JPH0159244B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a shampoo composition that has high foaming properties, does not cause squeaks during hair washing, and is gentle on the skin and eye mucous membranes. More specifically, the present invention relates to a shampoo composition containing a specific sulfosuccinate monoester salt type anionic surfactant and a specific nonionic surfactant. Conventionally, anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates, and alpha olefin sulfonates have been widely used as active surfactants for shampoos, but these surfactants All drugs are recognized to have irritating effects on the skin and ocular mucous membranes, albeit to varying degrees. On the other hand, there are imidazoline-type amphoteric surfactants such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine as surfactants that are mild to the skin and eye mucous membranes, but these surfactants foam. was secreted especially from the scalp. It has the disadvantage of poor lathering in the presence of oils or oils derived from hair conditioners, and its practical use is limited to baby shampoos and the like that do not require high lathering properties. Conventionally known higher alcohol or polyoxyethylene higher alcohol ether sulfosuccinate monoester salt type anionic surfactants are known to be mild surfactants for the skin, eye mucous membranes, but they also have poor foaming power. Moreover, depending on its structure, it can cause an unpleasant squeaky sound during hair washing. In order to improve these drawbacks, attempts have been made to improve the foaming power by using a known foam enhancer such as lauric acid diethanolamide, but the effect is not sufficient. Furthermore, in order to reduce damage to the hair, it is preferable that the pH of the shampoo is weakly acidic, but lauric acid diethanolamide has the disadvantage that it is susceptible to hydrolysis when it is weakly acidic, and the stability of the shampoo over time becomes insufficient. As a result of repeated research by the present inventors to improve these drawbacks, we found that by using a specific sulfosuccinate monoester salt type anionic surfactant and a polyoxyalkylene higher fatty acid amide type nonionic surfactant, The inventors have discovered that it is possible to obtain a shampoo composition that has high foaming properties, does not cause squeaks during hair washing, and is gentle on the skin and eye mucous membranes, and has thus arrived at the present invention. That is, the present invention is based on the general formula () [In the formula, R ₁ is an alkyl group with an average carbon number of 9 to 15, R ₂ is hydrogen or a methyl group, and AO is an alkyl group with an average carbon number of 2
~3 oxyalkylene group, n is an integer from 0 to 20
M ₁ and M ₂ represent one selected from the group consisting of hydrogen ions, alkali metal ions, ammonium ions, and hydroxyalkylammonium ions. ] 4 to 40% by weight of an anionic surfactant represented by and general formula () [In the formula, R ₃ is an alkyl group having an average carbon number of 9 to 15, R ₄ is hydrogen or a methyl group, and AO' is an alkyl group having an average of 2 to 15 carbon atoms.
3 is an oxyalkylene group, m is an integer of 0 to 20. This is a shampoo composition characterized by containing 1 to 10 weight percent of a nonionic surfactant represented by the following formula, and having a system pH of 4 to 7. In the compound of general formula () used in the present invention, R ₁ is a linear or branched alkyl group having an average carbon number of 9 to 15, and is a nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl group, or any of these groups. It may be a mixture of these or an alkyl group having an average carbon number of 9 to 15 including an alkyl group outside the range of 9 to 15 carbon atoms, and a linear alkyl group having an average of 11 to 13 carbon atoms is particularly preferred. If the average carbon number is less than 8 or more than 16, the foaming power will be insufficient. n may be from 0 to 20, but preferably 5 or more, and particularly preferably 1 to 3, in order to eliminate the squeaky feeling during hair washing. M ₁ and M ₂ represent one selected from the group consisting of a hydrogen ion, an alkali metal ion, an ammonium ion, and a hydroxyalkylammonium ion, but they may be the same. The alkali metals mentioned here are lithium, sodium, and potassium, and the hydroxyalkylammonium ions include monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, isopropanolammonium ion, dimethylmonoethanolammonium ion, and methyldiethanolammonium ion. etc. Particularly preferred are hydrogen ions, sodium ions, and triethanolammonium ions. In the compound of general formula (), R ₃ is an alkyl amount having an average carbon number of 9 to 15;
The same alkyl groups as R ₁ can be mentioned, and R ₁
It can be the same or different. In particular, if the average carbon number is less than 8 or more than 16, the foaming power will be insufficient. m is an integer of 0 to 20, preferably 5 or less in order not to give a squeaky feeling during hair washing, particularly preferably 1 to 3, particularly preferably 1 to 3, and is represented by the general formula ()
may be the same as or different from n. The method for producing the nonionic activator of general formula () is not particularly limited. Any method that produces the structure of general formula () may be used, such as a method in which higher fatty acids and monoethanolamine are first reacted and then alkylene oxide is added, or β
-Can be produced by the reaction of aminoethoxyethanol with higher fatty acids or lower alcohol esters of higher fatty acids. However, the following production method is preferred from the viewpoint of easy availability of raw materials and the ability to reduce by-products. That is, a lower alcohol ester of a higher fatty acid is reacted with an equivalent molar amount or more of an alkanolamine in the presence of an alkali metal catalyst, then excess alkanolamine is removed, and then an alkylene oxide is reacted at 60 to 100°C. The nonionic surfactant obtained in this way usually has an amine value of 1 to 15, and in order to further reduce skin irritation, manufacturing conditions are selected so that the amine value is 10 or less (hereinafter this manufacturing method will be referred to as method A). ). This Law A has been separately explained in detail in a patent application filed by the present patent applicant (Japanese Patent Publication No. 59-28599), so please refer to it. Alternatively, a higher fatty acid alkanolamide produced by a conventionally known method or a compound to which an alkylene oxide is added is purified by methods such as distillation, fractional precipitation + recrystallization, etc., and the amine value is 0 to 15, more preferably 10 or less. It is also possible to use compounds having the structure of the general formula () to a certain extent. Similarly, the manufacturing method for the compound of the general formula () is not particularly limited, and any compound having the structure of the formula may be used. However, an example of a method that is usually easy to manufacture is the compound of the above general formula (), maleic anhydride, and ester. It is produced by reacting with sodium sulfite. The sulfosuccinate monoester salt type anionic surfactant produced in this way is a mixture of compounds represented by the following general formula () in addition to the compound represented by the general formula (). may also include a compound represented by the general formula (). Further, when producing the compound of the above general formula (), the molar ratio of maleic anhydride may be lowered so that the compound of the general formula () remains. In this case as well, it is preferable to use compounds in the form of esters of the compound obtained by process A and sulfosuccinic acid in order to reduce coloration and to reduce by-products that cause skin irritation. This manufacturing method is also described in detail in the patent application cited above. In the composition of the present invention, the content of the compound of general formula () is 4 to 40% by weight, preferably 10 to 25% by weight in the shampoo formulation.
If it is less than 4% by weight, the foaming power will be insufficient,
In addition, it cannot exhibit low irritation to the skin and eye mucous membranes, and its content at a high concentration exceeding 40% by weight is not actually necessary. The content of the compound of general formula () is 1 to 10% by weight, preferably 3 to 10% by weight.
6% by weight. If the content is less than 3% by weight, the foaming power will be insufficient, and if the content exceeds 10% by weight, it is not actually necessary. The pH of the system is from 4 to 7, and if it is less than 4 or more than 7, the compound of general formula () will be susceptible to hydrolysis over time, and if it is alkaline, it will damage the hair. The composition of the present invention may further include ingredients commonly included in conventional shampoo compositions, such as anionic surfactants such as higher alkyl sulfates and polyoxyethylene alkyl sulfates, 2-alkyl-N-carboxymethyl-N- Ampholytic surfactants such as hydroxyethylimidazonium betaine and lauryldimethylaminoacetic acid betaine, nonionic surfactants such as higher fatty acid alkanolamides, alkyldimethylamine oxides, and polyoxyethylene alkyl ethers, higher alcohols, isopropyl myristate, etc. oil components, antioxidants,
Chelating agents, builders, ultraviolet absorbers, bactericides,
Preservatives, dyes, fragrances, etc. can be added. In the case of surfactants, these additive components can be added in an amount of 0 to 30% by weight, or can replace up to 80% of the active agent components of general formulas () and () in the shampoo formulation. The oil component may be varied depending on the intended use of the shampoo and the desired amount of residual oil after shampooing, and is usually about 0 to 10%, more preferably about 1 to 5%. Other additives can be added at the same amount as normal shampoo, usually 2%.
It is as follows. The shampoo composition of the present invention not only fully satisfies various properties required for shampoo, but also has the feature of being extremely gentle on the skin and eye mucous membranes without causing any squeaks during hair washing. Examples will be described below, but the present invention is not limited thereto. Example 1 The following shampoos were prepared using the surfactants shown in Tables 1 and 2, and their foaming power and squeaky feeling were tested. Surfactant from Shampoo Prescription Table-1 15g Surfactant from Table-2 5g Water 80g The pH (current solution) of Shampoo was adjusted to 5.5 with citric acid. Foaming power was determined by adding 0.05% lanolin and 0.05% liquid paraffin as oil stain ingredients to a 2% aqueous solution of shampoo, rotating at 1000 rpm with a flat propeller at 30°C.
The mixture was stirred in a cylinder for 5 minutes under the condition of being turned over every 10 seconds, and the amount of foam was evaluated based on the amount of foam 30 seconds after the stirring was completed. For the squeaky feeling, a hair washing test was conducted by 5 people, and those that felt the squeaky feeling were judged as poor by 2 or more people. The results are shown in Table 3, and it can be seen that the composition of the present invention is particularly excellent.

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【table】

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【displayed.
Example 2 The pH of Shampoos A and B having the following compositions was adjusted with citric acid, left at 40°C for 3 months, and the hydrolysis rate of the sulfosuccinate monoester salt type anionic surfactant was measured. The results are as shown in Table 4, PH4~
It turns out that 7 is suitable. Shampoo A Sample No. 1-3 in Example 1 20g Sample No. B-2 in Example 1 5g Water 75g Shampoo B Sample No. A-10 in Example 1 20g Sample No. in Example 1 B-7 5g Water 75g

[Table] Example 3 Sample No. A-2 in Example 1 10g Sample No. B-6 in Example 1 4g Polyoxyethylene (2) lauryl ether sulfate
TEA salt 6g Pigment, fragrance Trace amount of water 80g PH was adjusted to 6.0 with citric acid. The shampoo produced with the above formulation foamed well, and the hair was supple after washing. Example 4 Sample No. A-11 in Example 1 20 g Sample No. B-3 in Example 1 3 g Propylene glycol 3 g Flavor, pigment Fine water 74 g PH was adjusted to 5.0 with lactic acid. The shampoo produced with the above formulation foamed well, caused no squeaks during hair washing, and was particularly gentle on the eye mucous membranes. Example 5 Sample No. A-6 in Example 1 10g Sample No. B-5 in Example 1 2g 2-Undecyl-N-carboxylmethyl-
N-Hydroxy 10g Ethylimidazolinium Betaine Propylene Glycol 2g Fragrance, pigment Trace amount of water 76g PH was adjusted to 5.5 with citric acid. The shampoo produced according to the above formulation foamed well, did not cause squeaks during hair washing, and the hair was supple after washing. Example 6 A primary skin irritation test was conducted using a patch test using 1% aqueous solutions of the shampoo compositions of the present invention obtained in Examples 3, 4, and 5 and the shampoo compositions of Comparative Examples 1 and 2 below. Specifically, a lint cloth coated with the sample was applied to the inner side of the upper arm of 15 men and 15 men, and the cloth was fixed with a batch test bandage. After 48 hours, the presence or absence of erythema and other changes was examined. With the shampoo composition of the present invention obtained in No. 5, no abnormalities were observed in any of the subjects, but with the shampoo composition of Comparative Example 1, five subjects found abnormalities, and in Comparative Example 2, nine subjects observed abnormalities. Comparative example 1 Sample No.A-14 in Example 1 10g Sample No.B-8 in Example 1 4g Polyoxyethylene (2) lauryl ether sulfate
TEA salt 6g Flavor, pigment Trace amount water 80g PH was adjusted to 6.0 with citric acid. Comparative example 2 Sample No. A-15 in Example 1 10g Sample No. B-9 in Example 1 4g Polyoxyethylene (2) Raul ether sulfuric acid
TEA salt 6g Pigment, fragrance Trace amount of water 80g PH was adjusted to 6.0 with citric acid.

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ is an alkyl group with an average carbon number of 9 to 15, R ₂ is hydrogen or a methyl group, and AO is an alkyl group with an average carbon number of 2 to 15.
3 oxyalkylene group, n is an integer of 0 to 20,
M ₁ and M ₂ represent one selected from the group consisting of hydrogen ions, alkali metal ions, ammonium ions, and hydroxyalkylammonium ions. ] 4 to 40% by weight of an anionic surfactant represented by and general formula () [In the formula, R ₃ is an alkyl group having an average carbon number of 9 to 15, R ₄ is hydrogen or a methyl group, and AO' is an alkyl group having an average of 2 to 15 carbon atoms.
3 is an oxyalkylene group, m is an integer of 0 to 20. ] A shampoo composition characterized by containing 1 to 10 weight percent of a nonionic surfactant represented by the following, and having a system pH of 4 to 7. 2 A nonionic surfactant represented by the general formula () reacts a lower alcohol ester of a higher fatty acid with an equimolar amount or more of alkanolamine in the presence of an alkali metal catalyst, then removes excess alcohol amine, and then The shampoo composition according to claim 1, which is a reaction product obtained by reacting alkylene oxide at 100°C. 3. The shampoo composition according to claim 1, wherein the anionic surfactant represented by the general formula () is a salt of a monoester of the reaction product according to claim 2 and sulfosuccinic acid.