JPH0632724A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic having excellent storage stability, having neither irritating feel nor tangle and providing hair with smoothness and soft feel in the case of application to hair and excellent smoothness, good slip and excellent fitness to skin in the case of application to skin. CONSTITUTION:This cosmetic comprises a phosphoric ester containing an organosiloxane group of formula I [Q is group of formula II or formula III (at least one of pQs is group of formula II); A is H or group of formula IV ((m) is 0 or 1; when m=0, R<1> is 1-36C alkyl or alkenyl, phenyl which is substituted with 1-15C alkyl or alkenyl; R<2> is 2-3C alkylene; (n) is 0-30; when m=1, (n) is 0 and (1) is 0 or 1; when (1) is 0, R<1> is 1-36C alkyl; when (1) is 1, R<1> is 1-36C alkyl or alkenyl); D is 1-22C alkylene which may be interrupted with a group of formula V; B is residue after removal of aminoalkyl bonded to Si from organosiloxane having a bond between alkyl and Si and a bond between aminoalkyl and Si; (p) is >=1].

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has good storage stability, has no squeaky feeling or tangle when applied to hair, gives a smooth and soft feeling to hair, and has smoothness when applied to skin, The present invention relates to a cosmetic which spreads well and has a good fit on the skin.

[0002]

2. Description of the Related Art In the field of cosmetics, dimethylpolysiloxane and cyclic silicone, which are not sticky and have high safety, are positively used as a finishing agent for hair and as an oil component for cosmetics. Recently, research on applying silicone to the field of fragrance and cosmetics has been very active and has a wide range of uses. Compared with conventional silicones, it has improved compatibility with other organic substances, improved chemical resistance, and water solubility. New required characteristics such as improvement, improvement of lubricity, and giving silicone a chemically reactive group are emerging.

Therefore, in order to satisfy the above-mentioned required characteristics, modified silicones having various functional groups introduced into silicones have been developed. Amino-modified, epoxy-modified, carboxyl-modified, mercapto-modified, alcohol-modified, polyether-modified, fluoroalkyl-modified, alkyl-modified, ester-modified, alkoxy-modified and the like have been developed as modified silicones. Such modified silicones have been used as cosmetic materials by taking advantage of their respective characteristics, but their performance is still insufficient.

For example, a polyether-modified silicone in which a silicone has a hydrophilic group to improve water solubility can control the hydrophilicity of the silicone by the amount of polyether bond, and is used as a raw material for cosmetics. And cyclic silicone can be emulsified, and because it is a nonionic type, it has good compatibility with ionic components. However, since the nonionic surfactant having a polyether bond has a cloud point phenomenon, which is a characteristic of the nonionic surfactant, the temperature stability of the emulsification system is poor and it is not suitable for an actual compounding system. Further, when a modified silicone such as polysiloxane or amino-modified silicone, polyether-modified silicone, stearoxy-modified silicone is used in a hair cosmetic composition, the hair treated with this gives good smoothness when dried. , There is a problem of lack of moistness and flexibility, and when wet, that is, when applying a hair cosmetic and rinsing,
There were defects such as a remarkable squeaky feeling and troubles such as tangling of hair.

On the other hand, even when a conventional modified silicone is blended with a skin cosmetic, the smoothness, the spread of the agent, the familiarity with the skin, etc. are not always satisfactory in addition to the problem of the emulsion stability described above. There was a problem.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to have good storage stability, no squeaky feeling or tangle feeling on hair, and excellent smoothness and softness imparting effect.
Another object of the present invention is to provide a cosmetic that is smooth and familiar to the skin.

[0007]

In view of such circumstances, the inventors of the present invention have conducted diligent research, and as a result, a cosmetic containing a phosphoric acid ester having an organosiloxane group represented by the following general formula (1) is stable. The present invention has been completed by discovering that it has excellent properties and is excellent in the effect of imparting smoothness and flexibility to hair and skin.

That is, the present invention provides a cosmetic composition containing a phosphoric acid ester having an organosiloxane group represented by the following general formula (1).

[0009]

[Chemical 2]

The phosphoric acid ester used in the present invention is not particularly limited as long as it is represented by the above general formula, but among them, the one represented by the following general formula (1-1) is preferable.

[0011]

[Chemical 3]

As described above, in the general formula (1-1), the phosphoric acid ester residue may be bonded to any position of the organosiloxane structure, but is bonded to both ends or side chains. preferable. As a particularly preferred example, the following general formula (1
-2), (1-3) or (1-4).

[0013]

[Chemical 4]

In the above general formula (1), the group R ^1-
_{[(OCH 2) l -CH (} OH) CH 2] m - (OR 2) n- ( wherein, l, m, n,
Examples of (as R ¹ and R ² have the same meaning as described above) include the groups shown below. That is, R ¹ is a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms which may be substituted by one or more fluorine atoms, m = 0, n
In the case of = 0, examples thereof include a linear or branched octyl group, decyl group, todecyl group, octadecyl group, tetracosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-tetra Decyl octadecyl group, monomethyl branched isostearyl group, octenyl group, decenyl group, dodecenyl group, hexadecenyl group,
Octadecenyl group, tetracocenyl group, triacontenyl group, tridecafluorooctyl group, heptadecafluorodecyl group, heneicosafluorododecyl group, pentacosafluorotetradecyl group, nonacosafluorohexadecyl group, triacontafluorooctadecyl group, 2-
Pentafluoroethyl pentafluorohexyl group, 2-
Tridecafluorohexyl tridecafluorodecyl group,
2-heptadecafluorooctyl heptadecafluorododecyl group, 2-heneicosafluorodecyl heneicosafluorotetradecyl group and the like; R ¹ has ¹ carbon atom
A phenyl group substituted with a straight-chain or branched-chain alkyl group of -15, and examples of m = 0 and n = 0 include an octylphenyl group and a nonylphenyl group; R ¹ is 1
1 to 36 carbon atoms which may be substituted by the above fluorine atoms
A straight chain or branched chain alkyl group or alkenyl group,
When m = 0 and 0 <n ≦ 30, examples include polyoxyethylene (3 mol) dodecyl ether group, polyoxypropylene (3 mol) decyl ether group, polyoxyethylene (8 mol) polyoxypropylene (3 mol). ) Dodecyl ether group, polyoxyethylene (4 mol) octadecenyl ether group, polyoxyethylene (3 mol) tridecafluorooctyl ether group, polyoxyethylene (5 mol) heptadecafluorodecyl ether group, polyoxyethylene ( 3 mol) heneicosafluorododecyl ether group, polyoxyethylene (5 mol) 2-tridecafluorohexyl tridecafluorodecyl ether group and other polyoxyalkylene alkyl ether groups or polyoxyalkylene alkenyl ether groups; R ¹ is one or more of hydrofluoric Atoms is a linear alkyl group with carbon atoms and optionally 1 to 36 substituted, l = 0, m = 1, n =
In the case of 0, 2-hydroxydodecyl group, 2-
2-hydroxyalkyl groups such as hydroxyhexadecyl group, 2-hydroxytridecafluorononyl group, 2-hydroxypentadecafluorodecyl group, 2-hydroxyheptadecafluoroundecyl group and the like; R ¹ is 1 or more. An alkyl group or an alkenyl group which may be substituted with a fluorine atom, and when l = 1, m = 1 and n = 0 are exemplified, 2-hydroxy-3-dodecyloxypropyl group and 2-hydroxy-3- Monomethyl-branched isostearyloxypropyl group, 2-hydroxy-3-octadecenyloxypropyl group, 2-hydroxy-3-heptadecafluorodecyloxypropyl group, 2-hydroxy-3- (2-pentafluoroethylpentafluoro 2-hydroxy-3-alkyloxyl group such as hexyloxy) propyl group 2-hydroxy-3-alkenyloxy-propyl group and the like.

The phosphoric acid ester (1) is produced, for example, according to the following reaction formula.

[0016]

[Chemical 5]

[In the formula, X represents a halogen atom, M represents a cation, and A, B, D, R ³ and p have the same meanings as described above.]

That is, the phosphoric acid ester (1) having an organosiloxane group is produced by reacting the phosphoric acid ester (2) with the amino-modified organosiloxane (3).

In this reaction, the phosphoric acid ester (2) used as a starting material is, for example, JP-A-62-12319.
It is produced by the method described in Japanese Patent Publication No. 1 and Japanese Patent Publication No. 59-4478. According to the method described in JP-B-59-4478, a compound in which A is a hydrogen atom in the formula (2) can be obtained. In this method, a ring-opened product of epihalohydrin or a by-product derived from epihalohydrin is contained in the reaction product. The unreacted phosphate is included. In the method for producing a phosphoric acid ester of the present invention, when a ring-opened product of epihalohydrin or a by-product derived from epihalohydrin is reacted with an amino-modified organosiloxane (3), a ring-opened product of epihalohydrin or a side product derived from epihalohydrin is produced. The product reacts with the amino-modified onanosiloxane (3) to form a by-product, which makes it extremely difficult to remove it from the reaction-terminated product. Therefore, impurities of ring-opened products of epihalohydrin and byproducts derived from epihalohydrin must be removed before reacting with amino-modified organosiloxane (3). On the other hand, the unreacted phosphate does not always react with the amino-modified organosiloxane (3), and since it is water-soluble, it can be easily removed from the reaction-terminated product by an operation such as washing with water. )
It need not be removed before reacting with. The ring-opened product of epihalohydrin and by-products derived from epihalohydrin are removed by reacting a suitable phosphate such as monoalkali metal phosphate with epihalohydrin in the presence of alkali, and then terminating the reaction product with ethanol, propanol, When the compound is put into a solvent such as 2-propanol or acetone, the desired phosphoric acid ester represented by the formula (2) [where A is a hydrogen atom] and unreacted phosphate are precipitated. It is possible by filtering and further washing with the above-mentioned solvent.

As the other raw material, amino-modified organosiloxane (3), bis (aminopropyldimethyl) siloxane, polydimethylsiloxane, both-terminal amino-modified organosiloxane such as aminopropyl, and 1- (3-amino) are used. Propyl) -1, 1, 3, 3,
One-terminal type amino-modified organosiloxane such as 3-pentamethyldisiloxane or pendant type or T
Examples thereof include aminopropyl-containing dimethylpolysiloxane called structural type, but are not limited thereto. As these amino-modified organosiloxanes (3), commercially available products can be used as they are. Examples of these organosiloxanes (3) include compounds represented by the following formulas (4) to (8).

[0021]

[Chemical 6]

[In the formula, R ¹⁹ is —CH ₃ , —OCH ₃ or —OC ₂ H
₅ is shown, and a to g show the degree of polymerization, respectively. However, this raw material is not limited to the types represented by the above formulas (4) to (8). These can be synthesized by a known method that is usually well known, but commercially available products may be used. As a commercial item, FM3311,
FM3321, FM3325, PS510, PS513 (above Chisso Corporation)
Made), X-22-161AS, X-22-161A, X-22-161B, X-22-161C,
X-22-161Z, KF-865, X-22-3680, KF-864, X-22-3801C, K
F-393, KF-857, KF-859, KF-860, KF-861, KF-862, KF-
867, X-22-380D, (Shin-Etsu Chemical Co., Ltd.), SF8417,
BY16-853, BY16-853B (above Toray Silicone Co., Ltd.)
), TSL9305, TSL9306, TSL9346, TSL9386, TSF4700,
Examples include TSF4701, TSF4702, XF42-702, XF42-703 (all manufactured by Toshiba Silicone Co., Ltd.).

The ratio of the amount of the phosphoric acid ester (2) to the amino-modified organosiloxane (3) used in this reaction is not particularly limited, but is based on the amino group equivalent of the amino-modified organosiloxane (3). Phosphate ester (2)
It is desirable that the halogen content of is not less than equimolar, and is preferably 2 to 10 times equivalent.

In order to carry out the above reaction, first, the amino-modified organosiloxane (3) is mixed with the amino-modified organosiloxane (3) in an amount of 10 to 10 times by weight, more preferably 2 to 5 times by weight of ethanol, Propanol, 2
Dissolving in a solvent that can dissolve the amino-modified organosiloxane (3), such as propanol, toluene, acetone. The type of solvent is amino-modified organosiloxane (3)
There is no problem as long as it is a solvent capable of dissolving the above, but it is preferable to use a solvent that is miscible with a solvent capable of dissolving the phosphate ester (2) described below. On the other hand, the solution of the phosphoric acid ester (2) includes a solvent capable of dissolving the phosphoric acid ester (2), for example, water, methanol, ethanol, propanol, 2-propanol, acetone and the like, and with respect to the phosphoric acid ester (2). It is dissolved in an equal weight to 10 times weight, preferably 2 times to 5 times weight of the solvent. The reaction is started by dropping the solution of the phosphoric acid ester (3) into the solution of the amino-modified organosiloxane (3), and the solution of the amino-modified organosiloxane (3) is dropped into the solution of the phosphoric acid ester (2). You may. The dropping temperature is 30 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C., and the dropping method may be batch dropping, divided dropping, or slow dropping over a certain period of time. After the dropping is completed, the above temperature is maintained and aging is performed. The end point of the reaction can be determined by measuring the amino group content in the reaction mixture by a method such as titration and determining the reaction rate. The reaction may be terminated if the required reaction rate can be achieved, but it is extremely difficult to separate the unreacted amino-modified organosiloxane (3) and the desired phosphoric acid ester (1) when the reaction rate is low. Therefore, it is preferable that the reaction rate of the amino group is as high as possible.

After the completion of the reaction, water and a solvent which is immiscible with water are added to the reaction product, and the mixture is stirred or shaken, allowed to stand, and separated into layers, and the aqueous layer is removed to remove excess phosphate ester (2). It is possible to remove the inorganic salt produced as a by-product. Solvents that are difficult to mix with water used at this time include butanol, toluene, chloroform, dichloromethane, hexane, ethyl ether and the like, and when it is difficult to separate layers or when emulsifying, ethanol, 2-propanol and the like are used. A demulsifier may be added. Further, the solvent is distilled off from the reaction-terminated product, and the resulting residue is washed with water to remove excess phosphate (2) and an inorganic salt produced as a by-product, or butanol, toluene, chloroform, dichloromethane, hexane. It is also possible to dissolve the residue with a solvent such as ethyl ether, and filter off the excess phosphoric acid ester (2) precipitated as an insoluble matter and the inorganic salt produced as a by-product. It is also possible to remove excess phosphate (2) and an inorganic salt by-produced through a reaction product through a mixed bed resin of anion exchange resin and cation exchange resin. In addition, these purification methods may be combined if necessary.

The amount of the phosphoric acid ester (1) thus obtained to be incorporated into the cosmetic composition of the present invention varies depending on the application, but is 0.1 to 45% by weight (hereinafter referred to as "%") of the total amount of the cosmetic composition. In particular, it is preferably 0.5 to 15%.

The cosmetic composition of the present invention can be applied to both hair and skin, but its dosage form and other components are different depending on whether it is for hair or skin, and will be separately described below.

The hair cosmetic composition of the present invention refers to all of the cosmetic compositions applied to the hair, for example, pre-shampoo, shampoo, hair conditioner, hair conditioner, hair treatment, set lotion, broth styling lotion, hair. Sprays, foam styling agents, gel styling agents, hair liquids, hair tonics, hair creams, hair dyes, permanent waving agents and the like are included. Further, its dosage form is not particularly limited, and various forms such as emulsion, suspension, gel, liquid crystal, solid type, and aerosol can be used depending on the application.

The hair cosmetic composition of the present invention may contain, in addition to the above-mentioned essential components, components normally used in hair cosmetic compositions, depending on the intended use.

In the hair cosmetic composition of the present invention, for example, alkylbenzene sulfonate, alkyl ether sulfate, olefin sulfonate, α-sulfofatty acid ester, amino acid type surfactant, phosphate ester type surfactant, sulfosuccinic acid. Anionic surfactants such as ester-based surfactants; cationic surfactants such as quaternary ammonium salts having a linear and / or branched alkyl group (for example, JP-A-61-267505, JP-A-1) -106811
JP, JP-A-1-117821, etc.); amphoteric surfactants such as sulfonic acid type surfactants, betaine type surfactants, alkylamine oxides, imidazoline type surfactants; polyoxyethylene Alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkanolamides and their alkylene oxide adducts, esters of polyhydric alcohols and fatty acids, sorbitan fatty acid esters, nonionic surfactants such as alkyl saccharide-based surfactants, etc. 1 One kind or a combination of two or more kinds can be used according to the performance of various hair treatment agents. In particular, when the hair cosmetic composition of the present invention is a shampoo, in consideration of irritation to the skin and hair,
Among the above surfactants, amino acid-based surfactants, phosphate ester-based surfactants, α-sulfo fatty acid esters,
It is preferable to use an imidazoline type surfactant, an alkyl saccharide type surfactant or the like. In addition, the hair cosmetic composition of the present invention contains a cationized cellulose derivative, a cationic starch, a cationized guar gum derivative, a diallyl quaternary ammonium salt / acrylamide copolymer, and a quaternized polyvinylpyrrolidone for improving the feel of hair and skin. One or more kinds of cationic polymers such as derivatives and polyglycol polyamine condensates may be blended. Preferred specific examples of these cationic polymers include, for example, cationized cellulose having a molecular weight of about 100,000 to 3,000,000, cationized starch having a cationization degree of about 0.01 to 1, and cationization degree of about 0.01 to. 1 cationized guar gum (manufactured by Celanese, Jaguar, etc.), diallyl quaternary ammonium salt / acrylamide copolymer having a molecular weight of about 30,000 to 2,000,000, a molecular weight of about 1
Quaternary polyvinylpyrrolidone derivative having a cationic nitrogen content in the vinyl polymer of 0.004 to 0.2% and a polyglycol polyamine having an alkyl group having 6 to 20 carbon atoms In addition to condensates and adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymers (Soldos Corp., caltaletin, etc.), JP-A-53-139734 and JP-A-60-
The cationic polymer described in 36407 can be mentioned.

The hair cosmetic composition of the present invention further comprises dimethylpolysiloxane other than phosphoric acid ester (1), methylphenylpolysiloxane, amino-modified silicone and fatty acid-modified silicone in order to further improve the feel of hair and skin. One or more silicone derivatives such as alcohol-modified silicone, aliphatic alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone and alkyl-modified silicone can be blended. The silicone derivative may be a single substance or a latex composition emulsion-polymerized according to the method described in JP-B-56-38609. Among these silicone derivatives, dimethylpolysiloxane (polymerization degree of 500 or more), polyether-modified silicone, amino-modified silicone, cyclic silicone and the like are particularly preferable because they give a good feel to hair.

Further, in the cosmetic composition of the present invention, a component which is usually used in hair cosmetic compositions, for example, a hair styling polymer having a film-forming ability such as an amphoteric polymer or an anionic polymer; higher fatty acid salt, alkylamine oxide, fatty acid alkanolamide. , Squalene, lanolin, and other texture improvers; propylene glycol, glycerin, sorbitol, amide derivatives, and other humectants; methyl cellulose, carboxyvinyl polymer, hydroxyethyl cellulose, polyoxyethylene glycol distearate, ethanol, and other viscosity modifiers; pearlizing Agents, fragrances, dyes, ultraviolet absorbers, antioxidants, bactericides such as triclosan, trichlorocarban, anti-inflammatory agents such as potassium glycyrrhizinate and tocopherol acetate; antidandruff agents such as zinc pyrithione and octopirox; methyl Raven, can be optionally added within a range not to impair the effects of such inventions preservatives such as butyl paraben.

When the hair cosmetic composition of the present invention is a hair dye, it is possible to use a commonly used coupler and color-developing substance or direct dye. Further, in the case of a permanent waving agent, a reducing agent, an oxidizing agent and the like which are usually used as the first agent and the second agent can be used.

When the cosmetic composition of the present invention is a skin cosmetic composition, in addition to the above-mentioned essential components, if necessary, other components that are added to ordinary skin cosmetic compositions, such as petrolatum, lanolin, ceresin, microcrystalline wax, Solid / semi-solid oils such as carnauba wax, candelilla wax, higher fatty acids and higher alcohols; water-soluble and oil-soluble polymers; inorganic and organic pigments, inorganic or organic pigments treated with silicon or fluorine compounds, colorants such as organic dyes Anionic activators, cationic activators, nonionic activators, surfactants such as dimethylpolysiloxane / polyoxyalkylene copolymers and polyether modified silicones; other water, preservatives, antioxidants, dyes, Thickener, pH adjuster, fragrance, ultraviolet absorber, moisturizer, blood circulation promoter, cooling sensation, antiperspirant, bactericide, skin activating agent, etc. It can be appropriately added in amounts not detrimental to the effects of the present invention. In particular, when a pigment surface-treated with a fluorine compound is used, sebum is not broken and it is preferable.
The skin cosmetic of the present invention is not particularly limited in its dosage form, kind, etc., and can be produced according to a usual method, and is applied as, for example, an emulsified cosmetic, a lipstick, a blusher, a foundation, a skin cleanser, etc. .

The cosmetic of the present invention can be produced by a conventional method.

[0036]

The cosmetic of the present invention has good storage stability, and when used as a hair cosmetic, the squeaky feeling of the hair when wet,
It has no tangle, gives a moist feel and softness to the hair after drying, and when used as a skin cosmetic, the smoothness, spreadability of the agent and familiarity with the skin are good.

[0037]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 506.4 g (3.2 mg of sodium monohydrogen phosphate dihydrate)
(5 mol) was dissolved in 1345 g of ion-exchanged water, 16.7 g of 96% sodium hydroxide was further added, and the temperature was raised to 80 ° C. 240.2 g of epichlorohydrin in this aqueous solution
(2.60 mol) was added dropwise over 5 hours and aged for 8 hours. The reaction completion product was put into 5000 g of acetone and -5 ° C.
After cooling to room temperature, the deposited precipitate was filtered off, washed with acetone, and dried to give a mixture of 3-chloro-2-hydroxypropylphosphoric acid sodium salt and monosodium hydrogenphosphate 51.
2 g was obtained. The content of sodium 3-chloro-2-hydroxypropylphosphate of this product was 33.5% by the determination of chlorine.

Synthesis Example 1 50 g of aminopropyl end-capped polydimethylsiloxane (X-22-161A amino group equivalent 840 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 150 g of ethanol and the temperature was raised to 80.degree. To this solution, a mixture of 151 g of a mixture of sodium 3-chloro-2-hydroxypropylphosphate sodium salt obtained in Reference Example 1 and monosodium hydrogenphosphate in 453 g of ion-exchanged water was added dropwise over 1 hour. . Then, it was aged at 80 ° C. for 12 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was performed 3 times to remove excess 3-chloro-2-hydroxypropylphosphoric acid sodium salt, monosodium hydrogen phosphate, and by-produced salt. . The solvent was distilled off under reduced pressure from the butanol layer to obtain 56 g of a desired phosphoric acid ester.

[0040]

[Chemical 7]

[0041] ¹ H-NMR External standard TMS, CDCl ₃ δ (ppm) -0.5 ~ 0.5 (m) Si-CH ₃ 1.8 ~ 2.2 (b) Si- (CH ₂ ) ₃ -N 2.8 ~ 3.2 (b) -NH _2- 3.5 to 3.8 (m) PO-CH ₂ CHCH ₂ 8.1 to 8.3 (b) -P-OH

Synthesis Example 2 Polydimethylsiloxane terminal aminopropyl (X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd. Amino group equivalent 840) 50
g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C. A solution prepared by dissolving 91 g (0.24 mol) of sodium dodecyl 2-hydroxy-3-chloropropylphosphate in 272 g of ion-exchanged water was added dropwise to this solution over 6 hours. Then, it was aged at 80 ° C. for 16 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was repeated 3 times to remove excess dodecyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt and common salt. The solvent was distilled off under reduced pressure from the butanol layer to obtain 49 g of a desired phosphoric acid ester.

[0043]

[Chemical 8]

[0044] ¹ H-NMR external standard _{TMS, CDCl 3 δ (ppm)} -0.5~0.5 (m) Si-CH 3 0.6~1.8 (m) -POC 12 H 25 2.7~2.8 (b) -NH 2 - 2.8~3.2 Si -(CH ₂ ) ₃ -N 3.4 to 4.2 PO-CH ₂ CHCH ₂

Synthesis Example 3 50 g of aminopropyl group-containing polydimethylsiloxane (KF-864, amino group equivalent 3800, manufactured by Shin-Etsu Chemical Co., Ltd.)
Was dissolved in 200 g of isopropanol and the temperature was raised to 80 ° C. 20 g (0.052 mol) of dodecyl 3-chloro-2-hydroxypropyl phosphate sodium salt was added to this solution.
What was melt | dissolved in 60 g of ion-exchange water was dripped over 3 hours. Then, it was aged at 80 ° C. for 15 hours. At this time, the reaction rate of the amino group was 100%. After aging,
The solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, 250 g of ion-exchanged water was added to the filtrate, and the mixture was stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was repeated 3 times to remove excess dodecyl 3-
Chloro-2-hydroxypropylphosphoric acid sodium salt and the salt produced as a by-product were removed. The solvent was distilled off from the butanol layer under reduced pressure to obtain 43 g of a desired phosphate ester.

[0046]

[Chemical 9]

[0047] ¹ H-NMR external standard _{TMS, CDCl 3 δ (ppm)} -0.5~0.5 (m) Si-CH 3 0.6~1.8 (m) -POC 12 H 25 2.7~3.0 (b) -NH 2 - 3.3~3.7 ( m) Si- (CH ₂ ) ₃ -N 3.8 to 4.2 (m) PO-CH ₂ CHCH _2-

Synthesis Example 4 50 g of aminopropyl group-containing polydimethylsiloxane (KF-864, manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 3800)
Was dissolved in 200 g of 2-propanol and the temperature was raised to 80 ° C. To this solution, the 3-chloro-2-obtained in Reference Example 1 was added.
Hydroxypropyl phosphate sodium salt and hydrogen phosphate 1
A solution prepared by dissolving 34 g of a sodium mixture in 100 g of ion-exchanged water was added dropwise over 5 hours. Then 80 ° C
Aged for 13 hours. At this time, the reaction rate of the amino group is 1
It was 00%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, add 250 g of ion-exchanged water to the butanol layer and stir it to perform the same operation 3
Repeat to remove excess 3-chloro-2-hydroxypropyl phosphate sodium salt, sodium phosphate monobasic and by-produced salt, and further use ion exchange resin AG501-X8 (20-50mesh) manufactured by Bio-Rad. Through
The solvent was distilled off under reduced pressure to obtain 40 g of a desired phosphoric acid ester.

[0049]

[Chemical 10]

[0050]

Synthesis Example 5 Bis (aminopropyldimethyl) siloxane (Toshiba Silicone Co., Ltd. TSL9306 amino group equivalent 124) 50
g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C. 21 g of the mixture of 3-chloro-2-hydroxypropyl phosphate sodium salt obtained in Reference Example 1 and monosodium hydrogen phosphate dissolved in 100 g of ion-exchanged water was added dropwise to this solution all at once. Then, it was aged at 80 ° C. for 10 hours. At this time, the reaction rate of the amino group was 100%. After the aging, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with 5
00g of butanol was added to remove insoluble matter by filtration,
Further, 250 g of ion-exchanged water was added to the filtrate and stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was performed 3 times to remove excess 3-chloro-2-hydroxypropylphosphoric acid sodium salt, monosodium hydrogen phosphate, and by-produced salt. . The solvent was distilled off from the butanol layer under reduced pressure to obtain 46 g of a desired phosphoric acid ester.

[0052]

[Chemical 11]

[0053]

Synthesis Example 6 3-aminopropyl-1,1,1,3,3-pentamethyldisiloxane (TSL9305, Toshiba Silicone Co., Ltd.)
50 g of amino group equivalent 205) was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C. To this solution was added dodecyl 3-chloro-2-hydroxypropyl phosphate sodium salt 371.
What melt | dissolved g (0.98 mol) in 1100 g of ion-exchange water was dripped over 1 hour. Then, it was aged at 80 ° C. for 8 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was repeated 3 times to remove excess dodecyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt and common salt. The solvent was distilled off from the butanol layer under reduced pressure to obtain 47 g of a desired phosphoric acid ester.

[0055]

[Chemical 12]

[0056]

Synthesis Example 7 50 g of aminopropyl group-containing polydimethylsiloxane (KF-862 manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent 1900)
Was dissolved in 150 g of 2-propanol and the temperature was raised to 80 ° C. A solution prepared by dissolving 40 g (0.11 mol) of sodium dodecyl 3-chloro-2-hydroxypropylphosphate in 120 g of ion-exchanged water was added dropwise to this solution over 3 hours. Then, it was aged at 80 ° C. for 10 hours. At this time, the reaction rate of the amino group was 100%. After aging,
The solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, 250 g of ion-exchanged water was added to the filtrate, and the mixture was stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was repeated 3 times to remove excess dodecyl 3-
Chloro-2-hydroxypropyl phosphate sodium salt and salt produced as a by-product were removed, and further passed through Bio-Rad Co., Ltd. ion exchange resin AG501-X8 (20-50 mesh),
The solvent was distilled off under reduced pressure to obtain 35 g of a desired phosphoric acid ester.

[0058]

[Chemical 13]

[0059]

Synthesis Example 8 Polydimethylsiloxane terminal aminopropyl (X-22-161AS amino group equivalent 450 manufactured by Shin-Etsu Chemical Co., Ltd.) 5
0 g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C.
To this solution, 194 g (0.44) of 2-hexyldecyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt.
(Mol) was dissolved in a mixed solvent of 450 g of ethanol and 150 g of ion-exchanged water, and the mixture was added dropwise over 3 hours. Then, it was aged at 80 ° C. for 10 hours. At this time, the reaction rate of the amino group was 100%. After completion of aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and the filtrate was deionized water 25
0 g was added and stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer and stirred, and the same operation was repeated 3 times to remove excess 2-hexyldecyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt and by-produced salt. It was passed through an ion exchange resin AG501-X8 (20-50 mesh) manufactured by Bio-Rad Co., and the solvent was distilled off under reduced pressure to obtain 31 g of a desired phosphate ester.

[0061]

[Chemical 14]

[0062]

Synthetic Example 9 Polydimethylsiloxane-terminated aminopropyl (X-22-161AS amino group equivalent 450 manufactured by Shin-Etsu Chemical Co., Ltd.) 5
0 g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C.
To this solution, trioxyethylene dodecyl 3-chloro-
2-Hydroxypropyl phosphate sodium salt 207g
What melt | dissolved (0.44 mol) in ion-exchange water 500g was dripped over 3 hours. Then, it was aged at 80 ° C. for 9 hours. At this time, the reaction rate of the amino group was 100%. After the aging, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with 5
00g of butanol was added to remove insoluble matter by filtration,
Further, 250 g of ion-exchanged water was added to the filtrate and stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer and stirred, and the same operation was repeated 3 times to remove excess trioxyethylene dodecyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt and common salt as a by-product, and to remove the solvent. The target phosphoric acid ester 37 was distilled off under reduced pressure.
g was obtained.

[0064]

[Chemical 15]

[0065]

Synthesis Example 10 Polydimethylsiloxane-terminated aminopropyl (X-22-161AS amino group equivalent 450, manufactured by Shin-Etsu Chemical Co., Ltd.) 5
0 g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C.
To this solution, 182 g (0.44 mol) of nonylphenyl 3-chloro-2-hydroxypropyl phosphate sodium salt and 400 g of 2-propanol and 100 ion-exchanged water were added.
What was melt | dissolved in g was dripped over 5 hours. Then 8
Aged at 0 ° C. for 11 hours. At this time, the reaction rate of the amino group was 100%. After aging, the solvent was distilled off under reduced pressure,
500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, 250 g of ion-exchanged water was added to the filtrate, and the mixture was stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer and stirred, and the same operation was repeated 3 times to remove excess sodium nonylphenyl 3-chloro-2-hydroxypropylphosphate and the by-produced salt, and distill the solvent under reduced pressure. After removal, 30 g of the desired phosphoric acid ester was obtained.

[0067]

[Chemical 16]

[0068]

Synthesis Example 11 Polydimethylsiloxane terminal aminopropyl (X-22-161AS amino group equivalent 450 manufactured by Shin-Etsu Chemical Co., Ltd.) 5
0 g was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C.
To this solution, a solution obtained by dissolving 156 g (0.44 mol) of octadecenyl 3-chloro-2-hydroxypropylphosphate sodium salt in 400 g of ethanol and 100 g of ion-exchanged water was added dropwise over 6 hours. Then, it was aged at 80 ° C. for 12 hours. At this time, the reaction rate of the amino group is 10
It was 0%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer and stirred, and the same operation was repeated 3 times to remove the excess sodium salt of octadecenyl 3-chloro-2-hydroxypropylphosphate and by-produced salt, and the solvent was distilled off under reduced pressure. And target phosphoric acid ester 33
g was obtained.

[0070]

[Chemical 17]

[0071]

Synthesis Example 12 Polydimethylsiloxane-terminated aminopropyl (X-22-161AS amino group equivalent 450 manufactured by Shin-Etsu Chemical Co., Ltd.) 5
0 g was dissolved in 200 g of 2-propanol and the temperature was raised to 80 ° C. To this solution was added tridecafluorooctyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt 245.
What melt | dissolved g (0.44 mol) in 600 g of 2-propanol and 50 g of ion-exchange water was dripped over 3 hours. Then, it was aged at 80 ° C. for 16 hours. At this time, the reaction rate of the amino group was 100%. After completion of the aging, the solvent was distilled off under reduced pressure, 500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, and 250 g of ion-exchanged water was added to the filtrate, followed by stirring for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Further, 250 g of ion-exchanged water was added to the butanol layer, and the mixture was stirred and the same operation was performed 3 times to remove excess tridecafluorooctyl 3-chloro-2-hydroxypropylphosphoric acid sodium salt and by-produced salt, and to remove the solvent. Evaporation under reduced pressure gave 34 g of the desired phosphoric acid ester.

[0073]

[Chemical 18]

[0074]

Synthesis Example 13 3-Aminopropyl-1,1,1,3,3-pentamethyldisiloxane (TSL930 manufactured by Toshiba Silicone Co., Ltd.)
50 g of 5 amino group equivalent 205) was dissolved in 150 g of ethanol and the temperature was raised to 80 ° C. To this solution, 462 g (0.98 mol) of dodecyl 3-chloro-2-hydroxypropyl phosphate triethanolamine salt was added to ion-exchanged water 120.
What was dissolved in 0 g was added dropwise over 1 hour. Then, it was aged at 80 ° C. for 8 hours. At this time, the reaction rate of the amino group was 100%. After aging, the solvent was distilled off under reduced pressure,
500 g of butanol was added to the obtained residue to remove insoluble matter by filtration, 250 g of ion-exchanged water was added to the filtrate, and the mixture was stirred for 30 minutes. The stirring was stopped and the mixture was allowed to stand to separate the butanol layer and the water layer, and the water layer was removed. Furthermore, 250 g of ion-exchanged water was added to the butanol layer and stirred, and the same operation was repeated 3 times to remove excess dodecyl 3-chloro-2-hydroxypropylphosphate triethanolamine salt and by-produced triethanolamine hydrochloride. Furthermore, Bio-Rad Co., Ltd. ion exchange resin AG501-X8 (20-50
The solvent was distilled off under reduced pressure to obtain 36 g of a desired phosphoric acid ester.

[0076]

[Chemical 19]

[0077]

Test Example 1 The compounds of Synthesis Examples 2 and 3 of the present invention and 0.5 g of a conventional polyether-modified silicone were respectively added to dimethylpolysiloxane (KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) 10
15 g of ion-exchanged water was added thereto while stirring with a homogenizer to emulsify, and the stability at 60 ° C. was compared. The results are shown in Table 1.

[0079]

[Table 1]

Test Example 2 The compounds of Synthesis Examples 2 and 3 of the present invention and 0.5 g of a conventional polyether-modified silicone were each dissolved or dispersed in 10 g of a cyclic silicone (KF994 manufactured by Shin-Etsu Chemical Co., Ltd.), and a homogenizer was used. While stirring, 15 g of ion-exchanged water was added to emulsify and the stability at 60 ° C. was compared. The results are shown in Table 2.

[0081]

[Table 2]

Hereinafter, hair cosmetics were produced in Examples 1 to 11, and skin cosmetics were produced in Examples 12 and 13.

[0083]

[Table 3] Example 1 (first agent composition for permanent wave) (%) Thioglycolic acid 6.0 Phosphobetaine modified silicone (Synthesis example 1) 1.0 Stearyltrimethylammonium chloride 0.3 Polyoxyethylene ( 23EO) Lauryl ether 0.2 Propylene glycol 2.0 Ammonium hydrogencarbonate 2.0 Monoethanolamine Appropriate amount (Note 1) Disodium edetate 0.5 Perfume 0.1 Water balance Note 1: pH is 8. Adjust to 5 100.0

[0084]

Table 4 Example 2 (Second agent composition for permanent wave) (%) Sodium bromate 5.0 Phosphobetaine modified silicone (Synthesis Example 1) 1.0 Cationized cellulose (Union Carbide: Polymer JR 400 ) 0.2 polyoxyethylene (2.5) lauryl ether sodium sulfate 3.0 disodium edetate 0.5 preservative 0.1 perfume 0.1 water balance 100.0

[0085]

[Table 5]

[0086]

Table 6 Example 4 (oxidative hair dye second agent composition) (%) Phosphobetaine-modified silicone (Synthesis Example 1) 0.5 hydrogen peroxide 5.0 propylene glycol 7.0 cetanol 9.0 polyoxy Ethylene (23EO) Lauryl ether 5.0 Phosphoric acid water (75%) Appropriate amount (Note 2) Preservative 0.1 Perfume 0.1 Water balance Note 2: Adjust pH to 4.8 100.0

[0087]

[Table 7] Example 5 (oxidative hair dye composition) (%) Phosphobetaine-modified silicone (Synthesis Example 1) 0.5 Ethanol 20.0 Benzyl alcohol 3.0 Brown No. 201 (C.I. No. 20170) ) 0.6 Yellow No. 4 (CI. No. 19140) 0.6 Black No. 401 (CI. No. 20470) 0.2 Xanthan gum 2.0 Preservative 0.1 Perfume 0.1 Water balance 100 .0

[0088]

Table 8 Example 6 (Shampoo composition) (%) Phosphobetaine modified silicone (Synthesis example 1) 0.5 Polyoxyethylene (3.0) lauryl ether sulfate triethanolamine salt 8.0 Lauroyl-N- Methyl-β-alanine sodium salt (Kawaken Fine Chemicals: Alanone A1E) 8.0 Lauric acid diethanolamide (Kawaken Fine Chemicals: Amizole CDE) 5.0 Cationized cellulose (Union Carbide: Polymer JR 400) 0.5 Preservative 0.1 Dye, fragrance, pH adjuster Appropriate amount of water Balance 100.0

[0089]

Table 9 Example 7 (Hair rinse composition) (%) Phosphobetaine modified silicone (Synthesis example 1) 0.5 N- (2-decyl) tetradecyl-N, N, N-trimethylammonium chloride 1.0 Chloride Stearyl trimethyl ammonium 0.5 Cetostearyl alcohol 3.0 Preservative 0.1 Perfume 0.2 Water balance 100.0

[0090]

Table 10 Example 8 (Hair conditioning composition) (%) Phosphobetaine modified silicone (Synthesis example 1) 0.5 Propylene glycol 5.0 Stearyl trimethyl ammonium chloride 0.5 Cetostearyl alcohol 3.0 Liquid paraffin 1 .5 Preservative 0.1 Perfume 0.2 Water Balance 100.0

[0091]

Table 11 Example 9 (conditioning mousse composition) (%) Phosphobetaine-modified silicone (Synthesis Example 2) 0.5 N- (2-decyl) tetradecyl-N, N, N-trimethylammonium chloride 0.5 Octyldodecyl myristate 1.0 Dipropylene glycol 1.0 Glycerin 2.5 Liquid paraffin 0.5 Polyoxyethylene sorbitan monostearate 0.2 Ethanol 5.0 Preservative 0.1 Perfume 0.1 Propellant (LPG) 10.0 Water balance 100.0

[0092]

Table 12 Example 10 (Styling lotion composition) (%) Phosphobetaine modified silicone (Synthesis Example 7) 0.3 N- (2-decyl) tetradecyl-N, N, N-trimethylammonium chloride 0.5 Acrylic resin liquid 2.0 Methacrylic acid ester polymer 1.0 Ethanol 20.0 Perfume 0.2 Water balance 100.0

[0093]

Table 13 Example 11 (Styling spray composition) (%) Phosphobetaine modified silicone (Synthesis example 7) 0.5 Methacrylic acid ester polymer 2.5 Propellant (LPG) 50.0 Perfume 0.1 Ethanol Balance 100.0

[0094]

Table 14 Example 12 (Hand lotion) (%) [Oil phase] Liquid paraffin 10.0 Phosphobetaine-modified silicone (Synthesis example 2) 5.0 Decamethylcyclopentasiloxane 10.0 α-monoisostearyl glyceryl Ether 1.0 Lauryl methicone copolyol Note 1) 1.5 Dextrin stearic acid ester Note 2) 1.0 Aluminum monooleate 1.0 [aqueous phase] Potassium sulfate 2.5 Glycerin 10.0 Sorbitol 70% aqueous solution 15. 0 preservative 0.1 fragrance 0.1 water balance 100.0

Note 1) DC Q2-5200 (Toray Dow Corning Silicone Co., Ltd.) Note 2) Leopard KL (Chiba Flour Milling Co., Ltd.) Production method Heat-dissolved at 70 degrees into an oil phase that was heated and dissolved at 70 degrees. After adding the water phase and stirring, the mixture was cooled to room temperature and a fragrance was added to obtain a finished product.

[0096]

Table 15 Example 13 (Liquid emulsion foundation) (%) [Oil phase] Squalane 4.0 Phosphobetaine-modified silicone (Synthesis example 2) 5.0 Dioctanoic acid neopentyl glycol 3.0 Myristic acid isostearic acid diglyceride 2 .0 Lauryl methicone copolyol Note 1) 2.5 Dextrin stearate Note 2) 1.5 Octamethylcyclotetrasiloxane 12.0 Decamethylcyclopentasiloxane 3.0 α-monoisostearyl glyceryl ether 1.0 Aluminum mono Oleate 0.2 [Water phase] Magnesium sulfate 0.7 Glycerin 3.0 Preservative 0.1 Perfume 0.1 Water balance [Powder] Titanium oxide 5.0 Sericite 2.0 Talc 3.0 Bengal 0.1. 4 iron oxide yellow 0.7 iron oxide black 0.1 100 0 Note 1) DC Q2-5200 (Dow Corning Toray
Silicone Co., Ltd.) Note 2) Leopard KL (Chiba Flour Milling Co., Ltd.)

Example 14 A permanent waving agent having the composition shown in Table 16 was prepared,
Using this, hair was treated by the following treatment method and evaluated according to the following evaluation criteria. The results are shown in Table 16. Treatment method: The first agent (bath ratio 1: 1) was applied to tress (5 g of untreated Japanese hair), and left at room temperature for 10 minutes after application,
The second agent (bath ratio 1: 1) was applied and left again for 10 minutes at room temperature. After this, the tress is rinsed and the wet condition is evaluated. Next, after drying with a dryer, evaluation was performed.

Evaluation Criteria: The treated hair of Comparative Product 1 in the table was evaluated according to the following criteria. Good ◎, Fair ○, Equivalent △, Bad ×

[0099]

[Table 16]

Example 15 A hair dye having the composition shown in Table 17 was produced, and the hair was treated by the following treatment method and evaluated by the following evaluation criteria. The results are shown in the table.

Treatment method: Torres (5 g of untreated Japanese hair)
A mixture of the first agent and the second agent (bath ratio 1: 1) was applied to and was left for 20 minutes at room temperature. After this, the tress was rinsed and evaluated when wet. Next, after drying with a dryer, evaluation was performed.

Evaluation Criteria: The treated hair of Comparative Product 1 in the table was evaluated according to the following criteria. Good ◎, Fair ○, Equivalent △, Bad ×

[0103]

[Table 17]

Example 16 Hair conditioning mousse:

[0105]

[Table 18]

Example 17 Shampoo:

[0107]

[Table 19]

Example 18 Hair Treatment:

[0109]

[Table 20]

Claims (1)

[Claims] 1. A cosmetic comprising a phosphoric acid ester having an organosiloxane group represented by the following general formula (1). [Chemical 1]