JPH0765070B2 - Emulsion hard surface cleaner composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a milky liquid hard surface cleaning composition, and more particularly to skin irritation and damaging properties which are remarkably alleviated, and which have excellent foaming power and detergency. The present invention relates to a milky liquid hard surface cleaner composition which has a good feeling after hand and is particularly suitable as a dishwashing agent.

[0002]

2. Description of the Related Art Generally, a hard surface cleaning agent used for cleaning hard surfaces such as tableware usually has a main purpose of removing greasy stains. In most cases, greasy dirt is removed. The function of the foam at this time is to relieve the force required to scrape off the dirt, and in many cases, the amount of foaming is often a measure of the cleaning property of grease stains.
Therefore, it is an important factor in such a detergent that its foaming power is high, and conventional hard surface detergents have alkylbenzene sulfonate as a main surfactant,
α-olefin sulfonate, alkyl sulfate,
Anionic surfactants such as paraffin sulfonates, ethoxylated alkyl ether sulphates have been used. Among them, sodium alkylbenzenesulfonate has been widely used as a base having excellent cleaning performance, but it has a degreasing power from the skin and has a drawback that it easily causes rough hands. For this reason, recently, a detergent composition containing a polyoxyethylene alkyl ether sulfate ester salt, which is less irritating to the skin, as a main detergent base has come to be predominant. However, even though this detergent composition has a milder effect on the skin than before, it has not yet reached a sufficiently satisfactory level.

Alkyl glycosides, which are sugar derivative surfactants, on the other hand, are not only mild surfactants but also nonionic surfactants, they not only generate stable foams themselves, It is known to act as a foam stabilizer against other anionic surfactants, and has been attracting attention in recent years. For example, JP-A-58-104625
A foaming surfactant composition containing an alkylglycoside and an anionic surfactant is disclosed in JP-A-62-74999 (EP21630).
1, US Pat. No. 4,732,704) describes a liquid dishwashing liquid detergent composition containing an alkylglycoside, an anionic surfactant and a fatty acid alkanolamide, which has low irritation, foaming power and detergency. In addition, JP-A 2-1
Japanese Patent No. 64819 (EP374702, US50250)
69) contains an alkylglycoside, an anionic surfactant, an amine oxide and an ethylene oxide addition type nonionic surfactant, and has a low irritation and excellent foaming power and detergency. A detergent composition having a good hand feel is described. JP-A-1-30419
No. 8 discloses a hard surface detergent composition containing an alkyl glycoside and a fatty acid ester of a polyhydric alcohol having a valence of 3 or more, which has low irritation, excellent foaming power and detergency, and which is well washed off. However, it is a transparent dissolution system,
It does not disclose or suggest the invention. Further, the performance of these compositions is superior to conventional polyoxyethylene alkyl ether-based detergents, but it is still insufficient, especially in the feel of the hands after washing, and in the mildness to the rough skin of the hands. Inferior

[0004]

Therefore, there has been a demand for a hard surface cleaning composition which is excellent in detergency and foaming power, is low in irritation, and has a good feeling of hand skin after cleaning.

[0005]

Under the above circumstances, the present inventors have earnestly studied to maximize the properties of alkyl glycosides, and as a result, surprisingly, they are rarely usually incorporated into detergents. 1 or 2 of a partial ester of an aliphatic hydrocarbon polyol having a melting point of 30 ° C. or higher
If more than one kind is added to the detergent, the irritation to the skin is further alleviated, the feel of the hand skin after washing is good, and the foaming power and the detergency are hardly impaired. It was found that these effects can be improved by using a nitrogen-containing surfactant such as the above together, and the present invention has been completed.

That is, the present invention provides the following components (a) and (b) (a) alkyl glycoside
1 to 50% by weight (b) One or two or more 1 to 20% by weight of a partial ester of a fatty acid having an average carbon number of 13 or more of an aliphatic hydrocarbon polyol having a melting point of 30 ° C or more and having a carbon number of 2 to 9 is contained. , A blending ratio of the component (a) and the component (b) is (b) / (a) = 1/10 to 10/1 in terms of a weight ratio, to provide a milky liquid hard surface cleaning composition. It is a thing. In the present invention, "milky liquid" means a state in which the component (b) is dispersed as solid fine particles in the aqueous phase, and an emulsion (emul) in which liquid oil is dispersed as fine particles in the aqueous phase.
sion).

The alkyl glycoside of component (a) in the present invention is used as a main surfactant,
Examples include those represented by the following general formula (1). _{^{R 1 - (OR 2) x}} -G y (1) wherein, R ¹ is straight or branched chain alkyl group having 8 to 18 carbon atoms, alkenyl or an alkyl phenyl group,
R ² represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, x is a number having an average value of 0 to 5, and y is an average thereof. Indicates a number whose value is 1-10]

In the formula (1), R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group, which is more preferable than the solubility, foaming property and detergency. The number is 10-14. R ² is an alkylene group having 2 to 4 carbon atoms, but an alkylene group having 2 to 3 carbon atoms is preferable from the viewpoint of solubility in water and the like.
Further, the structure of G is determined by a monosaccharide or a raw material of two or more sugars. Examples of the raw material of G include glucose, galactose, xylose, mannose, lyxose, arabinose and the like, and mixtures thereof. Examples of disaccharides or more include maltose, xylobiose, isomaltose, cellobiose, gentiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose and the like, and mixtures thereof. Of these, preferred monosaccharide raw materials are
Due to their availability and low cost, they are glucose and fructose, and those with two or more sugars are maltose and sucrose.

X is a number whose average value is 0 to 5, and this value controls the water solubility and crystallinity of the alkyl glycoside. That is, the higher x, the higher the water solubility and the lower the crystallinity. Preferably the value of x is 0-2. Further, y is a number having an average value of 1 to 10, preferably an average value of about 1.0 to 3.0, particularly preferably 1.0 to 1.42. Further, when the average of y is greater than 1, that is, when it contains a surfactant represented by the general formula (1) having a sugar chain of two or more sugars as a hydrophilic group, the sugar chain has a binding mode of 1-2. 1-3, 1-
It is possible to include 4,1-6 linkages, as well as α-, β-pyranoside or furanoside linkages and any mixture thereof with mixed binding modalities. In the present invention, the measuring method of y is based on the proton NMR method.

The component (a) alkylglycoside may be used alone or in combination of two or more, and it is contained in the composition of the present invention in an amount of 1 to 50% by weight, preferably 1 to 40% by weight, more preferably 5 to 30% by weight. % By weight, more preferably 5 to 20% by weight
Be compounded. If the blending amount is less than 1% by weight, the basic performance such as excellent foaming power and detergency cannot be satisfied, and the blending amount is 5
If it exceeds 0% by weight, the viscosity of the composition increases remarkably, which causes another problem that it is difficult to take out the composition-filled container.

[0011]

The partial ester of the aliphatic hydrocarbon polyol having a melting point of 30 ° C. or higher, preferably 50 ° C. or higher, of the component (b) in the present invention is, for example, glycerol, ethylene glycol, propylene glycol and glycerol. Dimer and trimer partial esters of ethylene glycol and propylene glycol,
Partial esters of fatty acids having an average carbon number of 16 or more, such as palmitic acid monoglyceride, stearic acid monoglyceride, ethylene glycol monostearate, and diethylene glycol monostearate, are particularly preferable. Particularly preferred is a fatty acid partial ester of glycerin.
Here, since glycerin fatty acid ester is also one of sebum components, it is left on the skin after use and gives a moisturizing feeling by adding it in a specific ratio in the composition of the present invention. Has a function of protecting the skin.
Therefore, in order for this component to remain on the skin, it can be said that a highly hydrophobic one is preferable. However, if a composition having a high content of triglyceride or diglyceride and a high hydrophobicity is used, the emulsion stability of the composition is deteriorated, the detergency and foaming power are impaired, and the oily feeling is enhanced and the usability is deteriorated. Therefore, the glycerin fatty acid ester has an appropriately balanced hydrophobicity / hydrophilicity, that is, the fatty acid residue has 16 to 24 carbon atoms, particularly 16 to 22 carbon atoms, and the monoglyceride content is 75 to 100% by weight. % Is preferable. In the present invention, a partial ether of an aliphatic hydrocarbon polyol having a carbon number of 2 to 9 and having a melting point of 30 ° C. or higher, preferably 50 ° C. or higher, a lipid having a melting point similar to this, for example, n-eicosane, n-pentacosane, Hydrocarbons such as paraffin, higher alcohols having 14 or more carbon atoms,
Fatty acids such as lauric acid, stearic acid and hydroxystearic acid, waxes represented by lanolin and beeswax, cholesterol and cholesterol esters such as cholesterol stearate may be used in combination.

Each of these components (b) has a melting point of 30.
It is necessary that the temperature is not lower than 0 ° C, preferably not lower than 50 ° C. When the melting point is less than 30 ° C., the composition is almost completely washed away by rinsing after washing and cannot be left on the surface of the skin, and a good hand and skin feel after washing cannot be obtained.

The total amount of component (b) is 1 in the composition of the present invention.
-20% by weight, preferably 3-20% by weight, particularly preferably 3-15% by weight. When the blending amount is less than 1% by weight, the ratio of being solubilized in the component (a) is high, the amount remaining on the skin surface after washing is small, and a good hand-skin feel after washing cannot be obtained. . Also, the compounding amount is 2
If it exceeds 0% by weight, the oily feeling is intensified, which is not preferable, and there is a problem that the composition is remarkably thickened.

Further, the above-mentioned (a) in the composition of the present invention.
The blending ratio of the component and the component (b) is a weight ratio of (b) / (a) = 1/10 to 10 / in consideration of detergency and foaming.
1, more preferably 1/3 to 5/1, and particularly preferably (b) / (a) is more than 1/2 and 5/1 or less.

In the composition of the present invention, as the component (c),
One or two selected from fatty acid amide, amine oxide, sulfobetaine, carbobetaine, alkylamide
By blending one or more nitrogen-containing surfactants, more preferable effects, that is, effects of further relieving irritation and damage to the skin and remarkably improving the sustainability of foam can be obtained.

The nitrogen-containing surfactant as the component (c) is a surfactant containing a nitrogen atom in the molecule, and specifically, the following are exemplified.

[0018]

[Chemical 1]

[0019]

[Chemical 2]

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

These nitrogen-containing surfactants can be used alone or in admixture of two or more. The component (c) is contained in the detergent composition in an amount of 1 to 20% by weight, preferably 1 to 10% by weight, particularly preferably 2 to 10% by weight. Of these components (c), amine oxides are particularly preferable, and those represented by the following general formula (7) are desirable.

[0024]

[Chemical 6]

[In the formula, R ²⁶ represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, and R ²⁷ and R ²⁸ represent a methyl group or an ethyl group]

In the general formula (7), R ²⁶ has 8 carbon atoms.
However, the preferable carbon number is 10-14.
When the composition of the present invention further contains an anionic surfactant as the component (d), the detergency is improved. As the anionic surfactant of the component (d) used in the present invention, any one may be used as long as it has good compatibility with the component (a), economy, etc., and is not particularly limited. is not. (D)
Examples of suitable components are shown below.

(1) Polyoxyalkylene alkyl ether sulfate or alkyl sulfate represented by the general formula (8). R ²⁹ O (R ³⁰ O) _m SO ₃ M ³ (8) (In the formula, R ²⁹ represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, R ³⁰ represents an alkylene group having 2 to 4 carbon atoms, m represents a number of 0 to 7, and M ³ represents an alkali metal, an alkaline earth metal, ammonium or an alkanolamine.) (2) An alkylbenzene sulfonate represented by the general formula (9).

[0028]

[Chemical 7]

(In the formula, R ³¹ represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, and M ³ represents an alkali metal, an alkaline earth metal, ammonium or an alkanolamine.)

(3) An α-sulfofatty acid ester salt represented by the general formula (10).

[0031]

[Chemical 8]

(In the formula, R ³² represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, R ³³ represents an alkyl group having 1 to 3 carbon atoms, M ⁵ represents an alkali metal, an alkaline earth metal or ammonium. Or alkanolamine)

(4) An α-olefin sulfonate having 10 to 18 carbon atoms. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like. (5) Alkane sulfonate having 10 to 18 carbon atoms. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like. These anionic surfactants can be used alone or in admixture of two or more. The component (d) is contained in the detergent composition of the present invention in an amount of 1 to 40% by weight, particularly 5 to 20% by weight.
It is preferably blended.

In the detergent composition of the present invention, in order to enhance the persistence of the component (b) on the skin and not to impair the detergency and foaming ability which are the basic performances as a detergent,
It is desirable to adjust the compounding ratio of the components. That is,
The sum of the components (a), (c) and (d) is preferably 5 to
40% by weight, and if the content is less than 5% by weight, the detergency
Foaming power is insufficient, and if it exceeds 40% by weight, solution stability tends to be impaired. The particularly preferred content is 10 to 40% by weight, and further 10 to 30% by weight. The components (a) to (d) are (b) / [(a) + (c) +
It is necessary that (d)] = 0.05 to 1 (weight ratio), and if it is less than 0.05, the persistence of the component (d) on the skin decreases, and if it exceeds 1, the detergency is high. -It is not preferable because it inhibits the foaming power. A particularly preferred range is 0.1
It is 0.5.

In addition to the above-mentioned essential components, the detergent composition of the present invention may contain various components as required within a range that does not impair the intended performance. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether. Examples of the solubilizer used in the liquid detergent include lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin and sorbitol, p-toluene sulfonate and m-xylene sulfonate. And aromatic sulfonates. In addition, flavors, pigments, antiseptic / antifungal agents, thickeners and the like can be added as desired.

[0036]

The emulsion hard surface cleaning composition of the present invention is not only excellent in detergency and foaming property, but also does not cause redeposition of dirt, does not cause rough hands, and is good for hand skin after cleaning. Give a feel. In addition, since it has a milky appearance, it gives the user a mild feeling. The composition of the present invention is particularly suitable for dishwashing by hand washing,
It can be used for general cleaning of other hard surfaces such as floors, walls, glass, furniture, toilet bowls, etc.

[0037]

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. First, the foaming power, the cleaning power, and the hand feel test after cleaning used in Examples 1 and 2 will be described.

(1) Foaming power test A commercially available butter was used as a stain component to obtain a detergent composition concentration of 1.0.
1% by weight of detergent solution (water: water with a hardness of 3.5 ° DH)
The foaming power when 0% by weight is added is measured. The measuring method was as follows. 40 ml of the above detergent solution containing butter was put into a glass cylinder having a diameter of 5 cm, and the mixture was rotatively stirred at 40 ° C. for 15 minutes, and the foam height immediately after the stop was measured, and the evaluation was made according to the following criteria. A: 50 mm or more B: 20 mm or more and less than 50 mm C: Less than 20 mm

(2) Evaluation of detergency 0.1% Sudan III (red pigment) as an indicator in beef tallow
2.5 g of this was added and applied to a porcelain dish (25 cm in diameter), 3 g of detergent, water (water: water with a hardness of 3.5 ° DH)
A sponge soaked with 27 g was used for scrubbing at 20 ° C., and the number of washed dishes until the beef tallow could no longer be removed cleanly from the dishes was examined and scored according to the following evaluation criteria. A: 4 sheets or more B: 1-3 sheets C: less than 1 sheet

(3) Evaluation of hand feel after washing Two kinds of detergents A and B are prepared, and a detergent solution of 40% at 10% by weight is prepared in a 2 liter beaker. Dip the wrist separately into the aqueous solutions of detergents A and B up to the left and right. After 15 minutes of immersion, the hands were thoroughly rinsed, and the hands were wiped with a dry towel, and the feel of the hands after 5 minutes was evaluated based on detergent A at the following evaluation points.・ Detergent B is moist or Detergent A is dry ... +2 ・ Detergent B is slightly moist or Detergent A is dry ... + 1 ・ Neither can be said ± 0 Detergent B is dry or Detergent A is slightly moist ...- 1 ・ Detergent B is dry or Detergent A is slightly moist ...- 2 The above test was conducted on 10 subjects. The feeling of use of detergent B is evaluated by the sum of the scores obtained for each item.
At this time, the total of the obtained scores was scored according to the following evaluation criteria. A: +7 points to +20 points B: -6 points to +6 points C: -20 points to -7 points

Example 1 Hard surface detergent compositions having the compositions shown in Table 1, Table 2, Table 3, Table 4 and Table 5 were prepared, and for each of them, a foaming power test, evaluation of cleaning power and after cleaning were conducted. The feel of the hand was evaluated. The results are shown in Table 1, Table 2, Table 3, Table 4 and Table 5.
In the evaluation of the feel of the hand after washing, the comparative product 14 was used as the comparative detergent A, and the comparative product 14 and the present invention products 1 to 4,
Comparative tests were performed on Comparative Products 1-14.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

In Tables 1 to 5, * 1: general formula (7); R ²⁶ = C ₁₂ , R ²⁷ = R ²⁸ = C ₁ * 2: alkyl group; C ₁₂ , HLB = 11.7 * 3: alkyl Group; C ₁₂ / C ₁₃ = 1/1

Example 2 Hard surface detergent compositions having the compositions shown in Table 6 were prepared, and for each of them, the foaming power test, the evaluation of the cleaning power, and the roughness of the hand were evaluated in the same manner as in Example 1. went. That is, the 5 wt% solution of each of Inventive Product 5 and Comparative Product 15 was kept at a liquid temperature of 35 ° C., and each of them was immersed in the left and right hands up to the wrist for 20 minutes and then thoroughly washed with water. After repeating this operation for 3 days, the condition of the hands of 12 subjects (all the subjects who were aware that "hands are likely to be rough" in this subject were all extracted.) Were visually judged according to the following criteria, The average score is shown. Further, in this test, the average score is preferably 4 or more. 5 points: Almost no rough hands are recognized 4 points: Rough hands are slightly recognized 3 points: Rough hands are slightly recognized 2 points: Rough hands are considerably recognized 1 point: Rough hands are significantly recognized

[0049]

[Table 6]

Foaming power, cleaning power adopted in Examples 3 and 4,
The redeposition property and hand roughness test will be described. (1) Foaming power test Commercially available butter was used as a stain component to obtain a detergent composition concentration of 0.5.
Add to a detergent solution (water: water with a hardness of 3.5 ° DH) of weight% of 0.
The foaming power when 1% by weight is added is measured. As the measuring method, 40 ml of the above detergent solution to which butter was added was put in a glass cylinder having a diameter of 5 cm, and the mixture was rotatively stirred at 20 ° C. for 15 minutes, and the foam height immediately after stopping was measured. (2) Evaluation of detergency Sudan III (red pigment) 0.1% as an indicator in beef tallow
2.5 g of this was added and applied to a porcelain dish (25 cm in diameter), 3 g of detergent, water (water: water with a hardness of 3.5 ° DH)
It was scrubbed with a sponge soaked with 27 g at 20 ° C., and the number of dishes washed until no more beef tallow could be removed from the dish (the effective number of dishes) was indicated.

(3) Redeposition test 0.1% by weight detergent solution (water: 3.
100 ml of 5 ° DH water) is prepared and 0.1 g of rapeseed oil is added. Soak a clean glass slide for 10 seconds while stirring the above detergent solution with a magnetic stirrer. Pull up the slide glass, and then soak it in 100 ml of rinsing water (3.5 ° DH water) for 10 seconds. After rinsing, it is air-dried at room temperature, and the adhered state of rapeseed oil on the slide glass is visually judged according to the following criteria. still,
The above test is conducted at 25 ° C. ◯: No adhesion of oil droplets is observed. Δ: Adhesion of a small amount of oil droplets is recognized. X: Significant adhesion of oil droplets is recognized. (4) Hand roughness test A 5% by weight detergent composition of a detergent solution was prepared and the liquid temperature was adjusted to 30.
Keeping the temperature at 0 ° C, immersing the hand for 20 minutes, and then thoroughly washing with water. This operation is repeated for 3 days. The condition of the hands of the five test subjects was visually judged after 4 days according to the following criteria, and shown as an average point. The evaluation criteria at this time are as follows. In this test, the average score is preferably 4 or more. 5 points: Almost no rough hands are recognized 4 points: Rough hands are slightly recognized 3 points: Rough hands are slightly recognized 2 points: Rough hands are considerably recognized 1 point: Rough hands are significantly recognized

Example 3 The compositions shown in Table 7 were prepared and tested for detergency, foaming power, feeling of use and hand roughness. The results are shown in Table 7.

[0053]

[Table 7]

Example 4 As shown in Table 8, the component (b) was changed and tested for cleaning power, foaming power, feeling of use, and rough hand. The results are shown in Table 8
Shown in.

[0055]

[Table 8]

Claims (7)

[Claims] 1. The following components (a) and (b) (a) alkyl glycoside
1 to 50% by weight (b) One or two or more 1 to 20% by weight of a partial ester of a fatty acid having an average carbon number of 13 or more of an aliphatic hydrocarbon polyol having a melting point of 30 ° C or more and having a carbon number of 2 to 9 is contained. The emulsion liquid hard surface cleaning composition, wherein the mixing ratio of the components (a) and (b) is (b) / (a) = 1/10 to 10/1 by weight. 2. A fatty acid amide as the component (c),
The emulsion hard surface cleaning composition according to claim 1, which contains 1 to 20% by weight of one or more nitrogen-containing surfactants selected from the group consisting of amine oxide, sulfobetaine, carbobetaine and alkylamide. . 3. The component (b) comprises glycerin and an average carbon number of 1.
The emulsion hard surface cleaning composition according to claim 1, which is a partial ester of 6 or more fatty acids. 4. The component (b) has a fatty acid residue having 16 carbon atoms.
~ 24, and the monoglyceride content is 75 ~
The emulsion hard surface cleaning composition according to claim 1, which is a glycerin fatty acid ester which is 100%. 5. An alkylglycoside (a) is represented by the following general formula (1): R ^1- (OR ² ) _x -G _y (1) [wherein R ¹ is a linear or branched carbon number 8]. To 18 alkyl groups, alkenyl groups or alkylphenyl groups,
R ² represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, x is a number having an average value of 0 to 5, and y is an average thereof. The value shows the number which becomes 1-10] The emulsion liquid hard surface cleaning composition of Claim 1. 6. The emulsion-type hard surface cleaning composition according to claim 1, further comprising 1 to 40% of an anionic surfactant as the component (d). 7. The following components (a) to (d) (a) the following general formula (1) R ^1- (OR ² ) _x -G _y (1) [wherein R ¹ is a straight chain or branched A chain is an alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group, R ² is an alkylene group having 2 to 4 carbon atoms, and G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. Where x is a number having an average value of 0 to 5 and y is a number having an average value of 1 to 10] 1 to 40% by weight (b) Carbon of fatty acid residue Glycerin fatty acid ester having a number of 16 to 24 and a monoglyceride content of 75 to 100% 1 to 20% by weight (c) a nitrogen-containing surfactant 1 to 20% by weight (d) an anionic surfactant 1 to 40% by weight, (a) + (c) + (d) is 5 to 40% by weight, and (B) / [(a) + (c) + (d)] is a milky liquid hard surface detergent composition whose weight ratio is 0.05-1.