JPH0553840B2 - - 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 per 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, the current situation is that there is a strong demand for the use of shampoos with low skin irritation, not only for professional use but also for general commercial use. The present inventors focused on the above points and as a result of intensive research, we found that surfactants and surfactant compositions with strong protein denaturing power can cause severe roughness of hands and dandruff when used repeatedly. On the other hand, surfactants and shampoo compositions with low protein denaturing power are less likely to cause skin disorders such as rough hands even if used for a long period of time, and also significantly reduce the occurrence of dandruff on the scalp. I found it. That is, for various surfactants and mixed surfactant compositions, we measured the protein denaturation rate, conducted rough hand tests using actual human hands, and measured the amount of dandruff caused by actual use (prolonged use). 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) R ₁ -O(CH ₂ CH ₂ O) _n -SO ₃ M (A) (wherein R ₁ is an alkyl group or alkenyl having an average number of carbon atoms of 7 to 21) group, m is the average number of added moles
It represents 0.5 to 3, and M represents monoethanolamine, diethanolamine, triethanolamine, or an alkali metal. ), and one or two selected from the group of monoethanolamine salts, diethanolamine salts, and triethanolamine salts.
An anionic surfactant which is a mixture of one or more types selected from the group of alkali metal salts and one or more types selected from the group of alkali metal salts, and the mixing ratio of amine salt/alkali metal salt is 10/1 to 1/10 by weight. and general formula (B) (In the formula, R ₂ is an alkyl group or alkenyl group having an average of 7 to 19 carbon atoms, R ₃ is a hydrogen atom or a lower alkyl group having an average of 1 to 3 carbon atoms,
R ₄ and R ₅ are lower alkyl groups having an average number of carbon atoms of 1 to 3; n is an integer of 1 to 4; ) and an alkyloylamide betaine type amphoteric surfactant represented by the general formula (C) (In the formula, R ₆ represents an alkyl group or 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 the present invention as an active ingredient is provided. The preferred blending ratio of the above three components is that the polymerization ratio of (A):(B) is 4:1 to 1:4, and (A)+(B):(C)
The weight ratio of (A) is in the range of 10:1 to 1:1;
+(B)+(C) accounts for 10 to 50% by weight of the total. Hereinafter, the configuration of the present invention will be explained in detail. 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. On the other hand, those having an average added mole number of polyoxyethylene exceeding 3 are satisfactory in terms of skin irritation, rough hands, etc., but are not preferable because they are insufficient in terms of foaming, creaminess of the foam, etc. The counter ion is a mixture of one or more selected from the group of monoethanolamine, diethanolamine, and triethanolamine and one or more selected from the group of alkali metals such as sodium, potassium, or lithium. . The mixing ratio of amine salt/alkali metal salt in the anionic surfactant of general formula (A) is 10/1 to 1/10 by weight. General formula (A)
Although the anionic surfactant represented by has sufficient surfactant properties such as foaming and detergent properties, it has strong protein denaturing properties, and when used alone, the desired low irritation detergent cannot be obtained. . On the other hand, the alkylamide betaine type amphoteric surfactant represented by the general formula (B) has low protein denaturation ability and weak irritation, but has foaming and
Since the surfactant ability such as detergency is inferior, when used alone, there is a drawback that a detergent with satisfactory performance cannot be obtained. The present inventors have discovered that when an anionic surfactant represented by the above general formula (A) and an alkylylamide betaine type amphoteric surfactant represented by the above general formula (B) are mixed at a certain ratio, each They discovered that phenomena such as an increase in viscosity and a decrease in critical micelle concentration occurred compared to when they were used alone, and it was assumed that a complex of anionic surfactant and amphoteric surfactant was formed. In the mixture, the surfactant ability such as foaming property and detergency is as good as that of the anionic surfactant represented by the general formula (A) alone.
At the same time, it was discovered that the protein denaturation ability was significantly reduced to an extent that was at least as good as that of the alkylamide betaine type amphoteric surfactant represented by general formula (B) 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. The weight ratio of (A):(B) is
It ranges from 4:1 to 1:4. 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 been conventionally used in anionic surfactant shampoos to have a foaming enhancement effect, a thickening effect, and low-temperature stability. It is blended for the purpose of improving (reducing Krafft point) effect, etc., but in the present invention, the above-mentioned
It has been found that by incorporating (C) into a mixture of (A) and (B) at a certain ratio, protein denaturation performance is further reduced. Preferable (A)+
The ratio of (B):(C) is in the range of 10:1 to 1:1 by weight, and if (A) + (B) is too much than this ratio, (C)
(C)
If there is too much, the detergency and foaming properties of the shampoo will be impaired. Also, (A) + (B) + (C) is
10 to 50 of the total to form liquid shampoo
It is desirable that it is in weight%. In the present invention, R ₁ in 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 −,
Alkyl groups such as C ₁₈ H ₃₇ - and mixed alkyl groups having 7 to 19 carbon atoms obtained from coconut oil fatty acids, etc.
Alternatively, alkenyl groups such as C ₁₈ H ₃₅ - can be mentioned. Examples of R ₂ of the alkylylamide betaine type amphoteric surfactant represented by the general formula (B) include:
C ₇ H ₁₅ −, C ₁₁ H ₂₃ −, C ₁₃ H ₂₇ −, C ₁₅ H ₃₁ −,
Alkyl groups such as C ₁₇ H ₃₅ −, C ₁₇ H ₃₅ −, mixed alkyl groups having 7 to 19 carbon atoms obtained from coconut oil, or C ₉ H ₁₇ −, C ₁₇ H ₃₃ −, C ₁₇ H ₂₉ −
In addition to hydrogen atoms, alkenyl groups such as R ₃ include
For example, an alkyl group such as -CH ₃ or -CH ₂ CH ₂ CH ₃ is used as R ₄ or R ₅ , such as -CH ₃ or -
Examples include alkyl groups such as CH ₂ CH ₂ CH ₃ . As R ₆ of the alkylolamide type nonionic surfactant represented by the general formula (C), for example,
7 carbon atoms obtained from alkyl groups such as C ₁₁ H ₂₃ −, C ₁₃ H ₂₇ −, C ₁₅ H ₃₁ −, C ₁₇ H ₃₅ − and coconut oil fatty acids
to 19 mixed alkyl groups, or C ₁₇ H ₃₃
Examples include alkenyl groups such as -. 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 polyoxyethylene polyoxypropylene block polymer, and water-soluble polymeric substances (anionic, nonionic, and cationic). ), sequestering agents, preservatives, bactericidal agents, PH regulators, ultraviolet absorbers, antioxidants, pigments, fragrances, etc. In particular, the polyoxyethylene polyoxypropylene block polymer acts effectively as a viscosity modifier for the cleaning composition of the present invention. In particular, anionic surfactants represented by the general formula (A): general formula (B)
The weight ratio of the alkyloylamide betaine type amphoteric surfactant represented by (A), (B) and the alkylolamide type nonionic represented by the general formula (C) is from 3:7 to 7:3. When the total amount of surfactants is in the range of 15 to 50% by weight, a cleaning composition with a desired viscosity can be obtained by blending the polyoxyethylene polyoxypropylene book polymer in an amount of 0.1 to 10% by weight. can be obtained. Next, the present invention will be explained in detail using examples. The present invention is not limited thereby. 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 foaming amount was measured using a cylindrical cylinder equipped with a stirrer at a temperature of 40°C. ○...Good foaming Foam volume 2000ml or more △…Normal foaming Foam volume 1500ml or more but 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 effect was determined from the reflectance before and after cleaning. Cleaning effect (%) = 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 but less than 80%×…Poor cleaning performance 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% ○...Ovalbumin denaturation rate 30% or more and less than 60% △...Ovalbumin denaturation rate 60% or more and less than 80% ×...Ovalbumin denaturation rate 80% or more Hand roughness 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 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 to 1 person out of 10 people Rough hands were observed on the sample side ○... Hand roughness was slightly weak 2 to 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 found that their hands were rough on the sample side ×... Extremely rough hands 8-10 out of 10 participants had rough hands on the sample side Dandruff production measurement method Usually, lauryl ether sulfate-based general commercial shampoo (Does not contain drugs for dandruff and itch) The panel was asked to wash their hair five times using the sample, using the same hair washing frequency and hair washing method as usual, before and after using the sample. The amount of dandruff was compared. The amount of dandruff on the third day after washing the hair with a 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 were measured. Dandruff is collected by suction from the head using a suction device with a cloth attached, and in order to eliminate errors caused by other foreign substances, the amount of nitrogen is fixed using the Kjeldahl method, and this is multiplied by 6.25 to determine the average protein amount. (mg/head). The number of panels was 3 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 Item ×...The amount of dandruff increased after using the sample Examples 1 to 2 A shampoo consisting of the formulation shown in Table 1 was prepared,
We investigated its foaming properties, detergency/protein denaturation, amount of dandruff caused by rough hands, usability (finger slippage), and low-temperature stability.

[Table] 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, usability (finger slippage), and low-temperature stability were investigated. As is clear from the results in Tables 1 and 2, the cleaning composition of the present invention exhibited excellent performance in all of the foaming properties, detergency, protein denaturation rate, roughness on hands, and amount of dandruff.

[Table] Example 7 A shampoo having the following composition was prepared. (Weight %) Polyoxyethylene (average 1.5) Sodium lauryl sulfate 4 Polyoxyethylene (average 1.5) Triethanolamine 2 Alkyloylamide betaine type amphoteric surfactant
3 (Note 1) Lauric acid diethanolamide 2 Glycerin 2 Fragrance 0.3 Pigment Trace amount of water Remaining Example 8 A shampoo consisting of the following formulation was prepared. (Weight %) Polyoxyethylene (average 2.0) Sodium lauryl sulfate 15 Polyoxyethylene (average 2.0) Triethanolamine 9 Alkylolamide betaine type amphoteric surfactant 12 (Note 1) Lauric acid diethanolamide 6 Coconut Fatty acid monoethanolamide 2 Ethylene glycol fatty acid ester 2.5 1,3 butylene glycol 1 Polyoxyethylene = polyoxyprolene = block polymer 3 Fragrance Trace color pigment Residual water Example 9 A shampoo having the following formulation was prepared. (Weight %) Polyoxyethylene (average 1.5) Sodium lauryl sulfate 8 Polyoxyethylene (average 1.5) Triethanolamine 7 Alkylolamide betaine type amphoteric surfactant 10 (Note 1) Lauric acid diethanolamide 4 Polyethylene Glycol 1 Kaotinated cellulose polymer 0.3 (UCC Polymer JR-400) Pigment Minor fragrance 0.3 Water Remaining Example 10 A shampoo consisting of the following formulation was prepared. (Weight %) Polyoxyethylene (average 1.0) Lauryl sulfate Na 7 Polyoxyethylene (average 2.0) Lauryl sulfate triethanolamine 6 Alkylolamide betaine type amphoteric surfactant 7 (Note 1) Coconut fatty acid diethanolamide 5 Protein derivative 0.5 Preservative Small amount Pigment Small amount Fragrance 0.25 Water Residual The shampoos obtained in Examples 7 to 10 were subjected to performance evaluation tests similar to those in Examples 1 to 6. As a result, foaming properties, cleaning properties, The shampoo was excellent in terms of protein denaturation rate, roughness on hands, and amount of dandruff.

Claims (1)

[Claims] 1 General formula (A) R ₁ -O(CH ₂ CH ₂ O) _n -SO ₃ M ... (A) (wherein R ₁ is an alkyl group having an average number of carbon atoms of 7 to 21 or Alkenyl group, m is the average number of added moles
represents 0.5 to 3, M is monoethanolamine,
Represents diethanolamine, triethanolamine, and alkali metals. ) and is a mixture of one or more selected from the group of monoethanolamine salts, diethanolamine salts, and triethanolamine salts and one or more selected from the group of alkali metal salts, and is a mixture of one or more selected from the group of alkali metal salts. / an anionic surfactant whose mixing ratio of alkali metal salt is 10/1 to 1/10 by weight, and general formula (B) (In the formula, R ₂ is an alkyl group or alkenyl group having an average of 7 to 19 carbon atoms, R ₃ is a hydrogen atom or a lower alkyl group having an average of 1 to 3 carbon atoms,
R ₄ and R ₅ are lower alkyl groups having 1 to 3 carbon atoms, and n is an integer representing 1 to 4. ) and an alkylylamide betaine type amphoteric surfactant represented by the general formula (C) (In the formula, R ₆ represents an alkyl group or 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.) and contains as active ingredients, the weight ratio of the anionic surfactant represented by the general formula (A) and the alkyloylamide betaine type amphoteric surfactant represented by the general formula (B) is 4:1 or more. The weight ratio of (A) + (B) and the alkylolamide type nonionic surfactant represented by the general formula (C) is in the range of 10:1 to 1:1, A cleaning composition characterized in that (A) + (B) + (C) is 10 to 50% by weight of the total.