tends to be impaired. Furthermore, if it is less than 0.5, it tends to increase irritation to hand skin. Particularly preferable number n of moles of ethylene oxide added is 2.0 to 5.5
is within the range of Furthermore, 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, or an alkanol-substituted ammonium residue such as a diethanol-substituted ammonium residue or a monoethanol-substituted ammonium residue. . The content of the former component (a) in the present invention is in the range of 3 to 25% by weight, and if this content is less than 3% by weight, the detergency and foaming power will be insufficient, and if the content is less than 3% by weight, the content will be insufficient. If it exceeds this, the stability of the composition will deteriorate. The preferred content is in the range of 8-12% by weight. The monolinear alkyl tertiary amine oxide used as component (b) in the composition of the present invention includes:
The following general formula (In the formula, R ₂ is a linear or branched alkali group having 12 to 14 carbon atoms, and R ₃ and R ₄ are a methyl group or an ethyl group.) Oxides are preferred. The number of carbon atoms in R ₂ is
If it is less than 12, the cleaning performance of the composition will be low, and if it exceeds 14, stability over time will be impaired, which is not preferable. Further, R ₃ and R ₄ in the general formula are a methic group or an ethyl group, and these may be the same or different from each other. It is necessary to contain this tertiary amine oxide at a ratio of 1 to 10% by weight in the cleaning composition, and if the content deviates from the above range, the cleaning power in combination with component (a) will be reduced. or stability is impaired. The higher fatty acid alkanolamide used as component (c) in the composition of the present invention has 10 carbon atoms.
Preferably, those synthesized from one or a mixture of two or more of ~18 saturated or unsaturated fatty acids and alkanolamines, such as:
Examples include lauroyl diethanolamide, cocoyl diethanolamide, cocoyl monoethanolamide, etc. Among these, particularly desirable are diethanolamide of coconut oil fatty acid or lauric acid. The content of these higher fatty acid alkanolamides is in the range of 1 to 10% by weight. Component (d) in the composition of the present invention is a polyalkylene oxide adduct of a polyhydric alcohol and/or a sulfuric ester salt thereof, and examples of the polyhydric alcohol include ethylene glycol, propylene glycol, neopentyl glycol, etc. Suitable examples include dihydric alcohols, glycerin, polyglycerin, trimethyl or higher alcohols such as trimethylolpropane, pentaerythritol, and sorbitol. The polyalkylene oxide is preferably one obtained by addition polymerization of one or two of ethylene oxide (EO) or propylene oxide (PO), and when PO and EO are addition polymerized, the addition state may be in the form of a block. It may be random. A polyalkylene oxide adduct of a polyhydric alcohol having an average molecular weight of 3,000 to 5,000 is preferably used. If it deviates from this range, the effects of the present invention will be poor. This polyalkylene oxide adduct of polyhydric alcohol or its sulfuric ester salt is produced according to a conventional method (for example, JP-A-57-5796). Further, the salt is a water-soluble salt, and preferable salts include alkali metal salts, alkaline earth metal salts, alkanolamine salts, and ammonium salts, among which alkali metal salts and alkaline earth metal salts are particularly preferable. These (d) components can be used alone or in combination of two or more. Note that it is possible to introduce a number of sulfate groups corresponding to the valence of the polyhydric alcohol into the sulfate ester salt, but in order to fully exhibit the desired effect, it is necessary to introduce a number of sulfate groups in one molecule. It is preferable that the number is 4 or less. The polyalkylene oxide adduct of polyhydric alcohol and/or its sulfate salt is blended in the total composition in an amount of 0.1 to 10% by weight. If the amount is less than 0.1% by weight, the effects of the present invention will not be exhibited, while if it exceeds 10% by weight, the stability of the composition will deteriorate, which is not preferable. The water-insoluble abrasive used as component (c) in the composition of the present invention has an average particle size of 1 to 100 microns and a Mohs hardness of 2 to 8. If the Mohs hardness is less than 2, the abrasive power is too small and it does not provide sufficient abrasiveness, and if it exceeds 8, there is a greater tendency to damage the items to be washed, which is inappropriate. Examples of suitable abrasives include agate, quartz, silica, alumina, diatomaceous earth, perlite, feldspar, aluminosilicate, aluminum hydroxide, emery, dolomite, magnesium oxide, titanium oxide, silicon carbide,
Examples include powdered plastics such as polystyrene, polyacrylate, and nylon, and pulverized natural materials such as sand. These may be used alone or in combination of two or more. If the particle size of this abrasive is less than 1 μm, the abrasive power will be extremely low, and if it is too large, it may damage base materials such as stainless steel or glass, which is not preferable. The content of the water-insoluble abrasive in the composition of the present invention is 1 to 25% by weight.
If the content is less than 1% by weight, the polishing power will be insufficient, and if it exceeds 25% by weight, the viscosity of the cleaning composition will increase, making it difficult to take it out of the container, etc. This is not preferable because it impairs the usability. The preferred content is in the range of 5 to 15% by weight. Components (a) and (b) in the composition of the present invention and
The ratio of the (c) component is the triangular coordinate points A [(a)73:(b)20:(c)7] and B [(a)20:(b)73:(c) shown in Figure 1 of the attached drawing. )
7], C [(a)11:(b)39:(c)50] and D[(a)39:(b)
11:(c)50], and deviations from this range tend to impair the dispersion stability of the abrasive. This can be easily explained based on the component ratio, viscosity, and phase diagram of the above components. 1st
The figure shows the scope of the present invention, and the outer quadrilateral is (a).
The ratio of the components to the components (b) and (c) is within a range that satisfies the scope of the above claims. Figures 2 and 3 show the ratio of components (a), (b), and (c) at 20°C and pH 4.0 to 6.5, respectively, and the phase with increased or moderate solubilization region. Phase diagram and viscosity showing a region that is stable over time and thermally due to its structural viscosity, that is, a region in which a smectic liquid crystal phase that exists as a stable one-phase region over a wide temperature range of -15°C to +70°C is obtained. FIG. In Fig. 2, a region exhibiting a phase with an increased stable solubilization region or a smectic liquid crystal phase that is stable over time and thermally with an appropriate structural viscosity (regions indicated by I and LC in the figure) and Fig. 3 The area in which the regions exhibiting appropriate viscosity (800 to 2000 cp) overlap in FIG. 1 is the region characterized by the present invention. In addition, the figure in Figure 2 is a liquid-liquid two-phase system, and the numbers in Figure 3 are viscosity (cp/20℃)
It is. In other words, if you create a composition with a high ratio of component (a) in an attempt to obtain only a composition with a lower viscosity and an emphasis on usability, the dispersion medium itself becomes thermodynamically unstable, leading to a composition that impairs dispersion stability. Moreover, if a composition with a high ratio of components (b) and (c) is created with only emphasis on dispersion stability, the viscosity will be too high, impairing the feel of use, and furthermore, the composition will have poor foaming power. . Preferably, the ratios of components (a), (b), and (c) are triangular coordinate points A [(a)73:(b)20:(c)7] and E[(a)55:(b) 38
:
(c)7], F [(a)55:(b)25:(c)20], G[(a)50:(b)
twenty five:
(c) 25] and H [(a) 50: (b) 14: (c) 36], and within this range, the composition has particularly excellent rinsability and finish after cleaning. You can get things. In addition, the PH of the composition in the present invention is 4.0 to 6.5, and if this PH is less than 4.0, it may cause irritation to the skin, problems with the finish such as water repellency remaining after washing glassware, and problems with the cleaning composition. This is undesirable because the viscosity increases, impairing the usability such as ease of removal from the container. Moreover, if the pH exceeds 6.5, the structural viscosity will be lost and the dispersion stability will be impaired, which is not preferable. The pH range is preferably 5.0 to 6.5 in terms of dispersion stability, low irritation to the skin, and rinsability. The composition of the present invention is formulated into a liquid using water as a medium, and has a viscosity that provides an appropriate feeling of use, for example, at room temperature.
Adjusted to 800-2000cp. In addition, the composition of the present invention may contain other optional ingredients used in ordinary liquid cleaning compositions, such as hydrotropes such as polyhydric alcohols, sulfuric acid, etc., to the extent that the intended performance is not impaired. Viscosity modifiers such as inorganic salts of hydrochloric acid, alkenylsuccinic acid, glycerin, sorbitol as foam improvers, fragrances, pigments, preservatives, fungicides, and other surfactants and cationized cellulose as feel improvers. A polymeric substance or the like can be added as desired. The dispersion stability of the present composition is not affected by the material of the container, and any container can be used, including containers made of plastic such as polyethylene, polyvinyl chloride, polypropylene, polystyrene, and polyethylene terephthalate, and containers made of glass. [Effects of the Invention] The cleaning composition of the present invention eliminates various drawbacks of conventionally known cleaning agents of this type, has excellent cleaning power, rinsing ability, polishing power, and dispersion stability,
Moreover, it is an abrasive-containing cleaning composition of high practical value that has mild irritation to the skin and gives a pleasant feel to the skin of the hands after use. [Example] Next, the present invention will be explained 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 cleaning power, foaming power, viscosity, storage stability, and hand feel after use of each composition were investigated. Cleaning compositions in each example The various performance measurements and evaluations were carried out as follows. <Test method> (Cleaning power) Sudan (red pigment) is added to beef tallow as an indicator.
0.1% by weight was added, and 5g of this was placed in a magnetic dish (diameter 25
cm) is washed, rubbed with a sponge soaked in water, and the number of plates washed until no more beef tallow can be removed from the plate is shown. (Foaming power) Commercially available butter as a stain ingredient was added to a detergent concentration of 0.5.
The foaming power is measured when 0.1% by weight is added to a detergent solution of 0.1% by weight. The measurement method is to put the above detergent solution to which butter has been added into a glass cylinder with a diameter of 5 cm, rotate and stir for 5 minutes, and measure the foam height after stopping. (Viscosity) Put each composition into a viscosity beaker kept at 20℃,
Measure using a B-type viscometer (rotor No. 3; if it exceeds 2000 cp, rotor No. 4; rotation speed 60 rpm). (Storage Stability) 100 ml of each composition was collected in a 100 ml glass bottle with an inner diameter of 40 mm and a height of 70 mm, and the appearance was visually observed after storage for 3 months after sealing. The criteria for judgment at this time are as follows. ○...Does not separate (stable) △...Slightly separates ×...Completely separates (feel on hand after use) Ten housewives actually used it at home and evaluated them as follows. Evaluation method +2...Very good +1...Good 0...Can't say either -1...Poor -2...Very bad

【table】

[Table] Example 2 The compositions shown in Table 2 were prepared and examined for detergency, foaming power, viscosity, storage stability, and hand feel after use.
Regarding the feel of the product on their hands after use, 30 housewives were asked to actually use it at home and evaluate it in the same manner as in Example 1.

【table】

【table】 [Brief explanation of the drawing]

Figure 1 is a diagram showing the ratio of components (a), (b), and (c) of the present invention, and Figure 2 is a diagram showing the phase equilibrium in the three-component system of (a), (b), and (c). Figure 3 shows the three-component system of (a), (b), and (c) at 20°C.
The isoviscosity curve diagram is shown.

Claims (1)

[Scope of Claims] 1 (a) One or more anionic compounds selected from the group consisting of polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and alkanesulfonates. Surfactant 3-25% by weight (b) Monolinear alkyl tertiary amine oxide 1-1
10% by weight (c) 1-10% by weight of higher fatty acid alkanolamide (d) 0.1-10% by weight of polyalkylene oxide adduct of polyhydric alcohol and/or its sulfate ester salt (e) Mohs with an average particle size of 1-100μ It contains 1 to 25% by weight of a water-insoluble abrasive having a hardness of 2 to 8, and the ratio of components (a), (b), and (c) is point A on the triangular coordinate [(a) 73:( b)20:(c)7〕,B〔(a)
20:(b)73:(c)7], C[(a)11:(b)39:(c)50] and D
An abrasive-containing cleaning composition, characterized in that the pH of the composition is within the range surrounded by [(a)39:(b)11:(c)50] and is 4.0 to 6.5. 2. The abrasive-containing cleaning composition according to claim 1, wherein component (a) is a polyoxyethylene alkyl ether sulfate represented by the general formula (I). R ₁ O (CH ₂ CH ₂ O) _o 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 the average
(M is an alkali metal, an alkaline earth metal, an ammonium group, or an alkanol-substituted ammonium group) 3. The polyalkylene oxide adduct of a polyhydric alcohol has an average molecular weight of 300 to 5000 The abrasive-containing cleaning composition according to item 1. 4 The ratio of components (a), (b) and (c) is at point A on the triangular coordinates.
[(a)73:(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].