JPH0631407B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition having significantly reduced irritation to the skin.

Conventionally, as surfactants for shampoos, whether they are for professionals such as those for hairdressing salons or general commercial products, mainly alkyl sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, alkylbenzene sulfonate salts, α -Olefin sulfonates and the like have been widely used.

However, although shampoos containing these surfactants have excellent detergency, they are known to be strongly irritating to the skin to some extent to some extent. As described above, professionals who often come into contact with shampoo are likely to have skin disorders such as rough hands. In addition, recently, young people who have developed a particularly fashionable sensation have many times of washing their hair, but even for ordinary people, the number of times of washing is increasing 3 to 4 times / week, such as daily washing of the hair. Continuing to wash hair with a shampoo containing a strong surfactant causes problems such as roughening of the scalp, leading to dandruff and itching.
From these points, there is a strong demand for the use of low-skin irritation shampoos not only for professional use but also for general commercial use.

The present inventors focused their attention on the above points, and as a result of repeated intensive research, in a surfactant or a surfactant composition having a high protein denaturation rate, a rough hand phenomenon of strength by continuously using these,
In contrast to the occurrence of dandruff, surfactants and shampoo compositions having a low protein denaturation rate are unlikely to cause skin disorders such as rough skin even after continuous use for a long period of time, and the occurrence of dandruff is significantly reduced on the scalp. I found a thing. That is, for various surfactants and mixed surfactant compositions, measurement of protein denaturation rate, hand rough test using human hands, actual use (continuous use)
The amount of dandruff was measured by the method, and in the case of a surfactant or a mixed surfactant composition having a low protein denaturation rate, it was found that there is a tendency that the amount of dandruff tends to be reduced, and the present invention is completed. It has come.

That is, the present invention provides (1) general formula (A) R ₁ COOCH ₂ CH ₂ SO ₃ M (A) (wherein R ₁ is an alkyl group or an alkenyl group having an average carbon number of 7 to 19, and M is One or more kinds of isethionate type anionic surfactants represented by alkali metal or organic amines), and (ii) one or more kinds selected from betaine amphoteric surfactants and semipolar surfactants. And a weight ratio of one or more isethionate-type anionic surfactants to one or more betaine-based amphoteric surfactants and one or more semipolar surfactants is 5: 1 to 1: 8. Range of
Further, the detergent composition is characterized in that the total of both is 10 to 50% by weight of the whole, and the protein denaturation rate by the following measuring method is less than 60%.

[Method of measuring protein denaturation rate]

Using aqueous high performance liquid chromatography, the denaturation rate of ovalbumin when a sample was added to an ovalbumin pH7 buffer solution so that the sample concentration was 1% was measured using an absorption peak at 220 nm.

Ho: Height of 220 nm absorption peak of ovalbumin.

Hs: 2 when the sample was added to the ovalbumin buffer solution
Height of 20 nm absorption peak.

As the betaine-based amphoteric surfactant, the general formula (B), Amidobetaine-type amphoteric surfactant represented by [a commercially available product such as Levon 2000 (Sanyo Kasei), Anon BDF (Nippon Yushi) or the general formula (C), Amidosulfobetaine type amphoteric surfactant represented by [Lonzain-CS (Lonza) Miratain CB as a commercial product
S (Milan), etc.] or general formula (D), Betaine-type amphoteric surfactant represented by [Commercially available Anon BL (NOF Corporation), Dehyton AB-30 (Henkel)]
Etc.] or general formula (E), Sulfobetaine-type amphoteric surfactant represented by [Ronzain 12CS (Lonza) etc. as a commercial product] or the general formula (F), Examples include imidazolinium-type amphoteric surfactants [commercially available, such as Obazoline 662-N (Toho Chemical Co., Ltd.) and Anon GLM (NOF CORPORATION)].

Further, as the semipolar surfactant, a general formula (G), The tertiary amine oxide type semipolar surfactant represented by (corresponding to Unisafe A-LM (NOF Corporation), Wandamine OX-100 (Nippon Rika), etc. as commercial products) is exemplified.

(In the general formulas (B) to (G), R ₂ represents an alkyl group or an alkenyl group having an average carbon number of 9 to 17, and R ₃ represents an alkyl group or an alkenyl group having an average number of carbon atoms of 10 to 18. x represents Two
Is an integer of 4 to 4, y is an integer of 0 to 3,
z is an integer of 1 or 2. ) The mixing ratio of the active ingredient varies slightly depending on the type of the amphoteric or semipolar surfactant represented by the general formulas (B) to (G), but one or more isethionate-type anionic surfactants and betaine. The weight ratio with one or more amphoteric surfactants and semipolar surfactants is 5: 1.
The ratio is 10 to 50% by weight of the total.

The present inventors have found that when an isethionate-type anionic surfactant and a betaine-based amphoteric surfactant or a semipolar surfactant are mixed at a specific weight ratio, the viscosity of each is increased and the critical micelle concentration is increased compared to the case of using them alone. It was found that a phenomenon such as a decrease was observed, and it was presumed that a complex was formed.However, in this mixture, the surface-active ability such as foaming property and detergency was superior to that of the single substance. However, at the same time, it was discovered that the protein denaturation rate is remarkably reduced as compared with the case where each protein is used alone. A suitable weight ratio of one or more of the isethionate type anionic surfactant and one or more of the betaine amphoteric surfactant and the semipolar surfactant is in the range of 5: 1 to 1: 8. It is desirable that the weight ratio be as close to 1: 1 as possible. If the mixing ratio is outside this range, a sufficient effect of lowering the protein denaturation rate cannot be obtained.

Further, in the detergent composition of the present invention, further the general formula (H) (Wherein R ₄ represents an alkyl group or an alkenyl group having an average carbon number of 7 to 19, m and n are integers, and m + n is 1 to 5) and an alkylolamide type nonionic surfactant represented by the formula: By blending in a certain ratio, the protein denaturation rate is further reduced. The preferred blending ratio is the total amount of one or more isethionate-type anionic surfactants and one or more of betaine-based amphoteric surfactants and semipolar surfactants: alkylolamide-type nonionic surfactant The agent is in the range of 15: 1 to 1: 1 (weight ratio), and the total amount of all the above surfactants is preferably 10 to 50% by weight based on the total amount of the detergent.

The detergent composition of the present invention comprises, in addition to the above-mentioned components, components generally blended with the detergent as desired, for example, higher alcohols, lanolin derivatives, protein derivatives, oily components such as fatty acid esters of polyethylene glycol, and propylene glycol. , Glycerin, humectant components such as polyethylene glycol, nonionic surfactants such as polyoxyethylene alkyl ether and polyethylene oxide polypropylene oxide block polymer, water-soluble polymer substances, cationic polymers, sequestering agents, preservatives, Disinfectant, pH
A regulator, an ultraviolet absorber, an antioxidant, a dye and a fragrance can be included.

Next, the present invention will be described in detail with reference to Examples, but prior to that, the test methods and evaluation methods adopted in each Example will be described.

Foaming test method CaCO ₃ 70 ppm artificial hard water was used to prepare 400 m of a 1% sample concentration solution, and the foaming amount was measured using a cylindrical cylinder equipped with a stirrer at a temperature of 40 ° C.

○ …… Good foaming amount 2,000m or more △ …… Normal foaming amount 1,500m or more and less than 2,000m × …… Poor foaming amount Less than 1,500m Detergency test method CaO / MgO = 3/1, 5 ° DH artificial hard water Then, a solution having a sample concentration of 1% was prepared, and artificial sebum dirt using wool surge was washed. Turgotometer (JIS K-337
After cleaning with 1), the cleaning rate was obtained from the reflectance before and after.

Ro: Reflectivity of original cloth (wool surge) Rs: Reflectivity of contaminated cloth Rw: Reflectivity of contaminated cloth after cleaning ○ …… Good cleaning property Cleaning efficiency 80% or more △ …… Cleaning property Normal cleaning efficiency 60% or more Less than 80% × ... Poor detergency Washing efficiency Less than 60% Measuring method of protein denaturation Egg white when a sample is added to ovalbumin pH7 buffer solution to a sample concentration of 1% using aqueous high performance liquid chromatography The albumin denaturation rate was measured using the absorption peak at 220 nm.

Ho: Height of 220 nm absorption peak of ovalbumin.

Hs: 220n when the sample was added to the ovalbumin buffer solution
m Height of absorption peak.

◎ …… Ovalbumin denaturation rate less than 30% ○ …… Ovalbumin denaturation rate 30% to less than 60% △ …… Ovalbumin denaturation rate 60% to less than 80% × …… Ovalbumin denaturation rate 80% or more Hand roughness test method For each sample, a panel of 5 men and 5 women, 10 people in total,
One of the left and right hands is immersed in an aqueous solution with a sample concentration of 5% and a temperature of 35 ° C, and the other hand is immersed in water of the same temperature for 10 minutes.
The test was performed twice a day for 2 consecutive days, and the difference between the rough skin conditions of the left and right hands was visually evaluated.

◎… Hand roughness is extremely weak 0 to 1 out of 10 people Roughness was observed on the sample side.

○: Roughness of hand 2 to 4 out of 10 people Roughness was observed on the sample side.

Δ: Roughness of hand 5 to 7 out of 10 people Roughness was recognized on the sample side.

X: Hand roughening is extremely strong 8 to 10 out of 10 people Roughness was observed on the sample side.

Method for measuring dandruff generation Ordinary commercial shampoo of lauryl ether sulphate type (without dandruff and chemicals for itch)
The panel using was washed with the sample 5 times with the same hair washing frequency and the same hair washing method as usual, and the amount of dandruff before and after using the sample was compared. The amount of dandruff 3 days after washing the hair with a general commercial shampoo and the amount of dandruff on the 3rd day from the last day of washing the sample 5 times were measured.

The dandruff is collected by suction from the head using a suction device with a cloth, and the nitrogen amount is quantified by the Kjeldahl method in order to eliminate errors due to other foreign substances, and this is multiplied by 6.25 to obtain the average protein amount, and the dandruff amount ( mg / head). The number of panels was 3 for each sample, and the average values were compared.

◎… The amount of dandruff decreased by 30% or more after using the sample.

○: The amount of dandruff decreased by 10% or more and less than 30% after using the sample.

B: The amount of dandruff decreased after use of the sample by 0% or more and less than 10%.

X: An increase in the amount of dandruff after using the sample Example 1 A shampoo having the composition shown in Table 1 below was prepared, and its foamability, detergency, protein denaturation rate, hand roughness, and dandruff generation amount were adjusted. I checked.

The results are shown in Table-1 (Examples) and Table-2 (Comparative Examples).
Shown in.

As described above, the examples showed excellent performances in all of foaming property, detergency, protein denaturation rate, hand roughening property, and dandruff generation amount.

Example 11 A shampoo having the following composition was prepared. Sodium Lauroyl Isetionate 3% by weight Sodium cocoyl isethionate 3 Lauryl betaine 8 Lauric acid dietanol-amide 5 Glycerin 2 Fragrance 0.3 Water Residue This shampoo is subjected to the same performance evaluation test as in Example 1. Foaming property ○ (foam amount 2,200m), cleaning property ○ (cleaning efficiency 8
5%), protein denaturation rate ◎ (bovine serum albumin denaturation rate 8
%), Hand roughening ◎ (no hand roughness was observed in all 10 people), and dandruff generation amount ◎ (dandruff reduction rate 36%).

Example 3 A shampoo having the following composition was prepared. Ethylene glycol fatty acid ester 1.5% by weight Sodium cocoyl isethionate 10 Cocamidopropyl betaine 6 Lauryl dimethylamine oxide 2 Coconut oil fatty acid dietanol-amide 5 cation cellulose 0.3 Propylene glycol 2 Perfume 0.3 Water Residual As a result of performing the same performance evaluation test as in Example 1, the cream type shampoo showed excellent performances in terms of foamability ◯, detergency ◯, protein denaturation rate ◎, hand roughening ◎, and dandruff generation ◎.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-58-134198 (JP, A) JP-A-58-134199 (JP, A)

Claims (3)

[Claims] (I) General formula (A) R ₁ COOCH ₂ CH ₂ SO ₃ M (A) (wherein R ₁ is an alkyl group or an alkenyl group having an average carbon number of 7 to 19, and M is Or two or more isethionate type anionic surfactants represented by the formula (1), which represents an alkali metal or an organic amine, and (ii) one or two selected from betaine amphoteric surfactants and semipolar surfactants. And one or more isethionate-type anionic surfactants and one or more betaine-based amphoteric surfactants and semipolar surfactants in a weight ratio of 5: 1 to 1 : 8 and the sum of both is 10 to 50 in total.
A detergent composition characterized in that the protein denaturation rate is less than 60% as measured by the following measurement method in a weight percentage. [Method for measuring protein denaturation rate] Using water-based high performance liquid chromatography, the ovalbumin denaturation rate is measured using an absorption peak at 220 nm when a sample is added to an ovalbumin pH7 buffer solution to a sample concentration of 1%. did. Ho: Height of 220 nm absorption peak of ovalbumin. Hs: 2 when the sample was added to the ovalbumin buffer solution
Height of 20 nm absorption peak. 2. A betaine-type amphoteric surfactant is a betaine-type amphoteric surfactant, a sulfobetaine-type amphoteric surfactant,
An amidobetaine-type amphoteric surfactant, an amidesulfobetaine-type amphoteric surfactant, or an imidazolinium-betaine-type amphoteric surfactant. Claim (1)
The cleaning composition according to the item. 3. The detergent composition according to claim (1) or (2), wherein the semipolar surfactant is a tertiary amine oxide type semipolar surfactant.