JPH0226677B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a detergent composition that satisfies essential requirements for a detergent, such as foaming properties and cleansing properties, while successfully reducing irritation to the skin significantly. Conventionally, as a surfactant for shampoos,
Whether it is products for professionals such as those used in hair salons or general commercial products, they mainly contain alkyl sulfate salts,
Polyoxyethylene alkyl sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, and the like have been widely used. However, although shampoos containing these surfactants have excellent cleaning power,
All of them are known to be highly irritating to the skin, although to varying degrees, and professionals who often come into contact with shampoo, such as barbers and beauticians, are more likely to experience skin problems such as rough hands. It is something. Also, these days, young people who have a particularly developed sense of cleanliness wash their hair more often, but even the general public washes their hair more often.
The number of hair washes has increased to 3 to 4 times a week or every day, and if you continue to wash your hair with shampoos that contain strong irritating surfactants, your scalp will become rough, leading to dandruff and itching. There are problems with connection etc. From these points of view, the current situation is that there is a strong demand for the use of shampoos that are hypoallergenic to the skin, not only for professional use but also for general commercial use. The present inventors have focused on the above points and have conducted intensive research. As a result, we have found that surfactants with strong protein denaturing power are used in surfactant compositions. In contrast, shampoo compositions containing surfactants with low protein denaturing power are less likely to cause skin disorders such as rough hands even after long-term use, and have been shown to significantly reduce the occurrence of dandruff on the scalp. I found it. That is, for a mixed surfactant composition containing various surfactants, the protein denaturation rate was measured, a hand roughness test using actual human hands was conducted, and the amount of dandruff caused by actual use (prolonged use) was measured. They found that a surfactant or a mixed surfactant composition with a low oxidation rate tends to cause less rough hands and a tendency to reduce the amount of dandruff, leading to the completion of the invention of the present cleaning composition. That is, the present invention provides general formula (A) (In the formula, R ₁ is an alkyl group or alkenyl group having an average number of carbon atoms of 7 to 19, R ₂ is an average number of carbon atoms of 1
to 3 lower alkyl groups, M represents an alkali metal or an organic amine. ) an alkylyl alkyl taurine salt type anionic surfactant represented by general formula (B) (In the formula, R ₃ is an alkyl group or alkenyl group having an average of 7 to 19 carbon atoms, R ₄ is a hydrogen atom or a lower alkyl group having an average of 1 to 3 carbon atoms,
R ₅ and R ₆ are lower alkyl groups having an average number of carbon atoms of 1 to 3, and m is an integer of 1 to 4. ) and an alkyloylamide betaine type amphoteric surfactant represented by the general formula (C) (In the formula, R ₇ represents an alkyl group or alkenyl group having an average number of carbon atoms of 7 to 19, m and n are integers, and m+n is 1 to 5.) The present invention provides a cleaning composition containing as an active ingredient. The preferred blending ratio of the active ingredients is that the weight ratio of (A):(B) is 5:1 to 1:8, and the weight ratio of (A)+(B):(C) is 15:1 to 1: 1, and (A)+(B)
+(C) accounts for 10 to 50% by weight of the total. Although the alkyloyl alkyl taurine salt type anionic surfactant represented by the general formula (A) has sufficient surfactant properties such as foaming properties and detergent properties,
It has a strong ability to denature proteins, and when used alone, the desired mild detergent cannot be obtained. On the other hand, the alkyloylamide betaine-type amphoteric surfactant represented by the general formula (B) has low protein denaturing ability and weak irritation, but has poor surfactant properties such as foaming and detergent properties. Therefore, when used alone, there is a drawback that a cleaning agent with satisfactory performance cannot be obtained. The present inventors have developed an alkyl taurine salt type anionic surfactant represented by the general formula (A) and an alkylyl amide betaine type surfactant represented by the general formula (B) in a certain amount. It was discovered that when mixed in proportion, phenomena such as increased viscosity and decreased critical micelle concentration occurred compared to when each was used alone, and it was assumed that a complex of anionic surfactant and amphoteric surfactant was formed. However, with this mixture at a certain ratio, the surfactant abilities such as foaming properties and detergent properties are not inferior to those of the alkylyl alkyl taurine salt type anionic surfactant represented by the general formula (A) alone. , at the same time, the protein denaturation ability is expressed by the general formula
It was discovered that the alkylamide betaine type amphoteric surfactant represented by (B) was significantly reduced to an extent that was at least as good as that of the amphoteric surfactant alone. In other words, by mixing to form a complex, a synergistic effect was clearly exerted, and it was possible to obtain a hypoallergenic surfactant composition with low protein denaturation ability while maintaining excellent surfactant ability. It is something. This (A):
The weight ratio of (B) ranges from 5:1 to 1:8. If the balance of the system is disrupted by using a mixing ratio outside this range or by adding a large amount of other anionic surfactants, etc., a sufficient effect of lowering protein denaturation performance cannot be obtained. In addition, the alkylolamide type nonionic surfactant represented by the general formula (C) used in the present invention has traditionally been used in anionic surfactant shampoos to have a foaming enhancement effect, a thickening effect, and a low temperature effect. It is blended for the purpose of improving stability (reducing Kraft point), etc., but in the present invention, a certain amount of (C) is added to the mixture of (A) and (B) above. It has been found that the protein denaturation ability is further reduced by blending at a ratio of . Preferable (A)+(B):
The ratio of (C) is in the range of 15:1 to 1:1 by weight, and if (A) + (B) is too much than this ratio, the effect of (C) on reducing protein denaturation performance will not be fully exerted. First, if there is too much (C), the detergency and foaming properties of the shampoo will be impaired. Also, (A) + (B) + (C) is 10 to 50% by weight of the total to form a liquid shampoo.
It is desirable that In the present invention, the alkylyl alkyl taurine salt type anionic surfactant represented by the general formula (A) is, for example, as an alkylyl group R ₁ CO-:
C ₁₁ H ₂₃ CO―, C ₁₃ H ₂₇ CO―, C ₁₅ H ₃₁ CO―,
C ₁₇ H ₃₅ CO—, C ₁₇ H ₃₃ CO—, mixed alkylyl groups having 8 to 20 carbon atoms obtained from coconut oil fatty acids, etc., and the alkyl group R ₂ is CH ₃ —, C ₂ H ₅ —,
C ₃ H ₇ -, and the counter ion M is -Li, -
Examples include K, -Na, monoethanolamine, diethanolamine, and triethanolamine. The alkylamide betaine type amphoteric surfactant represented by the general formula (B), for example, has an alkyl group.
As R ₃ , C ₇ H ₁₅ ―, C ₉ H ₁₇ ―, C ₁₁ H ₂₃ ―,
C ₁₃ H ₂₇ ―, C ₁₅ H ₃₁ ―, C ₁₇ H ₃₅ ―, C ₁₇ H ₃₃ ―,
C ₁₇ H ₃₁ --, C ₁₇ H ₂₉ --, mixed alkyl groups having 7 to 19 carbon atoms obtained from coconut oil, etc., R ₄ is --H, --CH _3, etc., and R ₅ and R ₆ are -- _CH3 ,
-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and the like. The alkylolamide type nonionic surfactant represented by the general formula (C) has an alkylyl group, for example.
R ₇ CO— is C ₁₁ H ₂₃ CO—, C ₁₃ H ₂₇ CO—,
Examples include C ₁₅ H ₃₁ CO—, C ₁₇ H ₃₅ CO—, C ₁₇ H ₃₅ CO—, and mixed alkylyl groups having 8 to 20 carbon atoms obtained from coconut oil fatty acids. The cleaning composition of the present invention may optionally contain components commonly added to cleaning agents, such as higher alcohols, lanolin derivatives, protein derivatives, and oily components such as fatty acid esters of polyethylene glycol.
Humectant ingredients such as propylene glycol, glycerin, and polyethylene glycol, nonionic surfactants such as polyoxyethylene alkyl ether and polypropylene oxide block polymer, water-soluble polymer substances (anionic,
(including nonionic and cationic), sequestering agents, preservatives, bactericidal agents, PH regulators, ultraviolet absorbers, antioxidants, pigments, fragrances, and the like. Next, the present invention will be explained in detail using Examples, but the present invention is not limited thereto. Prior to the examples, the test methods and evaluation methods employed in each example will be explained. Foaming test method: 400 ml of a 1% solution with a test concentration of 70 ppm CaCO ₃ was prepared, and the foaming amount was measured using a cylindrical cylinder equipped with a stirrer at a temperature of 40°C. 〇…Good foaming Foam volume 2000ml or more △…Normal foaming Foam volume 1500ml or more Less than 2000ml×…Poor foaming Foam volume Less than 1500ml Cleaning test method CaO/Mgo=3/1, 5゜DH artificial hard water, sample concentration 1% solution and washed artificial sebum-contaminated cloth using wool surge. Tergotometer (JIS K) at a temperature of 40℃
-3371), and the cleaning efficiency was determined from the reflectance before and after cleaning. Cleaning efficiency (%) = Rw-Rs/Ro-Rs×100 Ro: Reflectance of original cloth (wool serge) Rs: Reflectance of contaminated cloth Rw: Reflectance of contaminated cloth after cleaning 〇…Good cleaning performance Cleaning efficiency 80% or more △...Cleanability normal Washing efficiency 60% or more Less than 80% ×...Poor washability Washing efficiency less than 60% Protein denaturation rate measurement method Using aqueous high performance liquid chromatography, sample concentration was added to ovalbumin PH7 buffer solution. The ovalbumin denaturation rate when the sample was added at a concentration of 1% was measured using the absorption peak at 220 nm. Denaturation rate (%) = Ho−Hs/Ho×100 Ho: Height of the 220 nm absorption peak of ovalbumin Hs: Height of the 220 nm absorption peak when the sample is added to the ovalbumin buffer solution. ◎...Ovalbumin denaturation rate less than 30%〇...Ovalbumin denaturation rate 30% or more but less than 60%△...Ovalbumin denaturation rate 60% or more but less than 80%×...Ovalbumin denaturation rate 80% or more Rough hand test method For each sample, male and female Using a panel of 5 people each, 10 people in total, with one hand on either the left or right side, sample concentration 5
%, and the other hand was immersed in water at the same temperature for 10 minutes, twice a day for 2 consecutive days, and the difference in rough skin between the left and right hands was visually determined. ◎... Extremely weak hand roughness 0-1 out of 10 people Rough hands were observed on the sample side 〇... Hand roughness was slightly weak 2-4 out of 10 people Rough hands were observed on the sample side △... Hand roughness was slightly strong 10 people 5-7 out of 10 participants Roughness of hands was observed on the sample side ×...Extremely rough hands 8-10 out of 10 participants Roughness was observed on the sample side Dandruff production measurement method Usually, general commercially available uralyl ether sulfate-based A panel of people using Shampoo (which does not contain drugs for dandruff and itch) were asked to wash their hair five times with the same frequency and method as usual, using the sample. The amount of dandruff before and after was compared. The amount of dandruff on the third day after washing the hair with a general commercially available shampoo and the amount of dandruff on the third day from the last day of washing the hair five times using the sample was measured. Dandruff is collected by suction from the head using a cloth-equipped suction device. To eliminate errors caused by other foreign substances, the amount of nitrogen is determined using the Kjeldahl method, and this is multiplied by 6.25 to determine the average protein amount. (mg/head). The number of panels was three for each sample, and the average values were compared. ◎…The amount of dandruff has decreased by 30% or more after using the sample 〇…The amount of dandruff has decreased by 10% or more but less than 30% after using the sample △…The amount of dandruff has decreased by 0% or more and less than 10% after using the sample Sample ×...The amount of dandruff increased after using the sample Examples 1 to 8 A shampoo consisting of the formulation shown in Table 1 below was prepared, and its foaming property, detergency, protein denaturation rate, roughness on hands, The amount of dandruff produced was investigated. These results are shown in Table 1 (Example) and Table 2 (Comparative Example).

【table】

【table】

【table】

[Table] As described above, the examples of the present invention exhibited excellent performance in all of the foaming properties, cleansing properties, protein denaturation rate, roughness on hands, and amount of dandruff. Example 9 A shampoo having the following composition was prepared. (Weight %) Cocoyl methyltaurine-Na 8 Cocoyl propylamide betaine 12 Coconut fatty acid diethanolamide 4 Glycerin 2 Fragrance 0.3 Water Residual This shampoo underwent the same performance evaluation tests as Examples 1 to 8, and was evaluated for foaming properties, cleaning properties, and The results were as follows: quality: ○, protein denaturation rate: ◎, roughness on hands: ◎, and dandruff generation: ◎. Example 10 A shampoo having the following composition was prepared. (Weight %) Ethylene glycol fatty acid ester 2 Lauryl methyl taurine-Na 8 Lauryl propylamide betaine 10 Lauric acid diethanolamide 5 Propylene glycol 2 Polyethylene oxide (molecular weight 100,000 to 5 million)
0.05 Fragrance 0.3 Water Residual This shampoo was subjected to the same performance evaluation tests as in Examples 1 to 8, and the results were ○ foaming property, ○ detergency, ◎ protein denaturation rate, ◎ roughness on hands, and ◎ amount of dandruff. Obtained. Example 11 A shampoo having the following composition was prepared. (Weight %) Cocoyl methyl taurine-Na 8 Laurylpropylamide betaine 10 Coconut fatty acid diethanolamide 4 Polyethylene glycol 2 Citric acid 0.3 Cationized cellulose ether 0.6 Fragrance 0.3 Water Residual This shampoo was subjected to performance evaluation tests similar to those in Examples 1 to 8. The results were as follows: foaming property: ○, cleaning performance: ○, protein denaturation rate: ◎, roughness on hands: ◎, and dandruff generation: ◎. Example 12 A shampoo having the following composition was prepared. (Weight %) Ethylene glycol fatty acid ester 2 Lauroylmethyltaurine-Na 10 Laurylpropylamide betaine 10 Coconut fatty acid diethanolamide 4 1,3-Butylene glycol 3 Poly(dimethyldiallylammonium chloride)
1 Fragrance 0.3 Water Residual This shampoo was subjected to the same performance evaluation tests as in Examples 1 to 8, and the results were as follows: foaming property ○, detergency ○, protein denaturation rate ◎, roughness on hands ◎, and dandruff generation ◎. It was done. Example 13 A body shampoo having the following composition was prepared. Ethylene glycol fatty acid ester 2 Cocoyl glutamic acid mono-sodium 3 Cocoyl methyl taurine-Na 6 Cocoyl propylamide betaine 8 Coconut fatty acid diethanolamide 3 Glycerin 3 Fragrance 0.3 Water Residual This body shampoo was subjected to performance evaluation tests similar to those in Examples 1 to 8. Foaming property 〇, cleaning property 〇,
The protein denaturation rate was ◎ and the roughness of hands was ◎.

Claims (1)

[Claims] 1 General formula (A) (In the formula, R ₁ is an alkyl group or alkenyl group having an average of 7 to 19 carbon atoms, R ₂ is a lower alkyl group having an average of 1 to 3 carbon atoms, and M is an alkali metal or an organic amine.) An alkylyl alkyl taurine salt type anionic surfactant and general formula (B) (In the formula, R ₃ is an alkyl group or alkenyl group having an average of 7 to 19 carbon atoms, R ₄ is a hydrogen atom or a lower alkyl group having an average of 1 to 3 carbon atoms, R ₅ ,
R ₆ is a lower alkyl group having an average number of carbon atoms of 1 to 3; m is an integer of 1 to 4; ) and an alkyloylamide betaine type amphoteric surfactant represented by the general formula (C) (In the formula, R ₇ represents an alkyl group or alkenyl group having an average number of carbon atoms of 7 to 19, m and n are integers, and m+n is 1 to 5.) A cleaning composition containing as an active ingredient. 2 The weight ratio of the alkyloyl alkyl taurate type anionic surfactant represented by the general formula (A) and the alkylylamide betaine type amphoteric surfactant represented by the general formula (B) is 5:1 to 1:8. The weight ratio of (A) + (B) and the alkylolamide type nonionic surfactant represented by the general formula (C) is in the range of 15:1 to 1:1, and (A) + ( B) + (C) is the total 10
The cleaning composition according to claim 1, wherein the cleaning composition has a content of from 1 to 50% by weight.