JPH06211634A - O/w-type emulsified composition for hair - Google Patents

Abstract

PURPOSE:To obtain an O/W-type emulsified composition for hair, easily and smoothly spreadable with palm, giving excellent gloss and softness to the hair and having excellent long-term stability. CONSTITUTION:This O/W-type emulsified composition for hair is composed of a silicone compound having high molecular weight, a dissolution agent for the high-molecular weight silicone compound, a nonionic surfactant having an HLB of 1-12, a t-amine oxide surfactant and a water-swelling clay mineral.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-in-oil type emulsion composition for hair. More specifically, it relates to a water-in-oil type emulsion composition of a polymeric silicone excellent in long-term stability.

[0002]

2. Description of the Related Art Emulsion compositions for hair using a high molecular silicone compound are easy to spread on the palm, light, and
It imparts excellent luster and supple feel to the hair (JP-A-63-37154, JP-A-1-252664).
Issue). However, this is an oil-in-water emulsion, and the water resistance is poor, so the effect does not last. A method of stabilizing a water-in-oil emulsion that is generally unstable with a water-swelling clay mineral in order to have excellent water resistance and long-lasting effect (JP-A-3-157317), or a solution-type emulsion Thing (JP-A-3
No. 209345) is proposed.

[0003]

However, although the conventional water-in-oil emulsions have been improved in stability, they are not satisfactory in long-term stability. Also, the conventional solution type causes squeaky hair,
It lacked flexibility. Therefore, today, there is a strong demand for the appearance of a water-in-oil type emulsion composition for hair, which is as good in use as the conventional one and is stable for a long period of time.

[0004]

In view of such circumstances, the inventors of the present invention have been able to extend the ability to extend in the palm of the hand, provide lightness, impart excellent luster and supple feel to the hair, and keep it for a long period of time. As a result of intensive studies to obtain a water-in-oil type emulsion composition for hair having excellent stability, the addition of a small amount of a tertiary amine oxide type surfactant and a water-swelling clay mineral resulted in a feeling of use and long-term stability. The inventors have found that the properties are dramatically improved and have reached the present invention. That is, the present invention provides a high molecular weight silicone compound (A), a high molecular weight silicone compound dissolving agent (B), a nonionic surfactant (C) having an HLB of 1 to 12, and a tertiary amine oxide type surfactant (D). ) And a water-swellable clay mineral (E), a water-in-oil emulsion composition for hair.

The high molecular weight silicone compound (A) used in the present invention has a weight average molecular weight of usually 50.
The compound having a polysiloxane bond as the main chain is used. For example, it is represented by the following general formula (1), and is a substance that exhibits flexible elasticity at room temperature.

[0006]

[Chemical 1]

(In the formula, R ₁ is a methyl group or a hydroxyl group, and R _{2 is}
Is a methyl group or a phenyl group, a is 2,000 to 50,
It is an integer of 000. R ₁ and R ₂ may be the same or different. )

Specific examples of the high molecular weight silicone compound (A) include dimethylpolysiloxane (weight average molecular weight 1
200,000), methyl-phenyl polysiloxane (weight average molecular weight 1.83 million), terminal silanol dimethyl polysiloxane (weight average molecular weight 1 million), terminal silanol diphenyl polysiloxane (weight average molecular weight 1.9 million) and terminal silanol methyl phenyl polysiloxane ( The weight average molecular weight is 1,000,000). Above, (A)
Those exemplified above may be used in combination of two or more kinds.

In the present invention, examples of the solubilizer (B) include those capable of uniformly dissolving the high molecular weight silicone compound (A), such as isoparaffin hydrocarbons, low molecular weight silicone compounds and branched ester compounds.

Examples of the isoparaffinic hydrocarbon include isoparaffinic hydrocarbons having a boiling point of 60 to 260 ° C. at room temperature, and examples thereof include Isopar (manufactured by Exxon), Sherbizol (manufactured by Shell) and Isosol [Nippon Petroleum ( Co., Ltd.].

As the low molecular weight silicone compound, a compound having a weight average molecular weight of 134 to 30,000 and having a polysiloxane bond as a main chain can be used. For example, the low molecular weight chain dimethyl polysiloxane represented by the general formula (2) and the low molecular weight cyclic dimethyl polysiloxane represented by the general formula (3) can be mentioned.

[0012]

[Chemical 2]

[0013]

[Chemical 3]

In the general formula (2), R ₃ is a methyl group or a hydroxyl group, R ₄ is a methyl group or a phenyl group, and b is 0-40.
Represents an integer of 0. Moreover, in general formula (3), c represents the integer of 3-7.

Specific examples of the low molecular weight chain dimethylpolysiloxane include dimethylpolysiloxane (weight average molecular weight 1,000), dimethylpolysiloxane (weight average molecular weight 5,000), methyl-phenylpolysiloxane (weight average molecular weight 1). , 1,000), methyl-phenyl polysiloxane (weight average molecular weight 1,500), terminal silanol dimethyl polysiloxane (weight average molecular weight 2,000)
0), terminal silanol diphenyl polysiloxane (weight average molecular weight 10,000) and terminal silanol methylphenyl polysiloxane (weight average molecular weight 5,000)
And so on.

Specific examples of the low molecular weight cyclic dimethylpolysiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

Examples of the branched ester compound include mono- or polyvalent esters each having a branched hydrocarbon group and / or alcohol component and having a hydrocarbon group having 3 to 18 carbon atoms. Of these, branched monoesters are preferred.

Examples of branched monoesters include branched monoesters of a branched carboxylic acid and a linear alcohol, branched monoesters of a linear carboxylic acid and a branched alcohol, and branched monoesters of a branched carboxylic acid and a branched alcohol.

Among these branched monoesters, branched monoesters of a branched carboxylic acid and a branched alcohol are preferable, and examples thereof include isopropyl isostearate, isobutyl isostearate, isopentyl isostearate,
Isoheptyl isostearate, isononyl isostearate, isocetyl isostearate, isostearyl isostearate, isohexyl isopalmitate, isooctyl isopalmitate, isodecyl isopalmitate, isopropyl isononanoate, isononyl isononanoate, isononanoate isodecyl, isononanoate isotridecyl, isononanoate. Examples thereof include isostearyl, isopropyl isovalerate, isononyl isovalerate, isostearyl isovalerate, isobutyl isobutyrate, isodecyl isobutyrate, and isomyristyl isobutyrate.

Among the examples of the solubilizer (B), preferred are dimethylpolysiloxane compounds having a weight average molecular weight of 1,000 to 20,000, isononyl isononanoate, isooctyl isononanoate, isononyl isomyristate, and isononane. Isodecyl acid.
As mentioned above, two or more kinds may be used in combination as exemplified as (B).

In the present invention, the nonionic surfactant (C) having an HLB of 1 to 12 can be used. HL
Various methods for determining B are known, such as the Atras company method and Kawakami method, but they are listed in the Handbook of Surfactants (edited by Nishiichiro, Ichiro Imai, Masatake Kasai, published by Sangyo Tosho Co., Ltd.). It can be shown by the method of Davies described in 313.

Examples of (C) include glycerin fatty acid esters such as glyceryl monolaurate, glyceryl monostearate, glyceryl monooleate, polyglycerin fatty acid esters such as diglyceryl diisostearate, triglyceryl diisostearate, decaglyceryl decaoleate, and poly. Oxyethylene alkyl ethers such as polyoxyethylene (2 mol) oleyl ether, polyoxyethylene (2 mol) nonylphenyl ether, polyoxyethylene hydrogenated castor oil esters, such as polyoxyethylene (5 mol) hydrogenated castor oil, polyoxyethylene (7 mol) hydrogenated castor oil, sorbitan fatty acid ester such as sorbitan trioleate, sorbitan monooleate, sorbitan monolaurate, monostearin. Sorbitan, polyoxyalkylene-modified organopolysiloxanes, for example, the following general formula (4), the compound having the structure of (5) or (6)

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

(Wherein R ₅ is a methyl group or a phenyl group,
R ₆ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, e
Is an integer of 1 to 5, f is 2 or 3, d, g, and h are average numbers, d is an integer of 1 to 200, g is an integer of 1 to 35, and h is an integer of 1 to 50. A number in which the oxyalkylene-modified organopolysiloxane contains 5 to 40% by weight of a polyoxyalkylene group in the molecule, and the polyoxyalkylene-modified organopolysiloxane has a molecular weight of 2,000 or more. ) And so on. General formula (4), (5)
And compounds having the structures of (6) include SH377
5C [manufactured by Toray Dow Corning Silicone Co., Ltd.],
KF-945A (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

In the compounds having the structures of the general formulas (4), (5) and (6), when the content of the polyoxyalkylene group is 5% by weight or less, the compound is dissolved in the branched ester compound (B) to give the active agent. As a result, no sufficient effect can be obtained. 40
When the content is more than 5% by weight, the hydrophilicity increases and the desired water-in-oil emulsion cannot be obtained. If the molecular weight is 2,000 or less, the obtained emulsion is unstable, which is not preferable.

Of these (C), polyglycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyalkylene-modified organopolysiloxane are preferable in terms of usability and long-term stability of the resulting emulsion.
As described above, two or more kinds exemplified as (C) may be used in combination.

The tertiary amine oxide type surfactant (D) used in the present invention is produced by oxidizing a tertiary amine with hydrogen peroxide, benzoyl peroxide, peroxysulfuric acid or hypochlorite. There are, for example, trimethylamine oxide, lauryldimethylamine oxide, myristyldimethylamine oxide, palmityldimethylamine oxide, stearyldimethylamine oxide, or JP-A-63-45213.
Publication, JP-A-3-58911, Synthesis of Surfactant and Its Application (Ryohei Oda, Kazuhiro Teramura, published by Maki Shoten)
P. Examples thereof include those described in 136. These (D)
Of these, palmityldimethylamine oxide and stearyldimethylamine oxide are preferable. Those exemplified above as (D) may be used in combination of two or more kinds.

The water-swellable clay mineral (E) used in the present invention is a silicate mineral having a 2: 1 type structure (three-layer structure), such as montmorillonite, hydelite, nontronite, saponite and hectorite. There are, for example, commercially available products such as Kunipia (manufactured by Kunimine Industry), Smecton (manufactured by Kunimine Industry), Veegum (manufactured by Vanderbilt), Laponite (manufactured by Nihon Silica Kogyo), and tetrafluorosilica mica (manufactured by Topy Industries). is there. Among these (E), smecton and laponite are preferable. Two or more kinds of those exemplified above as (E) may be used in combination.

Various additives can be used in combination with the composition of the present invention. For the purpose of adjusting the feel as an additive,
Monohydric alcohols (ethanol, propanol, butanol, butanol, etc.) and polyhydric alcohols (ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, sorbit, sorbitan, etc.) can be used in combination. Preferred of these alcohols are
These are ethanol, propylene glycol, 1,3-butylene glycol and glycerin. The amount of the alcohol compounded is within the range of 50% by weight based on all the components of the composition of the present invention.

Similarly, an alkylene oxide adduct of alcohol can be used together for the purpose of adjusting the feel. The alkylene oxide adduct of alcohol is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the above-mentioned alcohol, for example, an adduct of ethylene oxide, an adduct of propylene oxide, an adduct of butylene oxide and a combination thereof. Can be given. When two or more kinds of alkylene oxides are used in combination, block or random addition may be used. Of these, preferred are ethylene oxide adducts and / or propylene oxide adducts. The number of moles of alkylene oxide added is usually 1 to 100 moles, preferably 2 to 50 moles. The content of the alkylene oxide adduct of alcohol is within the range of 20% by weight based on the total amount of all the components of the composition of the present invention.

As the luster-imparting agent, non-drying vegetable oils such as avocado oil, almond oil, olive oil, camellia oil, persic oil, castor oil and the like, and non-volatile liquid hydrocarbons such as liquid paraffin and squalane can be used in combination. The compounding amount is 20% by weight based on the total amount of the components of the composition of the present invention.
Within the range of.

Thickeners such as CMC and xanthan gum, and antioxidants such as 2,6-di-tert-butyl-p-cresol and 2,2-methylene-bis- (4-methyl-6-tert-butylphenol). ) And the like, benzophenone-3 or the like as an ultraviolet absorber, pantothenic acid, cholesterin or the like as a hair restorer, and l as a refreshing agent.
-Menthol and the like can be used in combination with preservatives such as methyl p-oxybenzoate. The blending amount is within the range of 5% by weight based on the total amount of all components.

The formulation of the water-in-oil type emulsion composition for hair of the present invention is shown in the following formula (A): 1 to 1 in general.
0 wt%, (B) 1-80 wt%, (C) 0.1-
10% by weight, 0.1 to 10% by weight of (D), 0.2 to 5% by weight of (E), and 10 to 80% by weight of water.

When the content of (A) is less than 1% by weight, the composition has poor gloss and suppleness of the hair, and when it exceeds 10% by weight, the feel is heavy, which is not preferable. If the content of (B) is less than 1% by weight, the composition has poor stability and
If it exceeds 0% by weight, a squeaky feeling is produced and the suppleness becomes poor. If the content of (C) is less than 0.1% by weight, the stability of the composition is poor, and if it exceeds 10% by weight, the feel of the composition becomes heavy, which is not preferable. (D) is 0.1
If it is less than wt%, the composition is not stable, and
If it exceeds 10% by weight, this composition is unlikely to be a water-in-oil emulsion. When (E) is less than 0.2% by weight, the composition has poor stability, and when it exceeds 5% by weight, the composition has high viscosity and lacks spreadability. If the amount of water is less than 10% by weight, the composition lacks spreadability, and if the amount of water exceeds 80% by weight, the hair using the composition has poor gloss lasting.

An example of the method for producing the composition of the present invention will be described. (A), (B), (C) and (D) are mixed and heated to 60 to 80 ° C. To this mixture, a mixture of water and (E) previously added is gradually added and emulsified. After emulsification, if necessary, additives and the like are mixed and cooled to room temperature to obtain the composition of the present invention.

[0038]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The test method is as follows.

Stability test 1 immediately after preparation at each temperature (0 ° C, room temperature, 45 ° C)
The appearance after 6 months was visually observed. Criteria Criteria Not separated: ○ Slightly separated: △ Completely separated: ×

Sensory evaluation Twenty panelists were asked to actually use it and a sensory test was performed on the palm (lightness of the spread) and on the hair (gloss and its durability, suppleness and its durability). It was Judgment Criteria Lightness is judged to be lightly spread by 15 or more panelists ◎ It is judged that 10 or more and less than 15 are lightly expanded ○ It is judged that 5 or more and less than 10 are lightly expanded △ It is judged that 4 or less are lightly expanded × Gloss and its durability 15 or more panelists judge that hair has gloss and its durability ◎ 10 or more and less than 15 people judge that hair has gloss and its durability ○ 5 or more and less than 10 hair It is judged that the hair has luster and its durability. △ 4 people or less judge that the hair has luster and its sustainability. × Suppleness and its durability. 15 or more panelists judge that the hair is supple and its durability is improved. 10 or more and less than 15 people judged that the suppleness and durability of the hair would be improved ○ 5 or more and less than 10 people judged that the suppleness and the durability of the hair would be improved △ 4 or less people had good suppleness of the hair and its durability × determined that that

Examples 1 to 3 and Comparative Examples 1 to 3 In the mixing ratios shown in Table 1, Examples 1 to 3 and Comparative Examples 1 to 1
A composition of 3 was obtained. The manufacturing method was as follows. Mixing (A-1) to (D-2) used in each example, 60 to 8
Heat to 0 ° C. To this mixture, a mixture of water and (E-1) or (E-2) was added gradually and emulsified.
After emulsification, mix well with pan, PG, GL and paraben,
It cooled to room temperature and obtained the target composition. Comparative Example 4 Comparative Example 4 was obtained with the mixing ratios shown in Table 1. This is a mixture of (A-1), (B-2), Noni 4, Noni 40 and water at room temperature, mixed and emulsified, and then blended with ET and paraben.

[0042]

[Table 1]

(A-1): Dimethyl polysiloxane (weight average molecular weight 1.2 million) (A-2): Dimethyl polysiloxane (weight average molecular weight 900,000) (B-1): Dimethyl polysiloxane (weight average molecular weight 1000) (B-2): decamethylcyclopentasiloxane (B-3): isononyl isononanoate (C-1): sorbitan trioleate (C-2): lipophilic glyceryl monostearate (D-1): stearyl Dimethylamine Oxide (D-2): Palmityl Dimethylamine Oxide (E-1): Smecton, Kunimine Industry (E-2): Laponite XLG, Nippon Silica Industry Noni 4: Polyoxyethylene (4 mol) Nonylphenyl Ether Noni 40: Polyoxyethylene (40 mol) nonylphenyl ether Pan: Liquid para Fin ET: Ethanol PG: Propylene glycol GL: Glycerin paraben: Methyl p-oxybenzoate

The compositions of the present invention (Examples 1 to 3) and comparative products (Comparative Examples 1 to 4) were evaluated for performance, and the results are shown in Table 2.

[0045]

[Table 2]

As shown in Table 2, the compositions of the present invention (Examples 1 to 3) were very excellent in long-term stability and sensory evaluation as compared with the comparative products (Comparative Examples 1 to 4).

[0047]

The water-in-oil type emulsion composition for hair of the present invention is
It spreads easily in the palm of the hand, is light, gives a glossy and supple feel to the hair, and has excellent long-term stability.

Claims (2)

[Claims] 1. A high molecular weight silicone compound (A), a high molecular weight silicone compound dissolving agent (B), and HLB of 1 to 1.
A water-in-oil type emulsion composition for hair, which comprises the nonionic surfactant (C) of item 2, the tertiary amine oxide type surfactant (D), and the water-swelling clay mineral (E). 2. A water-in-oil type emulsion composition for hair, wherein (A) is 1 to 10% by weight, and (B) is 1 to 80% by weight,
2. The composition according to claim 1, wherein (C) is 0.1 to 10% by weight, (D) is 0.1 to 10% by weight, (E) is 0.2 to 5% by weight, and water is 10 to 80% by weight. Composition.