JP2955032B2 - Hypoallergenic detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition which satisfies essential conditions for a detergent such as foaming property and detergency, and has extremely low skin irritation.

[0002]

2. Description of the Related Art Conventionally, in a surfactant or a surfactant composition having a strong protein denaturing power, a roughening phenomenon of strength has been recognized by continuously using them, whereas a surfactant having a low protein denaturing power or a surfactant thereof have been used. Composition (eg shampoo)
It is well known that skin is difficult to cause skin damage such as rough hands even if it is used for a long period of time, and that its irritation to the skin is extremely low.

On the other hand, higher alcohol sulfates and polyoxyethylene alkyl ether sulfates represented by the following general formulas (B) and (C) are excellent in detergency, and are used for washing face wash and shampoo. Although it is used as a compound, it has a drawback that it has high protein denaturing power and skin irritation and easily causes skin disorders such as rough hands. With this background and the sophistication of living standards, there has been a strong demand for the development of low-skin irritating surfactants and cleaning compositions having high safety for the human body. is the current situation.

[0004]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to improve the above-mentioned disadvantages of the prior art, and as a result, have found that the silicon-based betaine-type amphoteric obtained by the invention described in Japanese Patent No. 2567284 filed earlier. When an appropriate amount of the surfactant is mixed with a higher alcohol sulfate or a polyoxyethylene alkyl ether sulfate represented by the following general formula (B) or (C), washing such as foaming property and detergency is performed. The present inventors have found that a detergent composition having small protein denaturing power and extremely low skin irritation can be obtained while satisfying the essential conditions as an agent, and have completed the present invention.

[0005] An object of the present invention is to provide a detergent composition having extremely low skin irritation while satisfying essential requirements as a detergent such as foaming properties and detergency.

[0006]

The above-mentioned object is achieved by a mild detergent composition containing the following components (I) and (II) as active ingredients. (I) General formula (A)

[0007]

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(Where R ¹ is the same or different and has 1 to 1 carbon atoms)
18 substituted or unsubstituted monovalent hydrocarbon group, R ² of which
One or all of the following general formula

[0009]

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(Where R ³ is a divalent carbon having 1 to 10 carbon atoms)
A hydrogen group, R ⁴ is an alkyl group having 1 to 3 carbon atoms, x and y are
Each is an integer of 1 to 3. ) Monovalent organic
Groups, the remainder being the same or different and having 1 to 18 carbon atoms
Substituted monovalent hydrocarbon group, m and n are integers from 0 to 1000
is there. One N-hydroxyalkyl group represented by
The introduced betaine group-containing siloxane compound, and (II) a general formula (B)

[0011]

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Or the general formula (C)

[0013]

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(Where R ⁵ is a long chain having 8 to 20 carbon atoms or
Is a branched alkyl group, M ¹ is sodium, potassium, or mag
Nesium, ammonium, alkanolamine or lower
Aliphatic amine, n is an integer of 1-8. ) Higher alcohol sulfates or polyoxyethylene alkyl ether sulfates.

The betaine group-containing siloxane compound represented by the general formula (A) in the present invention can be produced, for example, as follows.

A thermometer, a stirrer, and a reflux condenser were attached.
Average composition formula shown below in flask

[0017]

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400 g of a siloxane compound having
23 mol), 169 g of N-methylaminoethanol
(2.25 mol) and 200 g of isopropanol are charged and reacted under reflux for 6 hours. Next, the low-boiling components in the reaction solution are distilled off under reduced pressure at 80 ° C./4 mmHg for 4 hours. The reaction product (siloxane compound) thus obtained has a viscosity at 25 ° C of 2932 cs and a specific gravity of 1.
044, refractive index 1.4493, amine equivalent 392 g
/ Mol.

Next, 200 g (0.09 mol) of the siloxane compound obtained by the above reaction, 54 g (0.46 mol) of sodium monochloroacetate dissolved in 130 g of water,
And 186 g of 1,2 propylene glycol were charged into an 11 flask, and reacted while stirring at 100 ° C. for 12 hours.

[0020]

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To obtain a water-propylene glycol solution of a betaine group-containing siloxane compound having the following formula:

The average molecular weight represented by the above composition formula is 1
100, propylene glycol (31) of a betaine group-containing siloxane compound having a betaine group amount (number / molecule) of 3;
%) And water (22%) are abbreviated as composition (a). The average molecular weight is 2400,
A solution of propylene glycol (30%) and water (20%) of a betaine group-containing siloxane compound having an amount of betaine groups (number / molecule) of 5 is abbreviated as composition (b). further,
According to the same production method, a solution of propylene glycol (30%) and water (20%) of a betaine group-containing siloxane compound having an average molecular weight of 920 and an amount of betaine groups (pieces / molecule) of 2 is abbreviated as composition (c). .

The higher alcohol sulfate represented by the general formula (B) in the present invention includes, for example, caprylic alcohol sulfate, lauryl alcohol sulfate, myristyl alcohol sulfate, palmityl alcohol sulfate, stearyl alcohol sulfate. Sodium, potassium, magnesium, ammonium and triethanolamine salts.

The polyoxyethylene alkyl ether sulfate represented by the general formula (C) includes, for example, polyoxyethylene capryl ether sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene myristyl ether sulfate, and the like. Examples thereof include sodium, potassium, magnesium, ammonium and triethanolamine salts of polyoxyethylene palmityl ether sulfate and polyoxyethylene stearyl ether sulfate.

The higher alcohol sulfates and polyoxyethylene alkyl ether sulfates represented by the general formulas (B) and (C) have sufficient surface activity such as foamability and detergency. The protein has a strong protein denaturing power, and when used alone, a desired hypoallergenic detergent cannot be obtained.

On the other hand, the betaine group-containing siloxane represented by the general formula (A) has a very low protein denaturing power, a low irritancy, and a good surface activity such as foaming properties and detergency. is there.

The present inventors have found that a higher alcohol sulfate represented by the general formula (B) or a polyoxyethylene alkyl ether sulfate represented by the general formula (C) is combined with the above-mentioned general formula (A) When mixed with a betaine group-containing siloxane represented by the formula below, it was discovered that phenomena such as an increase in viscosity and a decrease in the critical micelle concentration occurred when each was mixed at a certain ratio. It was presumed that a complex of ethylene alkyl ether sulfate and betaine group-containing siloxane was formed, but with this fixed ratio mixture, the surfactant activity such as foaming and detergency was higher than that of higher alcohol sulfate. Alternatively, polyoxyethylene alkyl ether sulfate alone is as good as, and at the same time, protein-modified. Force are those found to significantly decrease the extent almost equal to that of betaine group-containing siloxane.

That is, by forming a complex by mixing, a synergistic effect is clearly exhibited, and it is possible to obtain a low-irritant detergent composition having a low protein-degrading property while maintaining excellent surface activity. Successful.

The mixing ratio (weight ratio) of (A) :( B)
Is preferably in the range of 3: 1 to 1:10. If the mixing ratio is out of this range, or if a large amount of other anionic surfactants or the like is added to disrupt the balance of the system, a sufficient effect of lowering protein performance cannot be obtained.

The content of (B) or (C) + (A) is preferably 5 to 40% by weight based on the total amount of the detergent composition.

The detergent composition of the present invention may contain, if desired, components generally incorporated in detergents, for example, higher alcohols, lanolin derivatives, protein derivatives, oily components such as fatty acid esters of polyethylene glycol, propylene glycol, Moisturizing ingredients such as glycerin and polyethylene glycol, nonionic surfactants such as fatty acid alkanol amides, polyoxyethylene alkyl ethers and alkylamine oxides, and water-soluble polymer substances (anionic, nonionic, cationic, etc.) ), Sequestering agents, preservatives, bactericides, pH adjusters, ultraviolet absorbers, antioxidants, dyes and fragrances.

Further, the cleaning composition of the present invention can be applied as a shampoo, a rinse, a hair treatment, and a hairdressing department.

[0033]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Prior to the examples, test methods and evaluation methods employed in each example will be described.

Foaming Test Method An aqueous solution having an activator concentration of 0.2% was prepared and subjected to a loss mild test method (ASTMD 1173-53).
The evaluation criteria were set as follows. ◎… Excellent foaming amount 230ml or more ○… Good foaming volume 200ml or more and less than 230ml △… Normal foaming amount 150ml or more and less than 200ml ×… Poor foaming Less than 150ml

Detergency test method A chloroform solution of 7% lanolin and 0.005% sudan (c) in a 5 cm × 5 cm wool muslin cloth 0.4 m
The stained cloth is placed in an approximately 100 ml glass cylinder containing 40 ml of a 3% detergent solution, shaken in a constant temperature bath at 40 ° C. for 15 minutes, and the stained cloth is washed with running water. After rinsing well, drying, and checking the reflectance, the cleaning rate was determined by the following equation.

[0036] The evaluation criteria were set as follows. ◎: Excellent cleaning performance Cleaning efficiency 85% or more ○: Good cleaning performance Cleaning efficiency 70% to less than 85% △: Normal cleaning performance 55% to less than 70% ×: Poor cleaning performance Cleaning efficiency less than 55%

Protein denaturation rate measurement method The density of egg white albumin denaturation when a sample was added to an ovalbumin pH 7 buffer solution to a test concentration of 1% using aqueous high performance liquid chromatography was determined by using the absorption peak at 220 nm. Measured. H _O : height of the 220 nm absorption peak of ovalbumin H _S : 2 when the sample was added to a buffer solution of ovalbumin
Height of 20 nm absorption peak The evaluation criteria were set as follows. ◎: Ovalbumin denaturation rate of less than 30% ○: Ovalbumin denaturation rate of 30% or more and less than 60% △: Ovalbumin denaturation rate of 60% or more and less than 80% ×: Ovalbumin denaturation rate of 80% or more

Hand Roughness Test Method For each sample, a panel of 5 persons each of 5 males and females was used.
The operation of immersing the other hand in an aqueous solution of 5 ° C. in water of the same temperature for 10 minutes was performed twice a day for two consecutive days, and the difference between the rough state of the left and right hands was visually determined. ◎: Extremely weak hand roughening 0 to 1 out of 10 people Hand roughening was observed on the sample side ○: Somewhat rough hand roughening 2 to 4 out of 10 Hand roughening was observed on the sample side △: Somewhat rough hand roughening 10 Medium 5 to 7: Hand roughening was observed on the sample side ×: Extremely strong hand roughening 8 to 10 out of 10 Hand roughening was observed on the sample side

[0039] In Examples 1-8, Comparative Examples 1-5 Examples 1-8 and Comparative Example 1 to 5 A shampoo consisting of blending composition shown in Table 1 and Table 2 were prepared and their foaming, washability Tables 1 to 4 show the results obtained by examining the protein denaturation rate and hand roughness.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

Industrial Applicability As described above, the present invention is a low-irritant detergent which has high safety, has a mild effect on skin and hair, has a mild action, and has excellent bubble power and detergency. Obviously, a composition is provided.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) A61K 7/075 A61K 7/06 C11D 1/90 C11D 1/94

Claims (1)

(57) [Claims] 1. A hypoallergenic detergent composition containing the following components (I) and (II) as active ingredients. (I) General formula (A) (Provided that R ¹ is the same or different and has 1 to 18 carbon atoms,
Is an unsubstituted monovalent hydrocarbon group, and R ² is one to all
The part has the following general formula : (However, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴
Represents an alkyl group having 1 to 3 carbon atoms, x and y each represent 1 to 3
Is an integer. ) Monovalent organic group, the rest are the same
Or different substituted or unsubstituted monovalent hydrocarbons having 1 to 18 carbon atoms
Elementary groups, m and n are integers from 0 to 1000. ]
Having one N-hydroxyalkyl group introduced therein
A siloxane compound having a thiol group, and (II) a compound represented by the general formula (B): Or the general formula (C): (Where R ⁵ is a long chain or branched alkyl having 8 to 20 carbon atoms)
And M ¹ is sodium, potassium, magnesium,
Ammonium, alkanolamine or lower aliphatic amine
And n is an integer of 1 to 8. ) Higher alcohol sulfates or polyoxyethylene alkyl ether sulfates.