JPH0639594B2 - Cleaning composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a detergent composition. More specifically, it relates to a detergent composition having a mild action on the skin and having excellent detergency and foaming ability.

The detergent composition of the present invention has versatile uses, but is particularly advantageous when used as a shampoo composition.

[Conventional technology]

Conventionally, detergent compositions include anionic surfactants such as alkyl sulfate ester salts and alpha-olefin sulfonates, nonionic surfactants such as fatty acid alkylolamides, and amphoteric ions such as alkyl betaines and alkyl amine oxides. Surfactants have been used.

[Problems to be solved by the invention]

In the case of anionic surfactants, these surfactants alone have strong detergency and foaming power, but they have strong irritation to the skin, and nonionic surfactants In the case of agents and zwitterionic surfactants, they are surfactants that are less irritating to the skin, but their detergency and foaming power are insufficient for terribly oily soil.

The present inventors have focused their attention on the above points, and as a result of earnest studies, as a result, a surfactant having a strong protein denaturing power or a surfactant composition has a strong skin irritation and a small protein denaturing power. It has been found that the skin irritation is significantly reduced in the case of the surfactant composition.

When a specific anionic surfactant and a specific nonionic surfactant are combined, the protein denaturation rate is synergistically reduced and the skin irritation is significantly reduced as compared with the case where each is used alone. I found it. The present invention is based on this finding.

[Means for solving problems]

That is, the present invention provides the following general formula (I) and / or (II) (In the formula, R ₁ , R ₂ and R ₃ are each a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, X and Y are each hydrogen,
It represents an alkali metal or an organic amine, and l, m and n each represent a number of 0 to 10. And a nonionic surfactant having a HLB of 8 to 16 at a weight ratio of 10: 1 to 3: 1. It is to provide things.

A particularly preferable mixing ratio of the active ingredient is such that the phosphoric acid ester-based surfactant represented by the general formula (I) or (II) and H
The weight ratio to the nonionic surfactant having an LB of 10 to 16 is in the range of 10: 1 to 3: 1, and the total of both is in the range of about 10 to 50 parts by weight.

The present inventors have established that the phosphate ester type surfactant represented by the general formula (I) or (II) and HLB are 10 to 16
When the nonionic surfactant of No. 1 is mixed at an appropriate mixing ratio, that is, in a weight ratio of 10: 1 to 3: 1, the surfactant ability such as foamability and detergency is represented by the general formula (A). It was discovered that the anion-type surfactant alone is not inferior to that of the anionic surfactant alone, and at the same time, the protein denaturing power, that is, skin irritation, is significantly reduced to the extent that it is not inferior to that of the nonionic surfactant alone. Is.

It is presumed that the phenomenon in which this synergistic effect is exhibited is due to the formation of mixed micelles when considering from the measurement of the critical micelle concentration and the like. When the HLB of the nonionic surfactants used is less than 8, the protein denaturing power is reduced, but the HLB is
The nonionic surfactant acts like an oil partly due to the fact that the water content is low, and the foamability and cleaning property are extremely poor.

Further, when a nonionic surfactant having an HLB of 16 or more is used, the protein degrading performance is not significantly lowered and the foaming property is also inferior. As mentioned above, nonionic surfactant H
LB is preferably 10 to 16, but 11 to 14 are preferred HLBs that exhibit such effects.

The phosphoric acid ester-based surfactant used in the present invention is preferably one having an ethylene oxide addition mole number of 0 to 3, particularly no ethylene oxide added, and an alkyl group having 12 to 14 carbon atoms. Those having are preferred. Preferred specific examples include sodium mono- or dilauryl phosphate, potassium mono- or dilauryl phosphate, mono- or diethanolamine dilauryl phosphate, mono- or triethanolamine dilauryl phosphate, mono- or sodium dimyristyl phosphate, mono- or potassium dimyristyl phosphate, mono- or Examples include dilauryl phosphate diethanolamine, mono- or dimyristyl phosphate triethanolamine, and the like.
This phosphoric acid ester-based surfactant contains a compound represented by the above formula (I) and formula (II) in a weight ratio of 10: 0.
It is more preferable to mix them at a ratio of 5: 5.

The nonionic surfactant used in the present invention is HLB.
10 to 16, preferably 11 to 14, nonionic surfactants, polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ester type, polyoxyethylene polyoxypropylene alkyl ester type, polyoxyethylene polyhydric alcohol Examples thereof include fatty acid ester type, polyglycerin fatty acid ester type, and polyoxyethylene hydrogenated castor oil type. A particularly preferred nonionic surfactant in the present invention is a polyoxyethylene alkyl ether type.

HLB is a balance between hydrophilic and lipophilic properties (Hydrophil
ic-Lypophilic Balance), and in the present invention, the value calculated using the formula by Oda / Teramura et al. is used.

The cleaning composition of the present invention may contain known cleaning composition components in addition to the above essential components. For example, amphoteric surfactants, cationic surfactants, higher alcohols, lanolin derivatives, protein derivatives, and oily components such as fatty acid esters of polyethylene glycol, propylene glycol, glycerin, polyethylene glycol, etc., which do not impair the effects of the present invention. Moisturizer components such as, botanical extracts such as crude drugs,
Cationic, anionic, nonionic, etc. water-soluble polymeric substances, sequestering agents, preservatives, bactericides and pH adjusters,
UV absorbers, antioxidants, dyes, fragrances, etc. can be added as required.

In particular, in a shampoo composition, a cationic polymer substance, which is blended for the purpose of improving usability, such as a cation-modified cellulose ether derivative (polymer JR (UCC))
Etc.), polyvinylpyrrolidone derivative quaternary ammonium (gaff coat (GAF) etc.), polymer of diallyldimethylammonium chloride (merket (Merk) etc.), polyacrylic acid derivative quaternary ammonium (Cartex (National
Starch), polyamide derivative quaternary ammonium (San
Doz and the like) can be adsorbed on the hair by being blended with the detergent composition of the present invention to improve the usability over blending with other bases.

〔The invention's effect〕

The present invention will be specifically described below with reference to experimental examples. The test methods examined in the experimental examples are as follows.

Foaming test method CaCO ₃ 70ppm Artificial hard water, sample concentration 1% solution 400ml
It was prepared and the amount of foaming was measured using a cylindrical cylinder with a stirrer at a temperature of 40 ° C.

○: Good foaming volume 2000ml or more △: Normal foaming volume 1500ml or more but less than 2000ml ×… Poor foaming volume less than 1500ml Detergency test method CaO / MgO = 3/1, 5 ° DH artificial hard water, sample concentration 1
% Solution was prepared, and the artificial sebum-contaminated cloth using wool surge was washed.

Targotometer (JISK-3371) under the condition of temperature 40 ℃
Was used to determine the cleaning efficiency from the reflectance before and after cleaning.

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

Ho: 220 nm absorption peak height of ovalbumin Hs: 220 nm when a sample is added to ovalbumin buffer
Absorption peak height ◎… 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 Skin irritation Test method A 10% sample concentration solution is prepared with ion-exchanged water, a guinea pig is immersed in this test solution for 4 hours every day, and this is repeated for 3 days. After the immersion for 12 hours, the reaction appears for 2 days. The reaction was judged according to the five items of erythema, edema, relaxation, desquamation, and cracks.

◎… There is almost no irritation.

(Erythema develops.) ○: Mild irritation (Erythema / relaxation develops) ×… Strong irritation (erythema / edema / relaxation / exfoliation develops) ×… Super-strong irritation (test Erythema, edema, relaxation, desquamation, and cracks develop) Experimental Example 1 A shampoo composed of a combination set forth in Table 1 below was prepared, and its foaming property, detergency, protein denaturation rate, and skin irritation were examined. It was

Experimental Example 2 A shampoo having the composition shown in Table 2 below was prepared, and its foamability, detergency, protein denaturation rate and skin irritation were examined.

Example 1 A liquid detergent having the following composition was prepared.

Monolaurylphosphate triethanolamine 20 Polyoxyethylene (EO average 12) 6 Lauryl ether Diethanolamide laurate 3 Propylene glycol 5 Ethanol 5 Perfume 0.3 Water Residual This liquid detergent was subjected to the same performance evaluation test as in Example 1, The following results were obtained: foamability ○, detergency ○, protein denaturation rate ◎, and guinea pig skin irritation ◎. Example 2 A creamy detergent having the following composition was prepared.

Sodium monolauryl phosphate 20 Sodium monomyristyl phosphate 10 Polyoxyethylene (EO average 30) 6 Hydrogenated castor oil Polyethylene glycol (Molecular weight 1500) 7 Glycerin 15 Sodium chloride 0.5 Perfume 0.3 Water Residual The same performance evaluation test as above was carried out, and the results were: foamability ◯, detergency ◯, protein denaturation rate ◎, and guinea pig skin irritation ◎.

Example 3 A shampoo having the following composition was prepared.

Monolauryl phosphate 15 Triethanolamine Polyoxy (EO average 12) 5 Secondary lauryl ether Polyoxyethylene (EO average 3) 5 Lauryl sulfate triethanolamine Lauryl dimethylamine oxide 2 Glycerin 3 Cationized cellulose 0.5 (Polymer JR-400 (UCC)) Fragrance 0.3 Water Residue This shampoo was subjected to the same performance evaluation test as in Example 1, and the results were that foamability ○, detergency ○, protein denaturation rate ◎, and guinea pig skin irritation ◎. .

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication C11D 1:74) (72) Inventor Yoshihiro Ohata 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Co., Ltd. In-house (72) Inventor Masataka Ogawa 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Examiner, Shiseido Research Institute Co., Ltd. Reiko Imamura (56) Reference JP 55-25458 (JP, A) JP 50- 33205 (JP, A) JP-B 43-2105 (JP, B1)

Claims (1)

[Claims] 1. The following general formula (I) and / or (II) (In the formula, R ₁ , R ₂ and R ₃ each have 8 to 18 carbon atoms.
X is a saturated hydrocarbon group, X and Y are each hydrogen, an alkali metal or an organic amine, and l, m and n are each a number from 0 to 10. And a nonionic surfactant having an HLB of 8 to 16 in a weight ratio of 10: 1 to 3: 1. Composition.