KR100275645B1 - Oil-in-water silicone emulsion composition - Google Patents

Abstract

The present invention provides a novel oil-in-water type silicone emulsion composition suitable for use in cosmetics and the like, which has excellent usability and good long-term shelf life.

The oil-in-water silicone emulsion composition of the present invention,

(1) organopolysiloxane represented by the general formula R ₃ Si (OSiR ₂ ) _n OSiR ₃ (wherein R is a monovalent hydrocarbon group having 1 to 6 carbon atoms and n is a number of 500 to 10,000 as an average value),

(2) an organopolysiloxane having a viscosity at 25 ° C. of 1 to 500 centistokes,

(3) polyoxyalkylene modified organopolysiloxanes having an HLB value of 5 to 12; and

(4) ionic surfactants

Basically, the ratio of [(1) component + (2) component] / [(3) component + (4) component] by weight ratio is in the range of 95/5-50/50, and (4) component It is characterized by emulsifying in water so as to contain 0.5 to 20% by weight in [(3) component + (4) component].

Description

Oil-in-Water Silicone Emulsion Composition

The present invention relates to an oil-in-water type silicone emulsified composition which has good usability, excellent emulsification stability, and can be suitably used as a base for hair cosmetics such as shampoos and rinses, skin cosmetics such as creams and emulsions, and ointments such as ointments. will be.

In conventional skin or hair cosmetics, silicone oil or silicone resin is used for the purpose of smoothing or glossing hair (Japanese Patent Laid-Open Nos. 61-161, 209, 61-161211, and 61-161214, 63-246, 309, 63-246310, 63-183,515, 63-183,516, 63-183,517, 63-243,018, 63-243,019, 63-246,309, 63-246,310, 63-313,712, 63-316,713, 63-316,718, 64-75,416, Japan Korean Patent Publication Nos. 1-203,314, 1-211,515, 1-211,517 and 1-211,518.

However, skin or hair cosmetics incorporating silicone oil or silicone resin have a drawback in that adhesion to the skin or hair is insufficient or stickiness is inferior in usability.

In addition, these cosmetic silicone oils or silicone resins are usually emulsified and dispersed in water by using a hydrocarbon-based surfactant, but there is a disadvantage in that stable emulsion particles cannot be obtained without using an emulsifying and dispersing device having a high shear force.

Therefore, there has been a demand for the development of an emulsion composition for providing silicone emulsion particles having excellent usability and storage stability and an underwater swimming silicone emulsion composition using the same.

The present invention has been made to meet the above-described requirements, and an object thereof is to provide an oil-in-water type silicone emulsion composition composed of emulsion particles having excellent usability, small particle alignment, and stable after long-term storage.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result, (1) the organopolysiloxane of heavy weight represented by following General formula (1), and (2) the viscosity in 25 degreeC is 1- A medium to low molecular organopolysiloxane of 500 cs (centistokes), (3) a polyoxyalkylene-modified organopolysiloxane having an HLB value of 5 to 12 as a silicone-based surfactant, and (4) an ionic surfactant The ratio of [(1) component + (2) component] / [(3) component + (4) component] in weight ratio is in the range of 95/5 to 50/50, and (4) component is [(3) component + ( (4) emulsified in water so as to contain 0.5 to 20% by weight of the component], it has excellent adhesion to skin and hair, and has excellent usability, non-stickiness, and low irritation, and high safety. High emulsifying and dispersing device as in the case of blending hydrocarbon type surfactant The present invention has been completed by discovering that emulsion particles having a small particle diameter can be uniformly dispersed without using C, thereby obtaining an oil-in-water type silicone emulsion composition having excellent storage safety.

In said formula, R is a C1-C6 monovalent hydrocarbon group, n is an average value of 500-10,000.

Hereinafter, the present invention will be described in more detail.

The 1st essential component of the oil-in-water type silicone emulsion composition of this invention is organopolysiloxane of the high polymerization degree represented with the following general formula (I).

In said formula, R is a C1-C6 monovalent hydrocarbon group and n is a number of 500-10,000 as average value.

Herein, R in the formula includes a monovalent hydrocarbon group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and the like. It is preferable that it is 90 mol% or more in it.

In addition, n is an average polymerization degree of 500-10,000, Preferably it is the number of 1,000-7,000, When smaller than 500, the adhesiveness of the obtained film may deteriorate, and larger than 10,000 may be difficult to manufacture industrially.

It is preferable that the compounding quantity of the said organopolysiloxane shall be 0.1-20% (same weight or less) of the whole composition, and it is especially preferable to set it as 5-15%. If the blending amount is less than 0.1%, the resulting film may have low adhesiveness, and the killing resistance may be insufficient. If the blending amount is more than 20%, the extension to the skin is low, and the dryness may be low. The coated film may be very sticky.

Next, the second essential component is a medium to low molecular organopolysiloxane having a viscosity of 1 to 500 cs at 25 ° C.

Among these, the low molecular organopolysiloxane may be cyclic, branched or straight chain, and as the cyclic organopolysiloxane, one represented by the following general formula (II) is preferably used.

In said formula, R is a C1-C6 monovalent hydrocarbon group as above-mentioned, p is a number of 3-6.

In addition, what is represented by following General formula (III) as a linear organopolysiloxane is used preferably.

In said formula, R is a C1-C6 monovalent hydrocarbon group as above-mentioned, q is a number of 1-250.

In addition, as the branched organopolysiloxane, those consisting essentially of R ₃ SiO _1/2 million and RSiO _3/2 units and R ₂ SiO units are suitably used. Here, R is a C1-C6 hydrocarbon group as mentioned above.

The organopolysiloxane has a viscosity of 1 to 500 cs at 25 ° C., but is preferably 2 to 400 cs. If it is less than 1 cs, the solubility of a 1st component will worsen, and if it exceeds 500 cs, a film-forming ability will fall.

The said organopolysiloxane as a 2nd component may be used individually by 1 type, and may use two or more types together. Moreover, it is preferable that the compounding quantity of this 2nd component is 5 to 70%, especially 20 to 50% of the whole composition, and when the compounding quantity is less than 5%, the solubility and emulsification property of a 1st component may worsen, and 70% If it exceeds, the film forming ability of a composition may fall.

In this invention, although polyoxyalkylene modified organopolysiloxane is mix | blended as a 3rd essential component, the HIB value is 5-12, Preferably it is 6-9. If the HLB value is less than 5 or greater than 12, the stability of the obtained emulsion composition is inferior.

Here, HLB value is the value computed from the following formula.

(CH ₂ CH ₂ 0% by weight of the group occupying in the molecule) / 5 = HLB value

As such polyoxyalkylene modified organopolysiloxane, what is represented by the following general formula (IV) is used suitably.

Wherein G is a formula-(CH ₂ ) _t -O- (R ¹ O) _u -Q (wherein R ¹ is a group selected from at least one of an ethylene group or a proylene group, and D is a hydrogen atom or carbon number) A monovalent organic group selected from 1 to 8 alkyl groups, acetyl groups, and isocyanate groups, t is 2 to 6, u is 3 to 50), and a group having a molecular weight of 200 to 3,000, a is 0 or 1, r is 10 to 150 and s is 1 to 50.

As the specific example, the compound shown in the following Example is mentioned.

In addition, the polyoxyalkylene-modified organopolysiloxane used in the present invention preferably has a viscosity of 100 to 3,000 cs.

It is preferable that the compounding quantity of the polyoxyalkylene modified organopolysiloxane which is a 3rd component shall be 1 to 50%, especially 5 to 30% of the whole composition, and when it is less than 1%, a stable emulsion composition may not be obtained, and 50 When it exceeds%, the obtained film may be a lot sticky.

As the ionic surfactant which is the fourth essential component of the composition of the present invention, any kind of anionic, cationic or amphoteric surfactant can be used as long as it contains an ionic group and can be used for cosmetic foam raw materials, pharmaceutical raw materials and the like.

Examples of such ionic surfactants include linear alcohol sulfate ester salts, branched alcohol sulfate ester salts, alkyl ether sulfate ester salts, sulfate ester salts of glycerin fatty acid esters, sulfate ester salts of higher fatty acid alkylolamides, and the like. Sulfuric acid ester salts, alkanesulfonates, olefin sulfonates, sulfonates of higher fatty acid esters, dialkyl sulfo succinates, sulfonates of higher fatty acid amides, sulfonates such as alkylaryl sulfonates, fatty acid soaps, ether carbonates and the like. Carboxylates, phosphate ester salts, condensates of higher fatty acids and amino acids, and collagen hydrolyzate derivatives.

Examples of cationic surfactants include amine salts such as alkyl amine salts, polyamines and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts, alkyl pydininium salts, and alkyl iso Cyclic quaternary ammonium salts, such as a quinolinium salt and a dialkyl morpholinium salt, benzenetonium chloride, etc. are mentioned.

Examples of amphoteric surfactants include carboxylic acid type (amino acid type and betaine type), sulfuric acid ester type and sulfonic acid type. Phosphoric acid ester types, such as lecithin, are mentioned.

Although the emulsion composition excellent in stability is obtained by using the ionic surfactant which is the said 4th component, the compounding quantity of this 4th component is made to contain 0.5 to 20 weight% in [3rd component + 4th component]. If it is less than 0.5 weight%, the stability of the obtained emulsion composition will become inadequate, and if it is more than 20 weight%, the obtained film will become sticky. Preferably it is in the range of 1 to 10% by weight.

At the same time, the ratio of [first component + second component] / [third component + fourth component] of the first to fourth components in weight ratio is 95/5 to 50/50, preferably 92/8 to 60/40. It is mix | blended so that it may become. When this compounding ratio is larger than 95/5, the emulsion composition obtained will lack stability, and when smaller than 50/50, the film obtained will become too sticky.

The oil-in-water silicone oil composition of the present invention can be obtained by warming a predetermined amount of the first to fourth components and water. In this case, the mixing order of each component is not particularly limited, but the first and second components are mixed first, and then the third and fourth components are added and mixed by using a machine such as a stirrer or a homo mixer, and then water is added. It is preferable to mix. In addition, it is preferable to adjust the temperature at the time of mixing of each component to 7 degrees C or less.

EXAMPLE

Hereinafter, the present invention will be described in detail by way of Examples and Remarks, but the present invention is not limited to the following Examples. In addition, all% in each case is weight%.

[Examples 1 to 17 and Comparative Examples 1 to 9]

After stirring and mixing each component other than water shown in Table 1, water was gradually added and stirred by the homo mixer, and the oil-in-water type silicone emulsion composition was obtained. The storage stability at 40 ° C. and particle size and feel of these compositions were measured by the following methods. The results are shown in Table 2.

Retention stability test method:

Preservation at 4 ° C. was observed visually over time.

How to measure the particle diameter:

It was measured using Submicron Particle Anlyzer Coulter Model N.

How to evaluate the feeling:

After application to the skin, the feeling of use of the dried film was evaluated sensory.

: Not sticky and neat.

X: It is very sticky.

In addition, the component used in the Example and the comparative example is as follows.

[First ingredient]

(A) In the general formula (I), R is a CH ₃ group, n is 3,500 dimethylpolysiloxane.

(B) In the general formula (I), R is a CH ₃ group, n is 4,200 dimethylpolysiloxane.

[Second component]

(A) In the general formula (III), R is a CH ₃ group, q is 27, and a dimethylpolysiloxane having a viscosity of 20 cs at 25 ° C.

(B) In the general formula (III), R is a CH ₃ group, q is 150 and a dimethylpolysiloxane having a viscosity of 25 cs at 25 ° C.

(C) 12% of cyclic siloxane in which R is a CH3 group, p is 5 and a viscosity of 4 cs at 25 ° C. is 15 cs at 25 ° C., and a phenyl group content is 30 mol% in the general formula (III). A mixture of phosphorus straight and branched methylphenylsiloxane 88%.

[Third component]

(A) The polyoxyalkylene modified dimethylpolysiloxane which is represented by following formula and whose viscosity in 25 degreeC is 1,60 cs and HLB value is 6.3.

(B) Polyoxyalkylene-modified dimethylpolysiloxane represented by the following formula, having a viscosity at 25 ° C of 40 cs and an HLB value of 8.5.

(C) The polyoxyalkylene modified dimeryl polysiloxane (comparative product) which is represented by following formula and whose viscosity in 25 degreeC is 220 cs and HLB value is 3.5.

(D) Polyoxyalkylene-modified dimethylpolysiloxane (comparative) which is represented by following formula and whose viscosity in 25 degreeC is 100 cs and HLB value is 12.5.

(E) Polyoxyalkylene-modified dimethylpolysiloxane (comparative product) which is represented by a following formula and whose viscosity in 25 degreeC is 130 cs and HLB value is 16.1.

[4th component]

(A) Polyoxyethylene (EO3) dodecyl ether sodium sulfate.

(B) sodium dodecyl sulfate.

(C) fine sodium sulfate.

(D) Sodium polyoxyethylene (EO) tridecyl ether.

(E) Sodium polyoxyethylene (EO5) cetyl ether.

(F) Cetyltrimethylammonium chloride.

(G) stearyltrimethylammonium chloride.

(H) Lauryl acetate betaine.

TABLE 1

TABLE 2

As apparent from the examples, the silicone emulsion composition of the present invention was found to have a small particle diameter of emulsion particles and excellent storage specificity, and furthermore, to have excellent adhesion of the dried film after application to the skin, and to be non-sticky and fresh. .

On the contrary, the composition of Comparative Example 7 in which the compounding ratio of Comparative Examples 1 to 6 and the components deviated from the range of the present invention had a large particle diameter and poor storage stability, and a comparative example 8 in which the compounding ratio of the components deviated from the range of the present invention. The composition of was good in storage stability, but after being applied to the skin, the dried film was very sticky. The composition of Comparative Example 9 having less fourth components was also inferior in stability.

The oil-in-water silicone emulsifying composition of the present invention is excellent in adhesion to skin and hair, and is not sticky after applying to skin, and has excellent usability, and is also hypoallergenic and safe, and emulsion particles having a small particle diameter are uniform. It is dispersed so that it has excellent storage stability. Therefore, the composition of the present invention is hypoallergenic with respect to skin, hair, and the like, and is used as a cosmetic base material having excellent gloss and extension, and is used for hair cosmetic creams such as shampoo and rinse, skin cosmetics such as emulsion, and the like. It can be effectively used also for ointment etc. as a base material.

Claims (1)

(1) organopolysiloxane represented by the following general formula (I), (2) an organopolysiloxane having a viscosity at 25 ° C. of 1 to 500 centistokes, (3) polyoxyalkylene modified organopolysiloxanes having an HLB value of 5 to 12, and (4) consisting essentially of an ionic surfactant, having a weight ratio of [(1) component + (2) component] / [(3) component + (4) component] in the range of 95/5 to 50/50; And (4) component is emulsified in water so that 0.5-20 weight% may be contained in [(3) component + (4) component], The oil-in-water type silicone emulsion composition characterized by the above-mentioned. In the above formula, R is a monovalent monovalent hydrocarbon group having 1 to 6, and n is an average value of 500 to 10,000.