JPH0699710B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a detergent composition, more specifically, the irritation and damage to skin and hair are remarkably alleviated, and the foaming power and detergency are excellent. Moreover, the present invention relates to a liquid detergent composition whose liquid color and odor do not change with time.

[Problems to be Solved by Prior Art and Invention]

Today, the awareness of the safety of the human body is increasing,
In detergents that often come into contact with human skin, such as laundry detergents, kitchen detergents, household detergents, hair detergents, and personal detergents, various detergents are used in order to moderate the action on the skin. Attempts have been made, for example, the pH of the composition.
Is adjusted to 5 to 6 (weakly acidic) to bring it closer to the pH of human skin so that its action on the skin becomes mild,
For example, the main cleaning base is one that is as mild as possible. Amino acid-based surfactants and alkylphosphoric acid-based surfactants are used as such mild detergent bases (Japanese Examined Patent Publication No. 40-40125, Japanese Examined Patent Publication No.
51-426023, JP-B-55-9093, JP-B-58-27319).

However, although these surfactants are hypoallergenic, they have drawbacks such as not being able to exert sufficient foaming power and detergency alone and poor solubility. In addition, in kitchen cleaners, sodium alkylbenzene sulfonate has been widely used as a base with excellent cleaning performance, but it has the disadvantage that it has a strong degreasing power from the skin and easily causes rough hands. ing.

For this reason, kitchen detergents based on sodium alkylethoxysulfate, which is less irritating to the skin, as the main washing base have recently become the mainstream, and further, tertiary amine oxides and higher fatty acids By using a co-surfactant such as diethanolamide together, various performances are further improved, and at the same time, the action on the skin has become milder.

However, although the action of various detergents on the skin has become milder than in the past, the present situation is that it has not yet reached a sufficiently satisfactory level.

On the other hand, although alkylglycoside, which is a derivative surfactant, is not only a mild surfactant but also a nonionic surfactant, it not only produces stable bubbles but also other It is known to act as a foam stabilizer for ionic surfactants, and has been attracting attention in recent years. For example, JP-A-53-104625 discloses a foaming surfactant composition containing an alkyl glycoside and an anionic surfactant, and JP-A-62-74999 discloses an alkyl glycoside, an anionic surfactant. A liquid dishwashing liquid detergent composition containing an activator and a fatty acid alkanolamide and having low irritation and excellent foaming power and detergency is described. However, although the various performances of these detergent compositions are superior to those of conventional detergents containing polyoxyethylene alkyl ether as a main component, they are still insufficient, and especially the liquid color and odor change with time, and the quality deteriorates. Have the problem of doing.

[Means for Solving the Problems]

In such an actual situation, the present inventors have conducted extensive studies to maximize the properties of alkyl glycosides,
If a surfactant containing a sulphate group and / or a sulphonate group is blended in a specific ratio, and a terpene hydrocarbon selected from monoterpenes and sesquiterpenes and 3-isothiazolone and / or its derivative are used in combination, the effect on the skin is improved. The inventors have found that a detergent composition in which the irritancy is further alleviated, the detergency and foaming ability are enhanced, and the deterioration of liquid color and odor due to aging is improved can be obtained, and the present invention has been completed.

That is, the present invention provides the following components (a) to (d) (a) the following general formula (I) R ₁ (OR ₂ ) xGy (I) (wherein R ₁ is a linear or branched carbon atom). Represents an alkyl group, an alkenyl group or an alkylphenyl group of the number 8 to 18,
R ₂ represents an alkylene group having 2 to 4 carbon atoms, and G represents 5 carbon atoms.
~ 6 is a residue derived from a reducing sugar, x is a number having an average value of 0 to 5, and y is a number having an average value of 1.0 to 1.42). 60% by weight (b) Surfactant containing a sulfate group and / or sulfonate group 0.1 to 40% by weight (c) Terpene hydrocarbon selected from monoterpenes and sesquiterpenes 0.01 to 3% by weight (d) The following general formula (II) and (III) (In the formula, R ₃ and R ₄ represent hydrogen, halogen or an alkyl group having 1 to 5 carbon atoms, and Y represents hydrogen or an alkyl group having 1 to 18 carbon atoms) and 3-isothiazolone and its derivative One or two or more types of 0.0001 to 0.1% by weight of (a) / (b) in a weight ratio of 50/1 to 1/50 are provided. is there.

In the present invention, the alkyl glycoside of the component (a) is used as a main surfactant, and in the above general formula (I), x has an average value of 0 to 5, but this value is water-soluble, Adjust crystallinity. That is, the higher x, the higher the water solubility and the lower the crystallinity. The preferred value of x is 0-2. Next, when the average of y is greater than 1, that is, when y contains a surfactant represented by the general formula (I) that is a hydrophilic group of a sugar chain of two or more sugars, the binding mode of the sugar chain is 1- It is possible to include 2, 1-2, 1-4, 1-6 bonds, as well as α-, β-pyranoside, or furanoside bonds and any mixtures thereof with mixed binding modalities. Also, the preferable average value of y is 1.0 to 1.42,
A particularly preferred average value is about 1.10 to 1.40. The measuring method of y is based on the proton NMR method. R ₁ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group,
From the viewpoint of foamability and detergency, the preferred carbon number is 10-14. R ₂ is an alkylene group having 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms from the viewpoint of water solubility. Further, the structure of G is determined by a monosaccharide or a raw material of two or more sugars. As the raw material of G, glucose, galactose, xylose, mannose, lyxose, arabinose and the like, and mixtures thereof, etc. Examples of disaccharides or more include maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose, and mating products thereof. Of these, preferred monosaccharide raw materials are glucose and fructose, and maltose and sucrose for disaccharides and above, because of their availability and low cost.

The component (a) is contained in the composition in an amount of 1 to 60% by weight (hereinafter simply referred to as%).
,), Preferably 10-40%.

Examples of the surfactant containing a sulfate group and / or a sulfonate group as the component (b) of the present invention include polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, alkane sulfonate, Examples thereof include α-sulfonated fatty acid derivatives, sulfobetaine, and acylmethyl taurine, which can be used alone or in combination of two or more kinds.

Of these, polyoxyethylene alkyl ether sulfates in terms of skin mildness, especially the following general formula (IV) R ₅ O (CH ₂ CH ₂ O) nSO ₃ M (IV) (wherein R ₅ is carbon A polyoxyethylene alkyl ether sulfate represented by the formula 10 to 18 alkyl group or alkenyl group, M is an alkali metal, ammonium or alkanolamine, and n is an average of 1 to 7). When the carbon number of R ₅ is less than 10, cleaning performance is insufficient, and when it exceeds 18, the low temperature stability of the composition is significantly deteriorated, which is not preferable. Particularly preferred carbon number is 12-14
Is the range. Further, when the ethylene oxide addition mole number n in the formula (IV) is less than 1, it is not preferable because it increases irritation to the skin, and when it exceeds 7, cleaning performance is significantly deteriorated, which is not preferable. A particularly preferable range of the number of moles of ethylene oxide added is 2 to 5.

The following general formula (V) (In the formula, R ₆ represents an alkyl group having 10 to 16 carbon atoms, and M has the same meaning as described above). If the carbon number of R ₆ is less than 10, the cleaning performance is insufficient, and if it exceeds 16, the low temperature stability of the composition is significantly deteriorated, which is not preferable. A particularly preferred carbon number is in the range of 11-13.

Further, as sulfobetaine, the following general formula (VI) (In the formula, R ₇ represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, and R ₈ and R ₉ represent an alkyl group having 1 or 2 carbon atoms;
Is a hydroxyl group or a hydrogen atom) is preferable.

The component (b) is 0.1 to 40%, preferably 0.5 to 40% in the total composition.
20% is included.

Examples of the component (c) used in the present invention include monoterpene hydrocarbons or sesquiterpene hydrocarbons contained in plant aromatic oils. As the monoterpene hydrocarbon, orange oil, D- or L-limonene contained in lemon oil and the like, α- or β-pinene contained in terpine oil, etc.,
Examples of α-terpineol and the like contained in pine oil and the like, as the sesquiterpene hydrocarbon,
Carophyllene, sedrene, etc., which are often contained in fern oil, clover oil, and cananga oil, can be exemplified. Each terpene-based hydrocarbon selected from monoterpenes and sesquiterpenes can be used alone as the component (c) of the present invention, and can also be used by mixing two or more kinds thereof, and further, orange oil, The terpine oil and the pine oil can be blended in the composition of the present invention as they are. The blending amount of the component (c) is 0.01 to 3 of the detergent composition.
%, Preferably 0.1 to 2%. This amount is 0.01
If it is less than 0.1%, the desired improvement of the liquid color and the deterioration of odor will be insufficient, while if it exceeds 3%, the coloring property and low temperature stability of the detergent composition will be deteriorated, which is not preferable.

The 3-isothiazolones represented by the general formulas (I) and (II) and their derivatives used as the component (d) in the composition of the present invention include an alkyl glycoside and a surfactant containing a sulfate group and / or a sulfonate group. The contained detergent composition exhibits a remarkable effect of preventing discoloration and odor.

This effect is exhibited when the pH of the detergent composition is within the range of 4 to 10, and when the pH is out of the above range, the effect is weak or does not appear at all. Such pH dependence is considered to be due to the stability of 3-isothiazolone and its derivatives in the composition.

3-isothiazolone and its derivatives were added to the detergent composition at 0.
It is necessary to contain 0001 to 0.1%, and if it is less than 0.0001%, the effect of preventing discoloration is small, and if it exceeds 0.1%, skin irritation is increased, which is not preferable.

In addition to the above-mentioned components, the cleaning composition of the present invention may contain known compounding ingredients which are usually compounded in cleaning composition. For example, anionic surfactants, amphoteric surfactants, nonionic surfactants, and viscosity modifiers such as ethyl alcohol, glycerin, propylene glycol, and inorganic salts in amounts that do not impair the effects of the present invention; lower alkylbenzene sulfones. Hydrotropes such as acid salts, urea, lower alkyl sulphates; viscosity modifiers for clay minerals and water-soluble polymers; water-insoluble abrasives such as calcite, silica stone, calcium phosphate, zeolite, polyethylene, nylon, polystyrene; glycerin A humectant such as sorbitol, a texture-improving agent such as cationized cellulose, an enzyme, a fragrance, a dye, an antiseptic / antifungal agent, and the like can be added.

The pH range of the undiluted solution of the detergent composition of the present invention is preferably 4 to 10, and particularly preferably 5 to 8.

〔The invention's effect〕

The detergent composition of the present invention has excellent detergency and rich foaming ability, has a mild action on the skin and hair and is less rough to the hands, and its liquid color and odor do not change with time. It has high intellectual value.

〔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.

<Test Method and Evaluation Criteria> The tests and evaluations in the examples were carried out as follows.

(1) Foaming power test The foaming power is measured when 0.1% of commercially available butter is added as a stain component to a detergent solution having a detergent concentration of 0.5%. The measurement method is
40 ml detergent solution with butter added to a glass cylinder with a diameter of 5 cm
And stir for 10 minutes, and measure the foam height immediately after stopping.

(2) Detergency test 0.1% Sudan III (red pigment) was added to beef tallow as an indicator, 2.5 g of this was applied to a porcelain dish (diameter 25 cm), 3 g of detergent, water (water; hardness 3.5 ° DH) Of water) Scrub with 27 g of impregnated sponge at 20 ° C and show with the number of dishes washed until no more beef tallow is removed from the dishes.

(3) Hand roughness test A 5% by weight detergent composition detergent solution was prepared and the liquid temperature was 30 ° C.
Soak your hands for 20 minutes every day, and then wash thoroughly 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 observed 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 (4) Liquid color and odor Stability test Put the detergent composition in a 50 ml glass bottle and store it in a constant temperature bath at 40 ° C for 1 month, and then evaluate the liquid color and odor. The evaluation criteria at this time are as follows.

A: There is almost no change.

B: Some changes are observed.

C: There is considerable change.

D: Significant change is observed.

Example 1 The compositions shown in Table 1 below were prepared and evaluated for detergency, foaming power, liquid color, odor and rough hands by the above-mentioned evaluation methods. The results are shown in Table 1.

Example 2 The following liquid detergent compositions were tested for detergency, foaming ability, liquid color stability, odor stability, and hand roughness.
The results are shown in Table 2.

[Composition] Alkyl glycoside 20 (wt%) Polyoxyethylene (4) alkyl (C _{12 to} C ₁₃ ) ether sodium sulfate (alkyl: straight chain / branched chain = 60/40 weight ratio) 3 Lauryl dimethylamine oxide 2 Vegetable aromatic oil (terpene hydrocarbon) (Table 2) Reference) 0.1 ~ 2
4-Benzo-3-isothiazolone 0.02 Ethanol 3 Dye, fragrance Suitable amount Water balance 100 Example 3 The following liquid detergent compositions were tested for detergency, foaming ability, liquid color stability and odor stability. The results are shown in Table 3.
Shown in.

[Composition] Alkyl glycoside 20 (wt%) Polyoxyethylene (4) alkyl (C _{12 to} C ₁₃ ) ether sodium sulfate (alkyl: straight chain / branched chain = 50/50 weight ratio) 3 Lauryl dimethyl hydroxy sulfobetaine 2
D-limonene 0.5 3-isocyazolone derivative (see Table 3) 0.00001 to 0.10 Ethanol 3 Perfume Suitable amount Water balance 100

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C11D 1:12 1:68) (56) Reference JP-A-58-104625 (JP, A) JP-A-62 -74999 (JP, A) JP-A-64-1796 (JP, A) JP-A-60-106898 (JP, A)

Claims (2)

[Claims] 1. The following components (a) to (d) (a) The following general formula (I) R ₁ (OR ₂ ) xGy (I) (wherein R ₁ is a straight or branched chain carbon number) 8 to 18 alkyl group, alkenyl group or alkylphenyl group,
R ₂ represents an alkylene group having 2 to 4 carbon atoms, and G represents 5 carbon atoms.
~ 6 is a residue derived from a reducing sugar, x is a number having an average value of 0 to 5, and y is a number having an average value of 1.0 to 1.42). 60% by weight (b) Surfactant containing a sulfate group and / or sulfonate group 0.1 to 40% by weight (c) Terpene hydrocarbon selected from monoterpenes and sesquiterpenes 0.01 to 3% by weight (d) The following general formula (II) and (III) (In the formula, R ₃ and R ₄ represent hydrogen, halogen or an alkyl group having 1 to 5 carbon atoms, and Y represents hydrogen or an alkyl group having 1 to 18 carbon atoms) and 3-isothiazolone and its derivative 1 or 2 types or more of 0.0001-0.1 weight%, and (a) / (b) are 50 / 1-1 / 50 by weight ratio, Cleaning composition characterized by the above-mentioned. 2. The component (b) is represented by the following general formula (IV) R ₅ O (CH ₂ CH ₂ O) nSO ₃ M (IV) (wherein R ₅ is an alkyl group or alkenyl having 10 to 18 carbon atoms). Group, M represents an alkali metal, ammonium or an alkanolamine, and n represents an average number of 1 to 7). The detergent composition according to claim 1, which is a polyoxyethylene alkyl ether sulfate.