JP2816888B2 - Detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel detergent composition, and more particularly, to foaming which is less irritating to the skin and hair and which is sufficient even in the presence of strong stains. The present invention relates to a novel detergent composition having power and a moisturizing effect.

[Problems to be solved by conventional technology and invention]

Phosphate salts of organic hydroxy compounds are known to be useful as surfactants that are less irritating to the skin and highly safe for the human body, and are used as raw materials for detergents and the like used directly on the human body. I have. However, with the diversification of lifestyles, the style of detergent has been changing from the conventional solid to the liquid, but long-chain alkyl alcohol, a typical phosphate base detergent base, has been changed. The sodium salt of a phosphoric acid monoester is difficult to use as it is as a liquid cleaning base because of its high Krafft point, and has been used in combination with various auxiliaries. Also,
Along with the sophistication of living standards, there is an increasing demand for development of cosmetics and cosmetic raw materials having higher safety and functions.

On the other hand, in order to give the skin or hair a moist feeling, it is necessary to keep a moderate amount of moisture in the skin or hair, and for this purpose, a moisturizing agent should be added to a detergent, shampoo, rinse, etc. Has been done. Glycerin, polyethylene glycol,
Sorbitol, urea, alkylene oxide adducts of alcohols and the like are used. Compounds having a hydroxyl group, a polyether group, etc. in the molecular structure are known to exhibit moisturizing properties, but when such a compound is used in a system requiring washing with a detergent or shampoo, etc. However, it was washed away with water and the effect could not be fully exhibited.

As an attempt to eliminate these disadvantages, the following equation (II) Wherein R is R ¹ (OR ² ) _m — or (Here, R ¹ is a linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted by a fluorine atom, or a linear or branched chain having 1 to 15 carbon atoms. A phenyl group substituted by a branched alkyl group; R ² represents an alkylene group having 2 to 3 carbon atoms;
Represents a number of 3030, and n represents a number of 0 or 1.)
Represents a hydrogen atom or a salt of an alkali metal, alkaline earth metal, ammonium, alkylamine or alkanolamine.] Has been developed (JP-A-63-205398).
issue).

However, the phosphate represented by the formula (II) is
Since it has a hydroxyl group in the molecule, it exhibits an effect of retaining an appropriate amount of moisture even after washing, but when used as a detergent, it has a somewhat strong hydrophilicity as a surfactant, and it has no problem in general washing but has a strong strength When oil stains were present, the foaming power was slightly insufficient.

Accordingly, there has been a long-felt need for a detergent composition that is less irritating to the skin and hair, has sufficient foaming power even in the presence of strong oil stains, and has a moisturizing effect.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies, and as a result, a phosphate ester having a specific structure is less irritating to skin and hair and has sufficient foaming power even in the presence of strong stains. At the same time, the present inventors have found that they have an effect of appropriately remaining on the skin and the like even after washing and have an effect of retaining moisture on the surface thereof, and have completed the present invention.

That is, the present invention provides the following general formula (I) [Wherein, X and Y each represent a hydrogen atom or a methyl group (except when X and Y are both methyl groups), and R and M have the above-mentioned meanings]. It is intended to provide a cleaning composition characterized by containing.

In the phosphate ester (I) used in the detergent composition of the present invention, the group represented by R ¹ (OR ² ) _m − in R is octyl, dodecyl, tetradecyl, octadecyl, tetracosyl, 2-ethylhexyl, 2-ethylhexyl, Hexyldecyl, 2-octyldodecyl, 2-tetradecyloctadecyl, monomethyl branched isostearyl, octenyl, dodecenyl, hexadecenyl, octadecenyl, triacontenyl, tridecafluorooctyl, heptadecafluorodecyl, heneicosafluorododecyl, pentacosafluoro Tetradecyl, nonacosafluorohexadecyl, 2-pentafluoroethylpentafluorohexyl, 2-tridecafluorohexyltridecafluorodecyl, 2-heptadecafluorooctylheptadecafluorododecyl, octa Butylphenyl, nonylphenyl, polyoxyethylene (3 mol) dodecyl ether,
Polyoxypropylene (3 mol) decyl ether, polyoxyethylene (8 mol) polyoxypropylene (3 mol) dodecyl ether, polyoxyethylene (4 mol)
Octadecenyl ether, polyoxyethylene (3 mol) tridecafluorooctyl ether, polyoxyethylene (5 mol) heptadecafluorodecyl ether,
Polyoxyethylene (3 mol) heneicosafluorodecyl ether, polyoxyethylene (5 mol) 2-tridecafluorohexyl tridecafluorodecyl ether, polyoxyethylene (5 mol) nonylphenyl ether, polyoxypropylene (2 mol) ) Octylphenyl ether group and the like. Also, As the group represented by, 2-hydroxydodecyl, 2-
Hydroxyhexadecyl, 2-hydroxytridecafluorononyl, 2-hydroxypentadecafluorodecyl, 2-hydroxyheptadecafluoroundecyl, 2
-Hydroxy-3-dodecyloxypropyl, 2-hydroxy-3-monomethyl branched isostearyloxypropyl, 2-hydroxy-3-octadecenyloxypropyl, 2-hydroxy-3-heptadecafluorodecyloxypropyl, 2- And a hydroxy-3- (2-pentafluoroethylpentefluorohexyloxy) propyl group. Among them, dodecyl group or tetradecyl group is particularly preferable from the viewpoint of foaming properties as a detergent and detergency.

Examples of the compound represented by M include a hydrogen atom, an alkali metal such as potassium and sodium, an alkaline earth metal such as calcium and magnesium, or ammonium, an alkylamine such as trimethylamine and tributylamine, or a triamine. Alkanolamines such as ethanolamine are exemplified, and alkali metals such as sodium and potassium are particularly preferable from the viewpoints of low Kraft point, foaming property and detergency.

The phosphate (I) used in the present invention can be produced, for example, according to the following reaction formula.

[Wherein, M ′ represents an alkali metal, and R has the above-mentioned meaning. That is, the phosphoric acid ester (I) reacts with the monoalkali metal salt (III) of an organic phosphoric acid monoester with ethylene oxide [Y = H in (IV)] or propylene oxide [Y = CH ₃ ] in (IV). To produce an alkali metal salt (Ia) of a phosphoric acid ester, and if necessary, convert it to a free acid or to another salt.

Further, when propylene oxide is used in the above reaction, a phosphoric ester represented by the following general formula (Ib) is generated in addition to a phosphoric ester represented by the formula (Ia) depending on the reaction conditions.

[Wherein, M ′ represents an alkali metal, and R has the above-mentioned meaning. Therefore, in the formula (I), the phosphate ester in which X is a methyl group and Y is a hydrogen atom is a compound of the phosphate (I
b) is isolated, converted to the free acid if necessary, or converted to another salt.

These reactions are carried out, for example, according to the method described in JP-A-62-48689.

The phosphate (I) thus obtained has a good balance between hydrophilicity and hydrophobicity as a surfactant, and exhibits excellent foaming properties even in the presence of strong oil stains. In the formula (I), a compound in which X and Y are both hydrogen atoms has particularly preferable performance. These phosphate esters (I) may be used alone or in combination of two or more.

The amount of the phosphate ester (I) in the detergent composition of the present invention is not particularly limited, but is 0.1 to 90% by weight, especially 0.5 to 20% by weight (hereinafter simply referred to as "% ").

The cleaning composition of the present invention contains, in addition to the above-mentioned essential components, a cationic polymer compounded for the purpose of a usability improver, particularly in a shampoo composition, to improve the feel of hair,
Usability can be improved. Examples of the cationic polymer include those described in JP-A-2-42013. Specific examples include a cation-modified cellulose derivative (eg, polymer JR (manufactured by UCC)) and a polyvinylpyrrolidone derivative quaternary ammonium. (Guff coat (GA
F)), polymers of diallyldimethylammonium chloride (Mercoat (manufactured by Merk), etc.), quaternary ammonium polyacrylic acid derivatives (Caltex
Starch)) and quaternary ammonium polyamide derivatives. These cationic polymers are preferably incorporated in the detergent composition of the present invention in an amount of 0.01 to 2.0%.

The cleaning composition of the present invention may further contain known components of the cleaning composition. For example, other anionic surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants, higher alcohols, lanolin derivatives, protein derivatives, silicone derivatives, fatty acids of polyethylene glycol which do not impair the effects of the present invention Oily components such as esters; moisturizing components such as propylene glycol, glycerin, urea, and polyethylene glycol; plant extracts such as crude drugs; water-soluble polymer substances such as anionic and nonionic; Other sequestering agents, preservatives, anti-dandruff agents, bactericides, pH adjusters, ultraviolet absorbers, antioxidants, pigments, fragrances and the like can be added as required.

〔The invention's effect〕

The cleaning composition of the present invention is less irritating to the skin and hair, and has excellent foaming power even in the presence of strong oily stains. And salt exchange to form a calcium salt of phosphate (I), etc., and remain on skin etc. appropriately.
It effectively exerts moisturizing properties by the hydroxyl group in the molecule.

〔Example〕

 Next, the present invention will be described specifically with reference to examples.

Example 1 (i) Synthesis example 20.0 g of monododecyl phosphate having a purity of 97% was placed in a pressure-resistant reactor.
(0.073 mol), 75.0 ml of a 1 N aqueous solution of sodium hydroxide was added, and the mixture was stirred and heated to 70 ° C. to be uniform.
At this time, the acid value of the reaction system (KO required to neutralize 1 g of sample)
Mg of H, the same applies to the following) was 42.9. Next, while maintaining the reaction system at 70 to 80 ° C., 12.8 g (0.29 mol) of ethylene oxide was introduced and reacted at this temperature for 5 hours. At this time, the acid value of the reaction system was 0. Next, 100 g of acetone was added to the residue obtained by extracting the reaction-completed product under reduced pressure and concentrating under reduced pressure for crystallization. The crystals are separated by filtration, washed with acetone, and white crystals of sodium dodecyl 2-hydroxyethyl phosphate (in formula (I), X = H, Y = H, R = C ₁₂ H ₂₅ , M = Na). 19.0 g was obtained.

(Ii) Test Example Kraft point, foaming and moisturizing ability of sodium dodecyl 2-hydroxyethyl phosphate obtained in (i) were measured by the following methods. The results are shown in Table 1.

Measurement method: Foaming CaCO ₃ 71ppm (4 （DH) artificial hard water with surfactant concentration of 2
% Aqueous solution is prepared and 100 g of this solution are poured into a graduated cylinder. Next, this solution was stirred in a cylinder at 40 ° C. for 30 seconds with a flat type propeller at a rotation speed of 1000 rpm every 6 seconds under a reversal condition, and the amount of foam after leaving the stirring for 10 seconds was measured. In addition, lanolin was added to the aqueous solution as an artificial stain.
0.5% was added, and the foaming amount was measured under the same conditions.

Moisturizing Acetone-ether treated skin is treated with a 5% aqueous solution of sodium dodecyl 2-hydroxyethyl phosphate, monosodium dodecyl phosphate, sodium dodecyl 2,3-dihydroxypropyl phosphate, and water for 10 minutes, and then rinsed with hard water After that, the conductance of the skin was measured over time.

From Table 1, the product of the present invention has a significantly lower Kraft point than the corresponding sodium dodecyl phosphate as a comparative product,
Further, it can be seen that foaming is extremely superior to sodium dodecyl 2,3-dihydroxypropyl phosphate, especially in the presence of oil stains. In the moisturizing ability test, the skin treated with the product of the present invention had higher conductance 120 minutes after the treatment than the case treated with sodium dodecyl phosphate or water, and the skin treated with sodium dodecyl 2,3-dihydroxypropyl phosphate. Was almost equivalent to

(Iii) A detergent composition as shown in Table 2 below, which contains the phosphoric ester (I), was prepared.

This body shampoo does not irritate the skin, shows very good foaming and detergency, and has no slimy feeling when rinsing. I was keeping it.

Example 2 In the same manner as in Example 1 (i), monododecyl phosphoric acid and propylene oxide were used to convert potassium dodecyl 2-hydroxypropyl phosphate (in the formula (I), X = H, Y = CH ₃ , R = C
₁₂ H ₂₅ −, M = K). Using this, a detergent composition shown in Table 3 below was prepared.

This shampoo has a delicate lather and volume, giving the hair after washing a moist feel,
Further, it was not irritating and was very preferable as a shampoo.

Example 3 A cleaning composition shown in Table 4 below was prepared by mixing sodium dodecyl 2-hydroxyethylphosphate obtained in Example 1 (i).

This dishwashing detergent was resistant to oil stains, had high detergency, had sufficient foaming, did not get rough, gave a moist feeling to hands after use, and was very preferable as a dishwashing detergent.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Tomihiro Kurosaki 1465 Tamawa, Misaki-cho, Sennan-gun, Osaka (56) References JP-A-62-48689 (JP, A) JP-A-63-205398 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C11D 1/34 C11D 3/37 A61K 7/07-7/08 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. The following general formula (I) Wherein R is R ¹ (OR ² ) _m — or (Here, R ¹ is a linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom, or a linear chain having 1 to 15 carbon atoms. Or a phenyl group substituted by a branched alkyl group, R ² represents an alkylene group having 2 to 3 carbon atoms, m represents a number of 0 to 30, and n represents a number of 0 or 1.) Show,
X and Y are each a hydrogen atom or a methyl group (however, X
And Y are both methyl groups), and M
Represents a hydrogen atom or a salt of an alkali metal, an alkaline earth metal, ammonium, an alkylamine or an alkanolamine.] A phosphoric acid ester represented by the formula: 2. The cleaning composition according to claim 1, further comprising a cationic polymer.