JPH08319221A - Shampoo composition - Google Patents

Abstract

PURPOSE: To obtain a stable shampoo composition retaining its foamability, sufficient in conditioning effect, and capable of imparting the hair with luster after treated therewith. CONSTITUTION: This shampoo composition comprises (A) an aqueous silicone emulsion containing an organopolysiloxane 3000000-30000000cp in viscosity at 25 deg.C made up of respective constitutive units of the general formulas R<1> 2 SiO2/2 and R<2> SiO3/2 (R<1> and R<2> are each a 1-20C monovalent hydrocarbon group) and (B) a silicone emulsion containing another organopolysiloxane 1-10000cp in viscosity at 25 deg.C made up of respective constitutive units of the general formulas R<3> 2 SiO2/2 and R<4> SiO1/2 (R<3> and R<4> are each a 1-20C monovalent hydrocarbon group).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to shampoo compositions.

[0002]

BACKGROUND OF THE INVENTION Known shampoo compositions include detergent compositions containing fatty acid soaps, alkylbenzene sulfonates, alkyl sulphates, alkyl ether sulphates, monoglycerin sulphates, alkyl phosphates, methyl taurides and fatty acid alkanolamides. However, when washing hair with this type of shampoo composition, natural oil is removed along with dirt and unnecessary oil, so frequent oil washing removes natural oil excessively, so hair It became difficult to rinse and put together hair, and there were some inconveniences such as hair becoming dry due to increased static electricity.

[0003]

Therefore, as a countermeasure, a method of recovering such a hair condition by adding a cationic conditioning agent has been proposed, but a preparation to which the cationic conditioning agent is added is Although it is effective in conditioning, it has the drawback of leaving a substance on the hair that causes the hair to lose its luster after drying. In addition, it has been proposed to add a non-volatile silicone oil for conditioning the hair, which has a viscosity of 5 to 60 at 25 ° C, for example.
A method has also been proposed in which a non-volatile silicone oil of 0,000 cSt is added to a shampoo composition and the composition is sheared with a high shear mixer until the average particle size becomes 10 μm or less (see JP-A-61-210022). ), The particle size is not stable by this method, and the defoaming effect may be brought about.

In addition, regarding this, a shampoo composition prepared by adding a non-volatile silicone oil to an aqueous medium containing various synthetic surfactants, or an aqueous medium containing a synthetic anionic surfactant and another quaternary ammonium conditioning agent. It has been proposed to add a non-volatile silicone oil therein (see Japanese Patent Publication No. 4-2566, 2567, 38723), and a secondary amide amino acid or an alkyl saccharide-based surfactant is used as a surfactant. However, it has been proposed to add and blend a non-volatile silicone oil thereto (JP-A-2-247113, JP-A-4-327520, JP-A-4-364).
No. 113), which partially uses an emulsion of amino-modified silicone oil, but most of them use non-volatile silicone oil or non-volatile silicone solution in the shampoo composition. These are added and compounded together with other components, and these have problems in dispersibility of silicone, and there are many problems such as separation of silicone and impairing foamability of shampoo.

Therefore, it has been proposed to add silicone to the shampoo composition in the form of an emulsion (see JP-A-4-36226, JP-A-4-224309, and JP-A-5-39212). ), And addition of silicone microemulsion has also been proposed (JP-A-63-1305).
12, JP-A-5-13994, JP-A-5-163122). According to these, the foaming property of the shampoo composition is not impaired and the stability is improved, but the conditioning effect is not sufficient. In order to improve the conditioning effect, it has been proposed to add a hard silicone polymer having a viscosity of 2 × 10 ⁵ poise or more, and it has been suggested to add an aqueous emulsion capable of forming a silicone elastomer. The stability was poor such that the silica and the catalyst had to be used in combination.

[0006]

The inventors of the present invention have conducted extensive studies to solve the problems of the prior art and completed the present invention. That is, the present invention provides (A) the general formulas R ¹ ₂ SiO _2/2 and R ²
SiO _3/2 (wherein R ¹ and R ² are monovalent hydrocarbon groups having 1 to 20 carbon atoms) as a constitutional unit and has a viscosity at 25 ° C. of 3,000,000 to 3,0
Aqueous silicone emulsions containing, 000,000 cp organopolysiloxane and (B) general formulas R ³ ₂ SiO _2/2 and R ⁴ ₃ SiO _1/2
(Wherein R ³ and R ⁴ are monovalent hydrocarbon groups having 1 to 20 carbon atoms) as a constituent unit, and comprising a silicone emulsion containing an organopolysiloxane having a viscosity at 25 ° C. of 1 to 10,000 cp, (A) Organopolysiloxane] / [(B) Organopolysiloxane] = 1/99 to 99/1 (weight ratio)
And the total content of the organopolysiloxane (A) and the organopolysiloxane (B) is 0.1 to 10% by weight.
Is a shampoo composition. The present invention will be described in detail below.

R ¹ and R ² are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl. An alkyl group such as a group; an alkenyl group such as a vinyl group or an allyl group;
Aryl groups such as phenyl group, tolyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cyclooctyl group; or some or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms, epoxy groups, carboxyl groups Examples thereof include monovalent hydrocarbon groups substituted with organic groups containing groups, amino groups, and the like. Of these, a methyl group and a phenyl group are particularly preferable.

(A) of the shampoo compositions of the present invention
The components are preferably produced by emulsion polymerization in water. That is, the compounds of the following formulas (Chemical formula 1) and (a) to (b) are used as the silicone raw material of R ¹ ₂ SiO _2/2 units, and R ² SiO _3/2
As the silicone raw material for the unit, a compound of the following formula (c) or a hydrolyzate thereof may be used.

[0009]

Embedded image ^{(A) ··· HO- (R 1} 2 SiO) b H (b = 1 ~1,000), (b) ··· R 5 O - (R 1 2 SiO) c R 5 (c = 1 ~1,000, R ⁵ is a monovalent hydrocarbon group having 1 to 6 carbon atoms), (c) ... R ² Si (OR ⁶ ) ₃ (R ⁶ is a hydrogen atom or carbon number
1 to 6 monovalent hydrocarbon groups).

This emulsion polymerization is carried out by a conventionally known method, that is, the above raw materials are emulsified and dispersed in water using an emulsifier, and then a catalyst is added to the mixture to carry out a polymerization reaction, and the catalyst is deactivated after the completion of the polymerization. Good. The emulsifier used in this emulsion polymerization is not particularly limited, and examples thereof include cationic emulsifiers such as quaternary ammonium salts and alkylamine salts; zwitterionic emulsifiers such as alkyl betaines; polyoxyethylene alkyl ethers, poly Nonionic emulsifiers such as oxyethylene alkyl phenyl ether, sorbitan fatty acid ester and glycerin fatty acid ester; acidic anion emulsifiers such as organic sulfonic acid, higher alcohol sulfuric acid ester, higher alkyl ether sulfuric acid ester, and the like. One or two or more of these can be used.

When a cationic emulsifier, a zwitterionic emulsifier, or a nonionic emulsifier is used as the catalyst, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, ammonia, tetrahydrochloride is used. Examples thereof include alkali compounds such as methylammonium hydroxide, triethylamine and triethanolamine, but acidic anionic emulsifiers such as organic sulfonic acids, higher alcohol sulfates and higher alkyl ether sulfates have a catalytic action as they are. For the deactivation of this catalyst, in the case of an alkaline compound, a method of neutralizing with an acid such as acetic acid, phosphoric acid, hydrochloric acid or citric acid can be mentioned. When an acidic anionic emulsifier is used as a catalyst, it is neutralized with an alkaline compound such as potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, ammonia, tetramethylammonium hydroxide, triethylamine, triethanolamine. There is a method of doing.

If the concentration of the organopolysiloxane in the component (A) produced in this way is less than 1% by weight, the amount of the compound must be increased, and the capacity of the production apparatus becomes large. Therefore, it becomes uneconomical, and if it exceeds 70% by weight, the viscosity of the component (A) becomes high and it becomes difficult to handle. Therefore, the range is 1 to 70% by weight, preferably 10 to 60% by weight. is there. The viscosity of the organopolysiloxane contained in the aqueous emulsion obtained by this emulsion polymerization must be 3 to 30 million cp at 25 ° C. If the viscosity is less than 3 million cp, the shampoo composition finally obtained will have insufficient conditionability of the hair after washing, and 3,000
If it exceeds 10,000 cp, the hair after washing will have poor gloss. More preferably, it is 5 to 20 million cp. In order to obtain an organopolysiloxane having this preferable viscosity, R ¹ ₂ SiO _2/2 / R ² SiO _3/2 (molar ratio) is 100/1 to 2,000.
It is necessary to mix the raw material organopolysiloxane so that it becomes 0/1. This is 3 million if it exceeds 2,000 / 1
It is difficult to obtain a viscosity of cp or more, and if it is less than 100/1, the finally obtained film has a large stickiness. It is more preferably 500/1 to 1,000 / 1.

[0013] This constitutes the silicone emulsion composition (B) component has the general formula R ³ ₂ SiO _2/2 and R ⁴ ₃ viscosity at 25 ° C. to the SiO _1/2 structural units 1 A silicone emulsion containing 10,000 cp of organopolysiloxane. R ³ and R ⁴ are selected from the same monovalent hydrocarbon groups as R ¹ and R ² described above. Of these, a methyl group and a phenyl group are particularly preferable. The component (B) is produced by emulsion polymerization in water, similar to the component (A). That is, as the silicone raw material of R ³ ₂ SiO _2/2 unit, compounds of the following formulas (Formula 2) and (d) to (e) are used, and R ⁴ ₃
As the silicone raw material of SiO _1/2 unit, the following formula (f)
The compound (g) may be used. As this emulsion polymerization method, the same method as in the case of producing the component (A) may be used. Further, the silicone emulsion of component (B) is
Viscosity at 25 ° C represented by the following formula (h) is 1 to 10,000 cp
It can also be obtained by emulsifying the above organopolysiloxane with a nonionic emulsifier, an anionic emulsifier, a cationic emulsifier, a zwitterionic emulsifier and the like.

[0014]

Embedded image

[0015] ^{(d) ··· HO- (R 3} 2 SiO) e H (e = 1 ~1,00
0), (e) ... R ⁷ O — (R ³ ₂ SiO) _f R ⁷ (f = 1 to 1,000, R ⁷ is a monovalent hydrocarbon group having 1 to 6 carbon atoms), (f) ...・ R ⁴ ₃ SiO- (R ³ ₂ SiO) _g SiR ⁴ ₃ (g = 0 to 100), (g) ... R ⁴ ₃ SiOR ⁸ (R ⁸ is hydrogen atom or carbon number 1
Monovalent hydrocarbon radical of ^{~6) (h) ··· R 4} 3 SiO- (R 3 2 SiO) h SiR 4 3 (h = 1~1000).

Examples of the nonionic emulsifier include polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, sorbitan monoalkylate, sorbitan trichelate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitanial chelate and polyoxy. Examples thereof include ethylene sorbitan tetraalkylate and glycerol monoalkylate, which can be used alone or in combination of two or more kinds. In addition to these general nonionic emulsifiers, fluorine-based compounds are used for this purpose. Although an emulsifier or a silicone-based nonionic emulsifier can also be used,
The nonionic emulsifier has an HLB in the range of 1.5 to 20, preferably 7.0 to 19.0.

The ionic emulsifier is anionic,
There are cationic and zwitterionic agents, and as the anionic emulsifier, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, potassium alkyl phosphate, polyoxyethylene lauryl ether sulfate are available. Sodium, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc., as the cationic emulsifier, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyl amine hydrochloride, coconut amine Hydrochloride, coconut amine acetate, stearyl amine acetate, alkyl Such emission Zen dimethyl ammonium chloride are exemplified. As the zwitterionic emulsifier, N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-
Examples include N, N'-dimethyl-N'-β-hydroxypropylammoniobetaine.

This emulsification operation may be carried out using a conventionally known emulsifying machine. For example, a homomixer, a high pressure homogenizer, a colloid mill, an ajihomomixer and the like can be mentioned. The organopolysiloxane used as the component (B) is
If the viscosity at 25 ° C is less than 1 cp or more than 10,000 cp, the washed hair does not have suppleness and has poor gloss, and therefore it is necessary to be 1 cp to 10,000 cp. More preferably, it is 10 to 1,000 cp. When the concentration of the organopolysiloxane in the component (B) produced as described above is less than 1% by weight, the amount of the component (B) must be increased, which increases the capacity of the production apparatus. Therefore, it becomes uneconomical, and when it exceeds 70% by weight, the viscosity of the component (B) becomes high and handling becomes difficult. Therefore, it is necessary to set the range of 1 to 70% by weight, more preferably 10 to 70% by weight. 60% by weight.

The components (A) and (B) are [(A)
[Organopolysiloxane] / [(B) organopolysiloxane] is added to the shampoo composition in a weight ratio of 1/99 to 99/1. If the weight ratio is less than 1/99, the combability and suppleness of the hair after washing the hair will be poor, and if it exceeds 99/1, the combability of the hair will be insufficient and the gloss will be poor. . More preferably 10/90 to 90
It is / 10. If the total amount of the components (A) and (B) is less than 0.1% by weight with respect to the shampoo composition, the conditioning property of the hair is not sufficient, and if it exceeds 10% by weight, the foaming property at the time of washing hair is obtained. 0.1 to 10% by weight is necessary because it hinders detergency, and more preferably 1 to 5%.
% By weight. The shampoo composition of the present invention can be obtained by adding and mixing the above-mentioned components (A) and (B) in the above-described amounts to the detersive composition.

As the detersive composition used here, a conventionally known composition can be used. That is, fatty acid soap, alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, monoglyceride sulfate, alkyl phosphate, methyl tauride, fatty acid alkanolamide and the like can be mentioned. Since it is used for human and animal hair shampoos, it is preferably alcohols derived from fats or alcohol ethoxylates derived from fats, especially those derived from lauryl and myristyl alcohol and salts thereof, for example lauryl sulphate. Aqueous solutions containing sodium, sodium lauryl ether sulphate, ammonium lauryl sulphate, triethanolamine lauryl sulphate, monoethanolamine lauryl sulphate, disodium lauryl ethoxy sulfosuccinate and sodium coco monoethanol amide ethoxy sulphosuccinate are suitable.

The components (A), (B) and the detersive composition can be mixed using a conventionally known mixing stirrer such as a paddle type or anchor type stirring blade, or a homomixer or an ajihomomixer. It can be easily carried out by using an emulsifying machine such as, but (A) component and (B) component are mixed in advance,
After that, the detersive composition may be added and mixed.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following, the viscosity indicates the value at 25 ° C.

[Preparation Example 1: Preparation of component (A) -1] 350 g of octamethylcyclotetrasiloxane and 1.3 g of phenyltriethoxysilane were placed in a 1 liter glass beaker and mixed with stirring with a homomixer at 2,000 rpm. ,
10% by weight 35 g of sodium lauryl sulfate aqueous solution and 10% by weight
Dodecylbenzene sulfonic acid aqueous solution 35g added 6,000
When stirring was continued at rpm, phase inversion occurred and thickening was observed, but water was added while stirring at 2,000 rpm.
280 g was added and then passed through a 300 kg / cm ² high pressure homogenizer to obtain an aqueous emulsion. Next, the aqueous emulsion was transferred to a glass reactor having a capacity of 1 liter equipped with an anchor type stirring blade, a thermometer and a reflux condenser, reacted at 50 ° C for 12 hours, and then allowed to stand at 25 ° C for 24 hours. After allowing to stand, it was neutralized with a 10 wt% sodium carbonate aqueous solution to obtain a desired aqueous emulsion [(A) component-1]. Isopropyl alcohol was added to this to destroy the emulsion, and then the organopolysiloxane was taken out and dried to obtain a Rheopex Analyzer R.
When viscosity was measured with PX-705 (Iwamoto Seisakusho)
It was 12 million cp.

[Preparation Example 2: Preparation of component (A) -2] The target aqueous milk was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 1.1 g of methyltrimethoxysilane. A suspension was obtained [Component (A)-
2]. Isopropyl alcohol was added to this to destroy the emulsion, and the organopolysiloxane was taken out and dried to obtain Rheopex Analyzer RPX-705 (described above).
The viscosity was measured by and was 19 million cp.

[Preparation Example 3: Preparation of component (A) -3] The intended aqueous emulsion was obtained in the same manner as in Preparation Example 1, except that phenyltriethoxysilane was not added. [(A) component-3]. After adding isopropyl alcohol to the emulsion to destroy the emulsion, the organopolysiloxane was taken out, dried, and the viscosity was measured by Rheopex Analyzer RPX-705 (described above).
It was, 000,000 cp.

[Preparation Example 4: Preparation of component (A) -4] The target aqueous milk was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 6.8 g of methyltrimethoxysilane. A suspension was obtained [Component (A)-
4]. After adding isopropyl alcohol to the emulsion to destroy the emulsion, the organopolysiloxane was taken out and dried to obtain Rheopex Analyzer RPX-705 (described above).
The viscosity was measured by and was 36 million cp.

[Preparation Example 5: Preparation of component (B) -1] In the same manner as in Preparation Example 1 except that 1.3 g of phenyltriethoxysilane was changed to 5.0 g of hexamethyldisiloxane, the desired aqueous milk was prepared. A suspension was obtained [Component (B)-
1]. After isopropyl alcohol was added to this to destroy the emulsion, the organopolysiloxane was taken out, dried, and the viscosity was measured with an EM type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) to find that it was 320 cp.

[Preparation Example 6: Preparation of component (B) -2] 40 g of polyoxyethylene nonylphenyl ether (HLB13) and polyoxyethylene octylphenyl were added to 300 g of organopolysiloxane represented by the following formula (i) and having a viscosity of 50 cp. Mix 3 g of a 30% by weight aqueous solution of sodium ether sulphate, add 100 g of water, and add 6,000 r with a homomixer.
When stirring was performed at pm, phase inversion occurred and thickening was recognized, but stirring was continued for 20 minutes to homogenize. Then, the homomixer was rotated at 2,000 rpm and 557 g of water was added and mixed while stirring. Furthermore 300kg of this
The mixture was passed through a high-pressure homogenizer of / cm ² to obtain the desired aqueous emulsion [(B) component-2]. _{(I) ··· (CH 3)} 3 SiO - [(CH 3) 2 SiO] 42 -Si (CH 3) 3

[Preparation Example 7: Preparation of component (B) -3] 60 g of polyoxyethylene lauryl ether (HLB = 14) and 1 g of 20% by weight aqueous solution of sodium polyoxyethylene lauryl ether sulfate (EO added mole number = 3) Was added to 539 g of water and dissolved with stirring. Then 6,000 rpm with a homomixer
The viscosity represented by the following formula (j) while stirring with
Emulsification was carried out by adding 400 g of 0.8 cp of organopolysiloxane. Further, this was passed through a high-pressure homogenizer of 300 kg / cm ² to obtain an intended aqueous emulsion [(B) component-3]. _{(J) ··· (CH 3)} 3 SiO (CH 3) 2 SiOSi (CH 3) 3

[Preparation Example 8: Preparation of component (B) -4] The desired aqueous milk was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 0.8 g of hexamethyldisiloxane. A suspension was obtained [Component (B)-
4]. After isopropyl alcohol was added to this to destroy the emulsion, the organopolysiloxane was taken out, dried, and the viscosity was measured with an EM type rotational viscometer (described above), and it was 15,000 cp. The components (A) and (B) obtained in the above Preparation Examples 1 to 8 are shown in (Table 1).

[0031]

[Table 1]

[Examples 1 to 6] and [Comparative Examples 1 to 8] A shampoo base having the following composition was prepared and used (Table 1).
Each of the organopolysiloxane emulsions shown in (A)
The components and the component (B) were added in the amounts shown in (Table 2) and mixed and dispersed by a propeller-type stirring device to prepare the shampoo composition shown in (Table 2). The numbers in this composition represent% by weight. [Shampoo base composition] Polyoxyethylene (EO addition mole number = 3) Sodium lauryl sulfate 16% by weight Lauryl sulfate diethanolamide 4% by weight Propylene glycol 2% by weight Preservatives, colorants, perfumes Appropriate amount Distilled water Remainder total 100% by weight %

The foaming properties of these shampoo compositions were confirmed by the method described below, and then the finish properties of the hair after actual hair washing were confirmed visually and by touch. The results of these evaluations are shown in (Table 2). [Method of confirming foamability] Into a 1 liter beaker, put 500 ml of a 1% by weight aqueous solution of each shampoo composition prepared,
2.5g of lanolin as an artificial stain was added to this, heated to 40 ° C, and then inverted by stirring at 1,000 rpm for 10 minutes every 5 minutes by a stirrer with a flat stirring blade. After the stirring, 1 liter graduated cylinder was used. And the foam volume after standing for 30 seconds was measured. [Criteria for Finishing Evaluation] Gloss: Sufficiently ... ○, Insufficient ... △, None ... ×, Smoothness: Sufficiently ... ○, Insufficient ... △, None ・・ ・ ×, Suppleness: Sufficiently present ... ○, Inadequate ... △, None ... ×

[0034]

[Table 2]

[0035]

EFFECTS OF THE INVENTION The shampoo composition of the present invention, when used for washing hair, does not impair foamability and is stable,
In addition, it also shows a sufficient conditioning effect.

Claims (1)

[Claims] 1. A constitutional unit comprising (A) the general formulas R ¹ ₂ SiO _2/2 and R ² SiO _3/2 (wherein R ¹ and R ² are monovalent hydrocarbon groups having 1 to 20 carbon atoms). An aqueous silicone emulsion containing an organopolysiloxane having a viscosity of 3,000,000 to 30,000,000 cp at 25 ° C and (B) a general formula R ³ ₂ SiO _2/2 and R ⁴ ₃ SiO _1/2 (where R ³ and R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms) as a constitutional unit and comprises a silicone emulsion containing an organopolysiloxane having a viscosity at 25 ° C. of 1 to 10,000 cp. Siloxane] / [(B) organopolysiloxane] = 1/99 to 99/1 (weight ratio)
And the total content of the organopolysiloxane (A) and the organopolysiloxane (B) is 0.1 to 10% by weight.
A shampoo composition.