JPH0479399B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to improved cleaning compositions.
More specifically, the present invention relates to a cleaning composition that foams quickly, has rich, creamy foam, has good low-temperature stability, and has significantly reduced skin irritation. Recently, this is especially common among young people who have developed a sense of fashion, but even among the general public, the number of times they wash their hair has increased to 3 to 4 times a week or every day. If you continue to wash your hair with the shampoo that contains it, your scalp will become rough.
There are problems such as leading to dandruff and itching. In addition to the speed and richness of the lather during shampooing, the creaminess of the lather makes it slippery on the fingers during shampooing, and foams that do not have a creamy quality can cause problems such as damaging the hair. . From these points of view, there is currently a strong demand for creamy foam shampoos that are low in skin irritation and do not damage hair, not only for professional use but also for general commercial use. Conventionally, alkyl sulfates, alkylbenzene sulfonates, α-olefin sulfonates, and the like have been widely used as surfactants for shampoos, both for professionals in beauty salons and as general commercial products. Although shampoos containing these surfactants have excellent foaming speed, richness, creaminess, and cleansing properties, they are all highly irritating to the skin and have been found to be highly irritating to the skin to varying degrees. There are drawbacks to freezing it.
In order to solve this problem, the irritation to the skin,
In order to improve the stability at low temperatures, an invention has been disclosed in which the number of moles of oxyethylene added to a polyoxyethylene alkyl sulfate salt is limited (Japanese Patent Application Laid-open No. 52-36106 and 52-36107); It is not satisfying in terms of abundance. In view of these circumstances, the inventors of the present invention have conducted extensive research to solve the above-mentioned drawbacks, and have found that the balance between the average number of added moles of oxyethylene and the counter ion of the polyoxyethylene alkyl sulfate salt can improve the creaminess and richness of the foam. It has been found that stability at low temperatures and skin irritation can be improved.
In addition, with surfactants and surfactant compositions that have strong protein denaturing power, repeated use can cause severe roughness and dandruff, whereas surfactants with low protein denaturing power It has been found that the shampoo composition is less likely to cause skin disorders such as rough hands even when used continuously for a long period of time, and also significantly reduces the occurrence of dandruff on the scalp. In other words, the present inventors used various surfactants,
As a result of measuring the protein denaturation rate of mixed surfactant compositions, conducting rough hand tests using actual human hands, and measuring the amount of dandruff caused by actual use (prolonged use), we found that surfactants with a low protein denaturation rate and The present invention was based on the discovery that a mixed surfactant composition is less likely to cause rough hands and tends to reduce the amount of dandruff. That _{is , the} present invention provides _the following formula _: is the average number of added moles of 0.5 to 3, and _M1 is the molecular ratio of organic amines consisting of mono-, di-, or triethanolamine or a mixture thereof to an alkali metal such as sodium, potassium, or lithium of 1:1 to 1:1. 5
is a mixture. ) and general formula (B) [In the formula, R ₂ is an alkyl group or alkenyl group having an average number of carbon atoms of 9 to 17, m and n are integers of 1 to 3, and Z is a hydrogen atom or -(CH ₂ )
lCOOY (l is an integer of 1 to 3, Y represents an alkali metal, alkaline earth metal or organic amine) group; M represents an alkali metal, alkaline earth metal or organic amine; ] Amphoteric surfactant represented by general formula (C) (In the formula, R ₃ represents an alkyl group or alkenyl group having an average number of carbon atoms of 7 to 19, and p and q
is an integer, and p+q is 1 to 5. ) as an active ingredient. The preferred blending ratio of the active ingredients is a weight ratio of (A):(B) of 3:
1 or 1:1, and the weight ratio of (A) + (B): (C) is
It is in the range of 15:1 to 1:1, (A) + (B) + (C)
is in the range of 10 to 50% by weight in the cleaning composition. The anionic surfactant represented by the general formula (A) has an average number of added moles of polyoxyethylene of 0.5 to
It is selected within the range of 3, preferably 1 to 2.5. Average number of added moles of polyoxyethylene is 0.5
If it is less than 100%, it has good properties in terms of foaming and creaminess of the foam, but it is not preferable because it increases skin irritation, rough hands, etc., and has insufficient low temperature stability. Moreover, polyoxyethylene having an average number of added moles of more than 3 is undesirable because it is unsatisfactory in terms of skin irritation, rough hands, etc., and is not satisfactory in terms of lathering, foam creaminess, etc. The counterion is mono,
A mixture of organic amines consisting of di-, triethanolamine or a mixture thereof and sodium, potassium or lithium, where the molecular ratio of the organic amines and an alkali metal such as sodium, potassium or lithium is 1:1 or 1:5. is a mixture. If the molecular ratio of the organic amine to the alkali metal exceeds 1:1, the low temperature stability will be poor, and if it is less than 1:5, the creaminess of the foam will be poor, which is not preferred. The amphoteric surfactant represented by the general formula (B) has low protein denaturation power and weak irritation, but has poor surfactant properties such as foaming and detergent properties.
When used alone, there is a drawback that a cleaning agent with satisfactory performance cannot be obtained. The present inventors discovered that when the anionic surfactant represented by the general formula (A) and the amphoteric surfactant represented by the general formula (B) are mixed at a certain ratio, when each of them is used alone, They discovered that phenomena such as an increase in viscosity and a decrease in critical micelle concentration occurred, and assumed that a complex of anionic surfactant and amphoteric surfactant was formed.
The surfactant ability such as foaming property and detergency is superior to that of the anionic surfactant represented by the general formula (A) alone, and at the same time, the protein denaturation ability is superior to that of the anionic surfactant represented by the general formula (B). It has been discovered that the surfactant is significantly reduced to a degree that is not inferior to that of the surfactant alone. The weight ratio of (A):(B) is 3:1 to 1:
It is desirable that the weight ratio be as close as possible to 1:1. If the mixing ratio is outside this range or if a large amount of other anionic surfactant is added to disrupt the balance of the system, a sufficient effect of lowering protein denaturation performance cannot be obtained. Furthermore, the general formula (C) used in the present invention
The nonionic surfactant represented by
It is blended for the purpose of thickening effect, improving low-temperature stability, etc., but in the present invention, this (C) is added to the mixture of (A) and (B) above at a certain ratio. It was found that the protein denaturing power was further reduced by blending with . Preferable (A)
+(B):(C) is in the range of 15:1 to 1:1 by weight, and if there is too much (A) + (B) than this ratio, the effect of (C) on reducing protein denaturation performance is insufficient. If the amount of (C) is too high, the shampoo's detergency, lathering speed, etc. will be impaired. Also, (A) + (B) +
(C) desirably accounts for 10 to 50% by weight of the total amount of the detergent composition in order to form a liquid shampoo. In the present invention, R ₁ of the anionic surfactant represented by general formula (A) is, for example, C ₁₁ H ₂₃ −, C ₁₂ H ₂₅
−, C ₁₃ H ₂₇ −, C ₁₄ H ₂₉ −, C ₁₆ H ₃₃ C ₁₈ H ₃₇ −, C ₁₈
Examples include _H35- , alkyl groups and alkenyl groups having 8 to 20 carbon atoms obtained from coconut oil fatty acids. R ₂ of the amphoteric surfactant represented by general formula (B) is C ₉ H ₁₉ −, C ₁₁ H ₂₃ −, C ₁₃ H ₂₇ −, C ₁₅ H ₃₁
- _{, C17H35-} , _{C17H33- , C17H31C17H29-} , alkyl groups _and alkenyl groups having 9 to ₁₇ carbon atoms obtained from coconut oil, and the _like . In the nonionic surfactant represented by the general formula (C), for example, as the alkyl group R ₃ 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
Examples thereof include CO-, a mixed alkylyl group having 8 to 20 carbon atoms obtained from coconut oil fatty acid, and the like. 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% sample concentration solution was prepared using CaCO ₃ 70 ppm artificial hard water, and the amount of foaming was measured using a cylindrical cylinder equipped with a stirrer at a temperature of 40°C. ○... Good foaming Foam volume 200ml 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 ○…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 220 nm absorption peak. Denaturation rate (%) = Ho-Hs/Ho×100 Ho: Height of the 220nm absorption peak of ovalbumin Hs: Height of the 220nm absorption peak when the sample is added to the ovalbumin buffer ◎...Ovalbumin denaturation rate 30 Less than % ○... 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 Hand roughness test method For each sample, 5 men and 5 men, 10 people in total Using either the left or right hand, 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 ○... 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, lauryl ether sulfate-based general commercial shampoo (Does not contain drugs for dandruff and itching) A panel of people using the sample were asked to wash their hair 5 times using the same frequency and method as usual, and the amount of dandruff before and after using the sample. compared. The amount of dandruff on the 3rd day after washing with a general commercial shampoo and the amount of dandruff on the 3rd day after washing with a sample 5 times.
The amount of dandruff on each day was measured. Dandruff is collected by suction from the head with a suction device equipped with a filter cloth, and the amount of nitrogen is determined using the Kjeldahl method to eliminate errors caused by other foreign substances.The amount of nitrogen is determined by multiplying this by 6.25 to obtain the average protein amount, and the amount of dandruff (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 ○...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 ×...The amount of dandruff increased after using the sample Usability (creaminess of the foam) A panel of 20 women with long hair divided their hair into left and right halves and washed their hair at the same time. Comparative sensory evaluation was conducted using Comparative Example 1 as a control. ◎…More than 10 out of 20 people rated it as better than Comparative Example 1 ○…Up to 10 out of 20 people rated it as better than Comparative Example 1 △…Up to 10 out of 20 people rated it as inferior to Comparative Example ×…20 At least 10 people out of the total evaluated that the sample was inferior to Comparative Example 1. Low-temperature stability evaluation method: Store the sample in a constant temperature bath at -10℃ for one month, and visually observe the appearance of the sample at -10℃ after one month. The low temperature stability was evaluated using the following criteria. ○...Dissolved transparently. △...Slight turbidity is observed. ×...Occurrence of white turbidity and precipitate is observed. Examples 1-2 A shampoo consisting of the composition shown in Table 1 was prepared,
Its foaming properties, cleansing properties, protein denaturation, amount of dandruff caused by rough hands, usability (finger slippage), and low-temperature stability were investigated. Examples 3 to 6 Shampoos having the composition shown in Table 2 were prepared,
Its foaming properties, cleansing properties, protein denaturation, roughness on hands, amount of dandruff generation, ease of use (finger slippage), and low-temperature stability were investigated. Examples 7 to 12 Shampoos having the formulations shown in Table 3 were prepared, and their foaming properties, detergency, protein denaturation, roughness,
The amount of dandruff generated, usability (finger slippage), and low-temperature stability were investigated.

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【table】 Example 13 A shampoo consisting of the following formulation was prepared. Polyoxyethylene (average 1.5) 6% by weight Sodium lauryl sulfate Polyoxyethylene (average 1.5) 4 lauryl triethanolamine Amphoteric surfactant (Note-1) 10 Lauric acid diethanolamide 5 glycerin 2 Fragrance 0.3 Pigment trace amount water residue Example 14 A shampoo consisting of the following formulation was prepared. Polyoxyethylene (average 2.0) 7% by weight Sodium lauryl sulfate Polyoxyethylene (average 2.0) 4 lauryl triethanolamine Amphoteric surfactant (Note-1) 6 Lauric acid diethanolamide 3 Coconut fatty acid monoethanolamide 1 Ethylene glycol fatty acid ester 2.5 1,3-butylene glycol 1 Fragrance 0.3 Pigment trace amount water residue Example 15 A shampoo consisting of the following formulation was prepared. Polyoxyethylene (average 1.5) 8% by weight Sodium lauryl sulfate Polyoxyethylene (average 1.5) 7 lauryl triethanolamine Amphoteric surfactant (Note-1) 10 Lauric acid diethanolamide 4 Polyethylene glycol 300 1 Cationized cellulose polymer 0.3 (UCC Polymer JR-400) Pigment trace amount Fragrance 0.3 water residue Example 16 A shampoo consisting of the following formulation was prepared. Polyoxyethylene (average 1.0) 7% by weight Sodium lauryl sulfate Polyoxyethylene (average 2.0) 6 lauryl sulfate triethanolamine Amphoteric surfactant (Note-1) 7 Coconut fatty acid diethanolamide 5 Protein derivative 0.5 Preservative small amount Pigment trace amount Fragrance 0.25 water residue

Claims (1)

[Claims] 1 General formula (A) R ₁ O(CH ₂ CH ₂ O) rSO ₃ M...(A) (wherein R ₁ is an alkyl group or alkenyl group having an average number of carbon atoms of 7 to 21, r is the average number of added moles
0.5 to 3, M ₁ is a mixture of organic amines consisting of mono-, di-, or triethanolamine or a mixture thereof and sodium, potassium or lithium; a molecule of organic amines and an alkali metal such as sodium, potassium or lithium; The mixture has a ratio of 1:1 to 1:5. ) and general formula (B) [In the formula, R ₂ is an alkyl group or alkenyl group having an average number of carbon atoms of 9 to 17, m and n are integers of 1 to 3, and Z is a hydrogen atom or -(CH ₂ )
lCOOY (l is an integer of 1 to 3, Y represents an alkali metal, alkaline earth metal or organic amino) group; M represents an alkali metal, alkaline earth metal or organic amine; Amphoteric surfactant represented by ] and general formula (C) (In the formula, R ₃ represents an alkyl group or an alkenyl group having an average number of carbon atoms of 7 to 19, p and q are integers, and p+q is 1 to 5.) A cleaning composition containing it as an ingredient. 2 The weight ratio of the anionic surfactant represented by general formula (A) and the amphoteric surfactant represented by general formula (B) is 3:
It is in the range of 1 to 1:1, and (A) + (B) and general formula (C)
The weight ratio of nonionic surfactant expressed as 15:
The cleaning composition according to claim 1, wherein the ratio is in the range of 1 to 1:1, and (A) + (B) + (C) is 10 to 50% by weight based on the total amount of the cleaning composition.