JPH0480298A - Detergent composition - Google Patents

Abstract

PURPOSE:To prepare a detergent compsn. excellent in foaming power and detergency and much lessened in the irritation to the skin by mixing together specified anionic, amphoteric and nonionic surfactants. CONSTITUTION:A detergent compsn. is prepd. by mixing together an N-acyl-N- hydroxy-beta-alanine salt type anionic surfactant of formula I (wherein R1 is alkyl or alkenyl and M is alkali metal or org. amine), an N-alkyl-N,N-dimethyl-alpha- betaine type amphoteric surfactant of formula II (wherein R2 is alkyl) and an alkylolamide type nonionic surfactant of formula III (wherein R3 is alkyl or alkenyl and m and n are 1-5). The detergent compsn. is much lowered in the irritativeness to the skin, while satisfying the indispensable conditions of detergents, such as foaming power, detergency, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a cleaning composition, more specifically foaming properties,
The present invention relates to a detergent composition that satisfies essential conditions for a detergent composition such as detergency and has extremely low irritation to the skin.

[Prior Art] As surfactants conventionally contained in cleaning compositions, fatty acid salts, alkyl sulfate ester salts, polyoxyethine alkyl sulfate ester salts, alkylbenzene sulfonates, α-olefin sulfonates, and alkyloyl alkyls have been used as surfactants. Anionic surfactants such as taurine salts, sulfosuccinates, and alkyl ether phosphates have been used.

However, although cleaning compositions containing these surfactants have excellent cleaning power, they are all known to be irritating to the skin to varying degrees.

From these points, the current situation is that there is a strong demand for cleaners that are less irritating.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a detergent composition that has extremely low irritation to the skin while satisfying the essential conditions for a detergent such as foaming properties and detergency. do.

[Means to solve the problem] The first gist of the present invention is at least, General formula (A) RICON CH2CH2COOM CH.

(wherein R1 represents an alkyl group or an alkenyl group, M represents an alkali metal or an organic amine)
-acyl-N-hydroxy β-alanine salt type anionic surfactant, and N-alkyl- represented by the general formula (B) CH3R2N" CH2COO- CH3 (in the formula, R2 is an alkyl group)
NN-dimethyl α-betaine type amphoteric activator, - General formula (C) (CH2CH20) m H / 3CON \ (CH2CH20) n H (wherein R3 represents an alkyl group or an alkenyl group,
m and n are integers, and m+n is 1 to 5. ) and an alkylonylamide type nonionic surfactant represented by:

The second gist of the present invention is at least N represented by the general formula (A) R1CON CH2CH2COOM H3 (wherein R1 represents an alkyl group or an alkenyl group, and M represents an alkali metal or an organic amine).
-acyl-N-hydroxy β-alanine salt type anionic surfactant, and N-alkyl-N represented by the general formula (B) H3 R2N" CH2COO- CH3 (wherein R is an alkyl group)
, an N-dimethyl α-betaine type amphoteric surfactant, and a general formula (D) R40(CH2CH20) r H (wherein R4 represents an alkyl group or an alkenyl group, and 1 is an integer of 1 to 40). It is present in a cleaning composition obtained by mixing the aliphatic alcohol ethoxylate type nonionic surfactant represented by:

[Function] The function of the present invention will be explained below along with the findings obtained in making the present invention.

In order to achieve the above object, the present inventor carried out sifting of various surfactants in order to investigate the basic characteristics of surfactants. In the process, we obtained the following knowledge.

First, although surfactant A has sufficient surfactant properties such as foaming and detergent properties, it has strong protein denaturing properties, and when used alone, the desired mild detergent cannot be obtained. I understand.

On the other hand, surfactant B has low protein denaturation performance and weak skin irritation, but it has poor surfactant properties such as foaming and cleansing properties, so when used alone, it is not satisfactory. It was also found that there is a drawback that a cleaning agent with high performance cannot be obtained.

In addition, we have investigated many other surfactants, but we have not been able to find one that has excellent foaming properties, cleansing properties, etc., and is low in skin irritation.

I also got the idea to try mixing two or more types of surfactants, but there are countless combinations of surfactants, and it is completely unknown what kind of properties will be obtained as a result of mixing them. Met. In particular, since surfactant A has the disadvantage of being highly irritating to the skin, and surfactant B has the disadvantages of poor foaming and cleansing properties, mixing them will not eliminate these disadvantages. It was not thought that these defects would disappear; rather, it was thought that a product in which these defects were compounded would be obtained.

However, when surfactant C was actually mixed in addition to surfactant A and surfactant B, contrary to the above expectations, foaming properties
Properties such as detergency are superior to those of surfactant A alone, and protein denaturation performance is superior to that of surfactant B11.
They found that the decline was markedly lower than that in Germany, to the extent that it was no better than that in Germany. That is, when surfactant A, surfactant B, and surfactant C are mixed, a synergistic effect is exhibited, and a hypoallergenic blush active agent composition with low protein denaturation ability can be created while maintaining excellent surfactant ability. succeeded in obtaining it.

Although it is not necessarily clear why such a synergistic effect occurs, it is clear that as a result of mixing, phenomena such as an increase in viscosity and a decrease in critical micelle concentration occur compared to when each component is used alone. This is presumed to be due to the formation of a complex of the agents.

Furthermore, in - general formula A, as the A functional group (-CO
ONa), as a functional group (S03Na
), it was discovered that the protein buying denaturation rate is much lower and the skin irritation is also significantly lower than that of the case where the protein has the following properties.This led to the present invention.

[Embodiments] (Surfactant A) In the present invention, an N-acyl-N-hydroxy-β-alanine salt type anionic surfactant represented by the general formula (A) is used.

- In the general formula (A), R is an alkyl group or an alkenyl group, and is a saturated or unsaturated fatty acid residue.

The alkyl group or alkenyl group preferably has an average carbon number of 12 to 18, and an average carbon number of 12 to 14.
is more preferable.

On the other hand, examples of M include -Na and -K.

Examples include Li1 monoethanolamine, jetanolamine, triethanolamine, and basic amino acids.

More specific examples of surfactant A include sodium lauroylmethylalanine (Alaninate LN-30, manufactured by Nikko Chemicals), sodium lauroylmethylalanine (Alanine ALE, manufactured by Yoken Fine Chemicals), sodium lauroylmethylalanine (Alanid, manufactured by NOF Corporation). LNS), among which alaninate LN
It is preferable to use

(Surfactant B) In the present invention, an N-alkyl-N,N-dimethyl α-betaine type amphoteric surfactant represented by the general formula (B) is used.

In general formula (B), R2 is an alkyl group, and the alkyl group preferably has an average carbon number of 7 to 19, particularly preferably 12.14. Roughly 90 to 98% by weight (more preferably 94 to 98% by weight) of carbon atoms with an average carbon number of 12
96% by weight) and 2 to 10% by weight of those with an average carbon number of 14.
(more preferably 4 to 6% by weight) is more preferably used.

More specific examples of surfactant B include dimethyl alkyl lauryl betaine (Nissan Anon BL manufactured by Oil & Fats Co., Ltd.), lauryl dimethylaminoacetic acid betaine (AM-301 manufactured by Nikko Chemicals Co., Ltd.), or carbon obtained from coconut oil. Number 7! Examples include activators having 9 mixed alkyl groups.

(Surfactant C)) In the present invention (claim 1), an alkylolamide type nonionic surfactant represented by the general formula (C) is used.

In general formula (C), R3 is an alkyl group or an alkenyl group, and is a saturated or unsaturated fatty acid residue.

The alkyl group or alkenyl group preferably has an average carbon number of 7 to 19, more preferably an average carbon number of 12 to 14.

A more specific example of the surfactant C is lauroyl jetanolamine (Toho Kagaku Co., Ltd. Tohol S 2 3).
0
Alternatively, there may be mentioned an activator having a mixed alkyl group having 7 to 19 carbon atoms obtained from coconut oil.

(Surfactant D) In the present invention (claim 4), an aliphatic alcohol ethoxylate type nonionic surfactant represented by the general formula (D) is used.

- In the general formula (D), R4 is an alkyl group or an alkenyl group, and is a saturated or unsaturated fatty acid residue.

The alkyl group or alkenyl group preferably has an average carbon number of 7 to 22, more preferably an average carbon number of 12 to 14.

More specific examples of surfactants include, for example, PO
E (2) Lauryl ether (BL-2 manufactured by Nikol)
, Dehydrol LS-2 (EO 2m manufactured by Henkel Hakusuisha)
oJZ addition), etc.

(Blending ratio) In the present invention, the weight ratio of (surfactant A): (surfactant B) is preferably 2=8 to 8:2, and preferably 4:6 to 6:4. More preferred.

Further, it is preferable that the weight ratio of surfactant C to the total of surfactant A and surfactant B is 15=1 to 1:1.

When the content is within this range, the effect of reducing protein denaturation performance, detergency, and foaming properties are significantly improved compared to cases outside this range.

Furthermore, it is preferable that the total amount of surfactant A, surfactant B, and blush active agent C is 10 to 50 parts by weight. Even if the total of the three types of surfactants is within this range, the effects of the present invention can be sufficiently exhibited, and therefore,
The amount of other selective additives can be increased for various purposes. For example, in consideration of face cleansing properties, the content of a humectant such as a polyol can be increased.

(Selective Additives) If desired, the cleaning composition of the present invention may contain ingredients commonly added to cleaning agents, such as higher alcohols, lanolin derivatives, protein conductors, oily components of fatty acid esters of polyethylene glycol, and propylene. Glycol, 1.3-butylene glycol, glycerin, polyoxyethylene glycol, sugar, moisturizing ingredients such as sorbitol, nonionic surfactants such as polyoxyethylene alkyl ether and polyethylene oxide polypropylene oxide block polymer, water-soluble polymers Substances (including anionic, cationic, and nonionic substances), sequestering agents, preservatives, disinfectants, PH adjusters, ultraviolet absorbers, antioxidants,
Inorganic salts such as NaCj2, dyes, fragrances, etc. can be included.

[Example] Next, the present invention will be explained in detail with reference to 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 A 1% sample concentration solution (400 ml) was prepared using CCaCO 370 pp 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 2000m 11 or more O...Slightly good foaming Foam volume 1800-2000m
12Δ...Normal foaming Foam volume 1500~18
00m fL×...Poor foaming Foam volume 1500
Less than m ft/Cleanability test method CaO/Mg0=3/1, 5° DH A solution with a sample concentration of 1% was prepared using artificial hard water, and an artificial sebum-contaminated cloth was washed using wool surge. It was washed using a turbotometer (Jl^-3371) at a temperature of 40°C, and the cleaning effect was determined from the reflectance before and after washing.

Ro: Reflectance of original cloth (wool serge) R8: Reflectance of contamination rate Rw: Reflectance of contaminated cloth after washing O... Good cleaning performance Cleaning effect 80% or more O...
・Cleanability is slightly good.Cleaning effect: 70-80%△...Cleanability is average.Cleaning effect: 60-70% Then, the ovalbumin denaturation rate when the sample was added to the ovalbumin PHTi buffer solution at a test concentration of 1% was measured using the absorption peak at 220 nm.

Ho: Height of the 220 nm absorption peak of ovalbumin H5: Ovalbumin &! ? #Height of 220 nm absorption peak when sample is added to solution ◎... Ovalbumin denaturation rate less than 30% O... Ovalbumin denaturation rate 30% to 60% △... Ovalbumin denaturation rate 60% to 80% ×... Ovalbumin denaturation rate 80% or more - Rough hand test method For each sample, a panel of 10 people in total, 5 men and 5 men, was used to test either the left or right hand at a sample concentration of 5% and a temperature of 35°C. An operation of immersing one hand in an aqueous solution and water at the same temperature for 10 minutes was performed twice a day for two consecutive days, and the difference in rough skin between the left and right hands was visually determined.

◎... Extremely weak hand roughness. Rough hands were observed on the sample side of 0 to 1 out of 10 people.

O: Roughness of hands is slightly weak. Roughness of hands was observed on the sample side of 2 to 4 out of 10 people.

Δ: Slightly rough hands Rough hands were observed in 5 to 7 out of 10 people on the sample side.

×: Extremely rough hands. 8 to 10 out of 10 people observed rough hands on the sample side.

(Examples 1 to 10, Comparative Examples 1 to 6) Cleaning agents having the formulations shown in Tables 1 and 2 were prepared, and their foaming properties, detergency, protein denaturation rate, and roughness on hands were examined.

table (IL rank weight%) table (Unit: 2% by weight) These results are shown in Table-1 and Table-2.

As can be seen from Tables 1 and 2, the examples of the present invention exhibited better performance than the comparative examples in all of the foaming properties, detergency, protein denaturation rate, and roughness of hands.

In particular, the examples (Examples 1 to 8) in which the blending ratio of the surfactant was limited to the range of claim 2 showed much better effects than the examples (Examples 10 and 11) outside the range. Indicated.

(Example 11) A facial cleanser having the following composition was prepared.

(Weight%) Lauroylmethylalanine-Na 12Lauryldimethylaminoacetic acid betaine 16Coconut fatty acid diethanolamide 3Glycerin
5 Citric acid 0.3 Flavor
0.3 water
The remaining face wash was subjected to the same performance evaluation test as in Examples 1 to 1o, and the results were as follows: foaming O1 cleaning property ◎, protein denaturation rate ◎, and hand roughening property ◎.

(Example 12) A shampoo consisting of the following formulation was prepared.

(Weight %) Lauroylmethylalanine-Na 15 Cocoyldimethylaminoacetic acid betaine 15 Lauric acid diethanolamide 4 Propylene glycol
Tricationized cellulose ether 0. 3
Fragrance 0.3 water
The remaining shampoo was subjected to the same performance evaluation tests as in Examples 1 to 10, and the results were as follows: foaming property ◎, detergency O1 protein denaturation rate ◎, and hand roughening property ◎.

(Example 13) A body shampoo having the following composition was prepared.

(weight i%) Lauroylmethylalanine-Na 16 Cocoyl dimethylaminoacetic acid betaine 10 Coconut fatty acid diethanolamide 31.3 Butylene glycol
5 Cocoyl glutamic acid-mono-Na 3 Fragrance 03 Water
Residual This body shampoo was subjected to the same performance evaluation test as in Examples 1 to 10, and was found to have foaming property of ○,
The results were that the O1 protein denaturation rate was ◎ for cleaning properties and ◎ for roughness of hands.

(Examples 14-23, Comparative Examples 7-12) Table-3, Table-4
A cleaning agent having the composition described in 1 was prepared, and its foaming properties, cleaning properties, protein denaturation rate, and roughness on hands were examined.

table (unit weight%) table (unit 12%) These results are shown in Table-3 and Table-4.

As can be seen from Tables 3 and 4, the examples of the present invention exhibited better performance than the comparative examples in all of the foaming properties, detergency, protein denaturation rate, and roughness of hands.

In particular, the examples (Examples 14 to 21) in which the blending ratio of the surfactant was limited to the range of claim 5 had much better effects than the examples (Examples 22 and 23) outside the range. showed that.

(Example 24) Both are the same A facial cleanser having the following composition was prepared.

(% by weight) Lauroylmethylalanine-Na 12lauryldimethylaminoacetic acid betaine 16POE (3)
lauryl ether 3 glycerin
5 Citric acid 0.3 Flavor
0.3 water
The remaining face wash was subjected to the same performance evaluation test as in Examples 14 to 23, and the foaming property was ○.
The results were as follows: , washability: ○, protein denaturation rate: ◎, and hand roughness: ◎.

(Example 25) Both are the same A shampoo consisting of the following formulation was prepared.

(Weight%) Lauroylmethylalanine-Na 15POE (3
) lauryl ether 4-propylene glycol
Tricationized cellulose ether 0.
3 fragrance 0.3 water
The remaining shampoo was subjected to the same performance evaluation test as in Examples 14 to 23, and the foaming property O1
The results were that the O1 protein denaturation rate was ◎ for cleaning properties and ◎ for roughness of hands.

(Example 26) A body shampoo having the following composition was prepared.

(Weight%) Lauroylmethylalanine-Na 16POE (3
) Lauryl ether 31.3 Butylene glycol 5NaCJl
1 fragrance 0.3 water
The remaining body shampoo was subjected to the same performance evaluation tests as in Examples 1 to 8, and the results were as follows: foaming property O1, cleaning property ◎, protein denaturation rate ◎, and hand roughening property ◎.

[Effects of the Invention] According to the present invention, it is possible to obtain a detergent composition that satisfies essential conditions for a detergent such as detergency and has extremely low irritation to the skin.

Claims (6)

[Claims] (1) At least, the general formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ N-hydroxy β-alanine salt type anionic surfactant (hereinafter this surfactant may be referred to as "surfactant A") and general formula (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2 is an alkyl group) N-alkyl-N,N-dimethyl α-betaine type amphoteric surfactant (hereinafter, this surfactant may be referred to as "surfactant B") , General formula (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_3 represents an alkyl group or an alkenyl group, m and n are integers, and m+n is 1 to 5.) type nonionic surfactant (
Hereinafter, this surfactant may be referred to as "surfactant C". ) and a cleaning composition obtained by mixing the following. (2) The weight ratio of surfactant A and surfactant B is 2:
2. The cleaning composition according to claim 1, wherein the ratio is in the range of 8 to 8:2, and the total ratio of surfactant A, surfactant B, and surfactant C is 10 to 50 parts by weight. (3) R_1 is an alkyl group or alkenyl group having an average carbon number of 12 to 18, R_2 is an alkyl group having an average carbon number of 12 or 14, and R_3 is an alkyl group having an average carbon number of 7 to 19. The cleaning composition according to claim 1 or 2. (4) At least the general formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ -Hydroxy β-alanine salt type anionic surfactant and general formula (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an alkyl group) N-alkyl-N
, N-dimethyl α-betaine type amphoteric surfactant, and the general formula (D) R_4O(CH_2CH_2O)_lH (wherein R_4 represents an alkyl group or an alkenyl group, and l is an integer from 1 to 40). Aliphatic alcohol ethoxylate type nonionic surfactant (
Hereinafter, this surfactant may be referred to as "surfactant D". ) and a cleaning composition obtained by mixing. (5) The weight ratio of surfactant A and surfactant B is 2:
5. The cleaning composition according to claim 4, wherein the ratio is in the range of 8 to 8:2, and the total ratio of surfactant A, surfactant B, and surfactant D is 10 to 50 parts by weight. (6) R_1 is an alkyl group or alkenyl group having an average carbon number of 12 to 18, R_2 is an alkyl group having an average carbon number of 12 or 14, and R_4 is an alkyl group or alkenyl group having an average carbon number of 7 to 22. The cleaning composition according to claim 4 or 5, characterized in that: