JPH0436199B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a stable suspension liquid cleaning composition, more specifically, it has excellent cleaning and polishing power,
In particular, the present invention relates to a liquid detergent composition containing an abrasive that has an excellent feel on the hands after use and 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 against such 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 non-aqueous 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, if a composition is created that emphasizes dispersion stability by having a viscosity mainly composed of smectite and/or multi-chain clay minerals, the viscosity will increase and the feeling of use will be impaired. 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 decreased significantly, and the composition tended to have extremely poor dispersion stability. [Means for solving the problem] For this reason, it has excellent cleaning properties such as polishing power, detergent power, and foaming power, and also has a low viscosity that is easy to remove from the container and maintains stability for a long time. There has been a demand for the development of an abrasive-containing cleaning composition. The inventors of the present invention have conducted extensive research in order to meet these demands. As a result, we have created a product that contains the following components as essential components and further adjusts its pH to 4.0 to 6.5.
It has excellent cleaning power, foaming power, and polishing power, and has an excellent feel on the skin after use.Although its viscosity is less than 2000 cp and it is very easy to remove from the container, it can be used at both low and high temperatures. It was discovered that the abrasive exhibits excellent dispersion stability, 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) 0.01-5% by weight of oil (e) 1-25% by weight of a water-insoluble abrasive with an average particle size of 1-100μ and a Mohs hardness of 2-8 %, and the ratio of components (a), (b) and (c) is 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
Provided is an abrasive-containing cleaning composition, which is within the range surrounded by [(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, n is a real number with an average of 0.5 to 7, and M is an alkali metal, an alkaline earth metal, an ammonium group, or an alkanol. (substituted ammonium group) is preferred. If the number of carbon atoms is less than 9, the cleaning performance will be low, and if it is more than 16, the rinsing performance will be markedly lowered, and the abrasive in the composition will tend to precipitate, resulting in a loss of stability over time, which 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 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, 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 alkyl 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. Furthermore, R ₃ and R ₄ in the general formula are a methyl group or an ethyl group, and these may be the same,
They may be 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. The oil used as component (d) in the present invention is preferably vegetable oil, animal oil, hydrocarbons, alcohol or its ester, aldehyde, fruit or pericarp oil, silicone oil or its derivatives, etc. Specific examples include olive oil, avocado oil, almond oil, safflower oil, soybean oil, rapeseed oil, cottonseed oil, sesame oil, sunflower oil, camellia oil, castor oil, coconut oil, palm oil, palm kernel oil,
Vegetable oils and fats such as corn oil; Animal fats and oils such as mink oil, egg yolk oil, beef tallow, lard, and hydrogenated oil; Animal waxes such as laurin, liquid lanolin, beeswax, and spermaceti; Plants such as jojoba oil, carnauba wax, and candelilla wax waxes; liquid paraffin;
Hydrocarbons such as paraffin, petrolatum, squalane, ozokerite, ceresin, and microcrystalline wax; Terpene hydrocarbons such as limonene, pinene, caryophyllene, cedrene, myrcene, and terpinolene; phenylethyl alcohol, benzyl alcohol, geraniol, citronellol, santalol, lauryl alcohol,
myristyl alcohol, palmityl alcohol,
C ₈ to ₁₈ primary alcohols such as stearyl alcohol and oleyl alcohol; C ₈ to ₁₈ secondary alcohols such as menthol, borneol, carpeol, ethylhexylcarbinol, and petiperol; linalool, terpineol, myrcenol, cedrol, Tertiary alcohols such as tetrahydrolinalool; Esters _of the above alcohols, such as linalyl acetate, porunyl acetate, geranyl acetate, etc.; _C8-18 aldehydes such as citral and citronellal; General formula R ₁ COOR ₂ (however, R ₁ is a C ₇ - C ₂₁ alkyl group or alkenyl group, R ₂ is a C ₁ - C ₂₀ alkyl group) Fatty acid ester, etc. such as orange oil, lemon oil, lime oil, grapefruit oil, mandarin oil, etc. Examples include fruit or pericarp oils, modified silicone oils, and the like. Component (d) is used alone or in combination of two or more, and its content is in the range of 0.01 to 5% by weight, and if this content is less than 0.01% by weight, a sufficient addition effect cannot be obtained, On the other hand, if it exceeds 5% by weight, the stability of the composition will deteriorate. The preferred content is 0.05~
It is in the range of 2% by weight. The water-insoluble abrasive used as component (e) 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 Figure 2, a region exhibiting a phase with an increased stable solubilized region or a smectic liquid crystal phase that is stable over time and thermally with an appropriate structural viscosity (region in the figure and indicated by LC) and a third region are shown. In the figure, the area where the areas exhibiting appropriate viscosity (800 to 2000 cp) overlap is the area characterized by the present invention in the figure. 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 ratio of components (a), (b) and (c) is the triangular coordinate point [(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], and within this range, a composition that is particularly excellent in terms of rinsing properties and finishing properties after washing can be obtained. It will be done. 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. Also, the pH is 6.5
Exceeding this is not preferable because the structural viscosity will be lost and the dispersion stability will be impaired. The preferred pH range is 5.0 to 6.5 in terms of dispersion stability, low irritation to the skin, and rinsability.
is within the range of The composition of the present invention is made 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. The composition of the present invention also includes short-chain aliphatic carboxylic acids having 1 to 6 carbon atoms, oxyacids or acidic salts thereof, acidic amino acids or acidic salts thereof, aromatic carboxylic acids, nicotinic acid, kainic acid, sorbic acid. A more stable and lower viscosity composition can be obtained by blending one or more organic acids or salts thereof selected from the group consisting of benzenesulfonic acid, toluenesulfonic acid, and pyrrolidonecarboxylic acid. tartaric acid,
Particularly preferred are oxycarboxylic acids such as malic acid, citric acid, and the like. The appropriate blending amount is 0.05 to 10% by weight, particularly 0.5 to 5% by weight. 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 is not only extremely easy to use, such as being easy to take out from the container, but also eliminates various drawbacks of conventionally known cleaning agents of this type, and provides excellent cleaning. This is an abrasive-containing cleaning composition with high practical value, which has good strength, rinsing properties, abrasive power, and dispersion stability, is mild in irritation to the skin, and gives a good feel to 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, ease of taking them out from the container, and feel on the hands after use of each composition were examined. The various performances of the cleaning compositions in each example were measured and evaluated as follows. <Test method> (Cleaning power) Sudan (red pigment) is added to beef tallow as an indicator.
Add 0.1% by weight and place 5g of this in a magnetic dish (diameter 25cm)
This is the number of dishes that have been cleaned until the tallow can no longer be removed by scrubbing with a sponge soaked in detergent and water. (Foaming power) The foaming power is measured when 0.1% by weight of commercially available butter is added as a stain component to a detergent solution with a cleaning concentration of 0.5% by weight. The measurement method is to put the 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 (easy to remove from container) Container of commercially available kitchen detergent of each composition (600ml)
A container filled with 150 ml was fixed on a support stand inclined at an angle of 45°, and a lead weight with a load of 2 kg was placed on it, and the weight of the composition coming out of the container cap (diameter 3.0 mm) was measured. The determination criteria at this time are as follows. ○...7.0g or more - Easy to dispense △...3.0g or more and less than 7.0 - Slightly easy to dispense ×...Less than 3.0g - Difficult to dispense (feeling on hand after use) We asked 10 housewives to actually use it at home and found the following: I had it evaluated. 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 ease of removal from a container. At this time, we asked 30 housewives to actually use the product at home and rate it as follows regarding ease of removal from the container. (Evaluation method) +2...Very easy to produce +1...Easy to produce 0...Not sure -1...Somewhat difficult to produce -2...Difficult to produce

【table】

【table】 [Brief explanation of drawings]

Figure 1 is a diagram showing the ratio of a component, b component, and c component of the present invention, Figure 2 is a phase equilibrium diagram for a three-component system of a, b, and c, and Figure 3 is a diagram showing the ratio of a, b, and c components. 20℃ for three-component system
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) 0.01-5% by weight of oil (e) 1-25% by weight of a water-insoluble abrasive with an average particle size of 1-100μ and a Mohs hardness of 2-8 %, and the ratio of components (a), (b) and (c) is 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. 2. The abrasive-containing cleaning composition according to claim 1, wherein component (a) is a polyoxyethylene alkyl ether sulfate represented by the general formula (). 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 0.5 to 7 on average. , M is an alkali metal, an alkaline earth metal, an ammonium group, or an alkanol-substituted ammonium group) 3 (d) component is vegetable oil, animal fat, hydrocarbons,
Containing the abrasive according to claim 1, which is one or more selected from the group consisting of alcohols or their esters, aldehydes, fruit or pericarp oils, silicone oils or derivatives thereof. Cleaning composition. 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].