JPS6328442A - Water-in-oil type emulsion composition - Google Patents

Abstract

PURPOSE:To enhance the keeping stability and stability of the title composition by incorporating metal oxide particles and/or metal hydroxide particles having a specified mean particle diameter and uniformly coated with a silicone compd. to form the water-in-oil type emulsion composition. CONSTITUTION:A silicone compd. expressed by formula I [R1 is a lower alkyl, R2 is a hydrogen atom, an alkyl, and an aryl, (a) is a positive integer, and (b) stands for 0 or a positive integer] is uniformly coated on metal oxide particles and/or metal hydroxide particles having 0.01-1mum mean particle diameter, and the material is incorporated to prepare the water-in-oil type emulsion composition. The (a) and (b) of the silicone compd. expressed by formula I are appropriately limited to conform to 20<=100a/(a+b)<=100. The molecular wt. of the silicone compd. is preferably >=200,000.

Description

Detailed Description of the Invention [Graduation Field of Application] The present invention is a water-in-oil (hereinafter referred to as W10) emulsifying composition, more specifically W10 which has excellent storage stability and skin safety over a wide temperature range. The present invention relates to an emulsified composition.

Conventional technology] Conventionally, as cosmetics such as creams, milky lotions, and foundations, aqueous particles are generally dispersed in an oil phase, and so-called W/O emulsion compositions are oil-in-water type (○/ It is known that it has advantages over emulsified compositions, such as protecting the skin, imparting flexibility, and being easier to remove when bathed in water.

However, W/○ emulsion compositions have the disadvantage of poor storage stability compared to O/W emulsion compositions.

Separation of emulsified compositions generally occurs by creaming (or settling), agglomeration, or coalescence of emulsified particles. W1
In an emulsified composition, water droplets tend to aggregate at low temperatures, resulting in a syneresis phenomenon, that is, the oil phase, which is a continuous layer, tends to separate into the upper layer, while at high temperatures, the particle size decreases due to the coalescence of water 'tffa. As a result, water droplets precipitate, leaving only the oil phase in the upper layer, which tends to separate the oil phase. If the coalescence proceeds further, separation of the aqueous phase will occur. Therefore, it has been difficult to obtain a W10 emulsion composition that is stable over a wide temperature range. In particular, relatively stable W10 emulsion compositions can be obtained with non-polar oils such as paraffin oil, but these also lack stability over a wide temperature range, and furthermore with respect to polar oils such as olive oil. Even the stability at room temperature was not satisfactory.

Particularly in the case of composite plate materials containing various pigments such as makeup cosmetics, it is difficult to ensure not only emulsion stability but also pigment dispersion stability.

Conventionally, emulsified compositions have generally been emulsified using surfactants. Surfactants are a group of substances that have a hydrophilic group and a lipophilic group in one molecule and exhibit surfactant ability, and have high solubility in base materials and strong permeability into the skin. Therefore, it may cause skin irritation for some people.

[Problems to be Solved by the Invention] In view of the above circumstances, the present inventors have conducted extensive research with the aim of obtaining a W10 emulsion composition with excellent storage stability and good safety. It has been discovered that if fine powder of metal oxide and/or metal hydroxide coated with a compound is used as an emulsifier, the above purpose can be achieved without the concomitant use of conventionally used surfactants. , we have completed the present invention.

[Means for Solving the Problems] That is, the present invention provides silicon compounds of formula (A) uniformly coated with an average particle size of 0.01 A1 m to 1.0 A1 m. ! ! This is a water-in-oil emulsion composition characterized by containing a gold mud oxide and/or a metal hydroxide (hereinafter referred to as a silicon-coated metal oxide/metal hydroxide) of m.

(RI 5i03/2) a CRs R25i
n) b (A'j Unlike the conventional concept of dissolving a surfactant in a base to emulsify an oil phase and an aqueous phase, the present invention directly disperses a solid having emulsifying ability in a base. It is based on a completely new idea of emulsifying oil and water phases.

5. This emulsification method is not affected by the polarity of the oil phase. However, unlike conventional methods, surfactants are selected based on the HLB (hydrophilicity and lipophilicity) balance. Since metal hydroxide powder is a substance that does not dissolve in either the aqueous phase or the oil phase, the balance of the system is less likely to be disrupted even when various pigments are added, and pigment aggregation is less likely to occur.

Furthermore, it has good safety to the skin and is clearly superior to lipophilic surfactants such as glycerin fatty acid ester and sorbitan fatty acid ester, which have been widely used in the past.

The configuration of the present invention will be described below.

The metal oxide and metal hydroxide used in the present invention are:
Magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, silica, iron oxide (α-Fe203, r-F
e203, Fe304, FeO) iron hydroxide, titanium oxide, lower titanium oxide, zirconium oxide, chromium oxide,
Chromium hydroxide, manganese oxide, cobalt oxide, nickel oxide, and composite oxides and composite hydroxides made from combinations of two or more of these; examples include iron titanate, cobalt titanate, cobalt aluminate, etc. .

The silicon compound covering the surface is (RI 5i03/2) a CRI R25i
n) It has the structural formula of (A) and preferably has a molecular weight of 200,000 or more. 0 If the molecular weight is 200,000 or more, the coated silicon will not be eluted with chloroform etc. and can be completely coated. .

In formula (A), R1 is a lower alkyl group or an aryl group, R2
represents a hydrogen atom, an alkyl group, or an aryl group, a is a positive integer, and b is O or a positive integer.

In the formula, the ratio of a and b is in the range of 20≦100a/(a+b)≦100.The larger the value of 100a/(a+b), the more network structure there is, and the more likely it is to be liberated if it enters the solvent system. small. The ratio of a and b can be calculated from the infrared absorption spectrum.

Specific examples of the silicon compound of formula (A) include:;1. ! I can give you something like.

(CH35i03/2 :l a ((CI(3)
HSiO) b,.

(CH35i(1+72) a ((CH3) (
C2R5) 5in) b.

(C1-+35i03/2) a ((CH3)
(C5Hty) 5in) b, (CII35i0
3/2) a ((CH3) (Ca R17)
5in) b, (C113SiO*/2)
a ((CH3) (CI811:IT)
5in) b.

The longer the alkyl chain of R2, the more nonpolar it becomes, and the more compatible it is with nonpolar oil.

The fiffi of the silicon compound in the silicon-coated metal oxide/metal hydroxide of the present invention varies depending on the surface area, but is approximately 0.1 to 20% by weight, preferably 0.2 to 5% by weight.
Weight%. If it is less than 0.1% by weight, it is not optimal for imparting effective stability to metal oxides and metal hydroxides, and conversely, if it exceeds 20% by weight, bonding between particles will progress. Agglomeration occurs and dispersibility is not optimal.

In the silicon-coated metal oxide/metal hydroxide used in the present invention, the metal oxide and/or metal hydroxide is
) is sufficient as long as it is coated with a silicon compound (resin).
Therefore, even plastics and mica that have been surface-treated with metal oxides or gold hydroxides can be made into stable composites by coating with silicone resin.

The silicon compound of the above formula (A) can be prepared, for example, by bringing a cyclic silicon represented by the following formula (%) into contact with the metal oxide and/or metal hydroxide to form a surface of the metal oxide and/or metal hydroxide. It can be easily obtained by polymerization reaction.

In the surface polymerization reaction, the desired product can also be produced by dissolving the silicon represented by formula (B) in a solvent, dispersing the metal oxide and/or metal hydroxide therein, and then drying it. Alternatively, the desired product can also be produced by directly spraying silicon dissolved in a solvent and drying it by heating.

One type or two or more types of silicon represented by formula (B) can be used.

Compounds of formula CB) include dihydrohexamethylcyclotetrasiloxane, trihydropentamethylcyclotetrasiloxane, tetrahydrotetramethylcyclotetrasiloxane, dihydrooctamethylcyclopentasiloxane, trihydrohebutamethylcyclopentasiloxane, tetra It is desirable that two or more hydrogen rings exist in one molecule, such as hydrohexamethylcyclopentasiloxane and pentahydropentamethylcyclopentasiloxane.

In addition to carrying out the reaction in a liquid phase, the reaction can also be carried out in a solid phase using a ball mill; however, in the case of a solid phase, the particle shape etc. may change, so care must be taken.

The following method is most preferred. In formula (B), +1 = 3 to 7
If one or more types of volatile silicon and metal oxides, etc. are placed in separate open containers and these containers are left in a common closed system, the silicon will turn into metal oxides and metal hydroxides. Adsorbs to the surface in molecular form.

In this state, silicon volatilizes due to the partial pressure at that temperature,
It maintains adsorption equilibrium on powders such as metal oxides. If the powder had no polymerization activity, silicon would be desorbed when it was taken out and the powder would return to its original surface, but if it had polymerization activity, it would polymerize on the powder. When polymerized, the partial pressure of silicon on the surface of the powder decreases, so the silicon in the container further volatilizes and is supplied.

Heat or a polymerization catalyst is generally used to cause polymerization on the surface, but according to the findings of the present inventors, 5i-H is present on the surface of metal oxides and/or metal hydroxides. It has a catalytic effect that crosslinks groups to form 5i-0-Si bonds.

Silicon adsorbed on the surface of the metal oxide and/or metal hydroxide forms a mesh-like silicone resin that is successively crosslinked due to this surface activity.

When the powder surface is coated with silicone resin in this way, the surface active sites on the metal oxide and/or metal hydroxide surface are blocked, and subsequent adsorption and crosslinking reactions do not proceed, preventing film formation. Stop.

Thereafter, by degassing, unreacted silicon is removed, and a metal oxide and/or metal hydroxide coated only with silicone resin can be produced.

It is sufficient to leave the metal oxide and/or metal hydroxide and silicon at a temperature of 100°C or less, and there is no need for the conventionally required temperature of 150°C. This is because it has surface activity.

The metal oxide and/or metal hydroxide to be treated may be dried in advance or may contain some moisture. Although high-temperature heating is not necessary to obtain powder coated with silicone resin in this way, heating at about 200°C would simply increase the value of 100a/(a + b), which would exceed the scope of the present invention. There isn't.

The silicon-coated metal oxide/metal hydroxide obtained as described above is further treated with unreacted 5i remaining on the surface.
Addition reaction of alkenes and alkynes using -H group,
More stable and polar controlled metal oxides and/or
Or it can be a metal hydroxide.

The silicon-coated metal oxide/metal hydroxide obtained above is
5i-H on metal oxide and/or metal hydroxide surfaces
Although the surface is coated by crosslinking the groups to form a network structure, crosslinking does not proceed 100% due to steric hindrance, etc. Therefore, residual Si--H groups exist, and they tend to become somewhat unstable under harsh conditions such as alkali or acid. By adding an alkene or alkyne to this remaining Si-H group to form a 5i-C bond, a metal oxide and/or metal hydroxide that is more stable against alkalis and acids can be made. Moreover, by adjusting the length of the hydrocarbon such as an alkene to be added, hydrophobicity can be further strengthened.

The alkenes or alkynes to be added to the 5i-H group are hydrocarbons having one or more unsaturated bonds (double bond, triple bond) at the terminal or any position, such as acetylene, ethylene, propylene, butene, octene, etc. , decene, and octadecene.

If alkenes etc. have an unsaturated bond, 5 at that position
Since it undergoes an addition reaction with the i-H group, a cyclic structure such as cyclohexane, benzene, naphthalene, etc. may be present at other positions.

Moreover, butadiene, isoprene, etc. having two or more double bonds can also be used.

The addition reaction of alkenes and alkynes to Si-H groups can be carried out by contacting them in the gas phase or liquid phase for 1 hour or more at 50 to 300° C. in the presence of a catalyst.

As the catalyst, platinum group catalysts, compounds of ruthenium, rhodium, palladium, osmium, iridium, and platinum are used, and compounds of palladium and platinum are particularly suitable. Examples of palladium-based materials include palladium chloride (■), ammonium tetraamminepalladate (n) chloride, palladium oxide (■), and palladium hydroxide (n). Platinum-based platinum chloride (If), tetrachloroplatinic acid (I
I), platinum chloride ([V), hexachloroplatinic acid (■)
, ammonium hexachloroplatinate (IV), platinum oxide (n) platinum hydroxide (■), platinum dioxide (■), platinum oxide (■), platinum disulfide (■), platinum sulfide (IV) hexachloroplatinum (rV ) acid potassium, etc. In addition, these palladium-based compounds and platinum-based compounds are
It is also possible to use an organic solvent layer obtained by adding alkyl (1 to 8 carbon atoms) methylammonium chloride or tri-n-alkylamine and performing ion pair extraction in a water/organic solvent system.

The average particle size of the silicon-coated metal oxide/metal hydroxide used in the present invention is 0.01 μm to 1 μm,
Preferably it is 0.2 μm to 0.5 μm.

When the particle size is less than 0.018 m or more than 1 μm, it is difficult to obtain a stable emulsion.

The amount of silicon-coated metal oxide/metal hydroxide is W1
0.1% to 10% by weight, preferably 0.5% to 5% by weight based on the total amount of the emulsion composition.

If the amount is less than 0.1% by weight, it may become difficult to stabilize the W10 emulsion composition, and if it exceeds 10% by weight, the viscosity tends to increase and it becomes difficult to manufacture.

As the oil used in the W10 emulsion composition of the present invention, oils generally used in foods, paints, medicines, cosmetics, etc. can be used, such as paraffin oil, squalane, paraffin wax, ceresin, etc. Hydrocarbons, natural animal and vegetable oils and fats such as olive oil, camellia oil, soybean oil, macadamia nut oil, castor oil, lanolin, carnauba wax, candelilla wax, spermaceti wax, beeswax, jojoba oil, waxes, fatty acids with 10 to 35 carbon atoms, carbon Alcohols having 10 to 35 carbon atoms, synthesized esters having 16 or more carbon atoms, such as isopropyl myristate, diglyceride isostearate, triglyceride 2-ethylhexanoate, diisostearyl malate, myristyl myristate, and the like.

Any one kind or two or more kinds of these oils can be used, and the blending amount is generally 20% by weight to 80% by weight.

The W10 emulsion composition of the present invention includes the above-mentioned organic polymer fine powder,
In addition to the essential ingredients of oil and water, other surfactants, humectants, dyes, pigments, ultraviolet absorbers, fragrances, medicinal agents,
Preservatives, antioxidants, etc. can be added as appropriate.

The W10 emulsion composition of the present invention can be used in foods, paints, medicines, cosmetics, etc., and is particularly suitable for cosmetics such as lipsticks, creams, and milky lotions.

[Examples] In order to further understand the present invention, below are production examples of silicon-coated metal oxides and metal hydroxides used in the present invention, and examples and comparative examples of the water-in-oil emulsion composition of the present invention. .

All parts in the examples are expressed by weight.

Silicon oxide (0.2 μm) as a production example 10. g and 5 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80'C.

After 72 hours, the silicon dioxide was removed and further heated to 100°.
The mixture was left in a dryer for 24 hours to obtain 10.2 g of silicon-coated silicon dioxide. Furthermore, this coated powder was
To this, 10 mg of chloroplatinic acid as a catalyst, 200- and 1-decene IOJ of isopropyl alcohol (hereinafter referred to as IPA) were added, and the mixture was heated under reflux in a water bath for 2 hours. ), and after further washing and filtration with IPAloo-, the mixture was placed in a dryer at 100° C. and dried for 12 hours to obtain alkyl-modified silicon-coated silicon dioxide.

Production Example 2 10 g of silicon dioxide (0.6μI11) and 5 g of tetrahydrotetramethylcyclotetrasiloxane were placed in a separate v container and left in a desiccator at 80°C.

After 72 hours, the silicon dioxide was taken out and further heated to 100°C.
The mixture was left in a dryer for 24 hours to obtain 10.2 g of silicon-coated silicon dioxide. Further, this coated powder was placed in a 500-sized eggplant-shaped flask, and 10111 g of chloroplatinic acid was added to it as a catalyst.
) 200- and 1-octene 10- were added and heated under reflux for 2 hours in a water bath.
), and after further washing and filtration with IPAloo-, the mixture was placed in a dryer at 100° C. and dried for 12 hours to obtain alkyl-modified silicon-coated silicon dioxide.

Production Example 3 Magnesium hydroxide (0.3 μm) Log and 5 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers and left in a desiccator at 80°C. After 72 hours, the magnesium hydroxide was taken out and further heated to 100°C.
The mixture was left in a dryer for 24 hours to obtain 10.05 g of silicon-coated magnesium hydroxide.

Further, this coated powder was placed in a 500-mm eggplant-shaped flask, and 10 mg of chloroplatinic acid was added as a catalyst, 200 d of isopropyl alcohol (hereinafter referred to as IPA), and 10 g of chloroplatinic acid as a catalyst.
- Add 10ai2 of hexene and heat for 2 hours in a water bath, then filter using a glass filter (G-4),
After further washing and filtration with IPAloo-, the product was placed in a dryer at 100°C and dried for 12 hours to obtain alkyl-modified silicon-coated magnesium hydroxide.

Example 1 Emulsified lipstick■ Castor oil 50 (parts)■
Glyceryl diisostearate 10 ■ Candelilla wax 8 ■ Solid paraffin
10■ Silicon dioxide obtained in Production Example 1 4■
Red No. 202 1■ Red No. 202 0.5■ Titanium oxide
1 ■ Red iron oxide 1
．． 5 [Phase] Yellow iron oxide 1■
ne blue water
10 [Phase] Glycerin 3 Manufacturing method Melt ① to ① uniformly at 80°C, add ① to [phase] to disperse, and further add ① and 0 to emulsify. While stirring, the mixture was filled into a molded container and cooled to obtain a lipstick.

Example 2 Cream foundation ■ Isopropyl myristate 17 (parts) ■ Squalane 10 ■ Lanolin
7■ Microcrystalline wax
3■ Silicon dioxide obtained in Production Example 2 3■ Butyl paraoxybenzoate 0.1■ Kaolin
5■ Talc
10 ■ Titanium oxide 2 [phase]
Red iron oxide 0.2■ Yellow iron oxide
0.80 Fragrance
0.10 Purified water
36.7 [Phase] Propylene glycol
5■ Methyl roseoxybenzoate 0.1 Production method Dissolve ■ to ■ uniformly at 80°C, add ■ to 0 to disperse, and further add 0 and @ to emulsify. The mixture was cooled while stirring to obtain a W10 cream foundation.

The W10 cream foundation produced in this example had good iron oxide dispersibility during production, and neither oil nor water separated even when stored for 3 months at temperatures of 0°C, room temperature, and 37°C. It had good stability and safety. It also had an excellent creamy feel and caused less makeup smearing.

Comparative Example 1 Comparative Example 1 was obtained in the same manner as in Example 1, except that silicon dioxide in Example 1 was replaced with 0.4 parts of glycerin monooleate and 3.6 parts of sorbitol aqueous solution.

Comparative Example 2 Comparative Example 2 was obtained in the same manner as in Example 1 except that silicon dioxide in Example 2 was replaced with POE (40 mol) hydrogenated castor oil.

fI! The emulsified type of the prepared sample was confirmed by electrical conductivity,
The emulsion particle size was observed using a microscope. Also, 15 at each temperature.
The samples were stored for several days, and their stability was examined based on the state of separation and changes in particle size.

In Comparative Example 1, water separated immediately after emulsification, and in Comparative Example 2, although it was emulsified, the iron oxide coagulated and the original color could not be obtained. The iron agglomeration progressed further and eventually it all settled.

In contrast, Examples 1 and 2 had good emulsion stability and dispersion stability, and were W/○ emulsified cosmetics that were stable for more than 3 months even when left at 37°C, room temperature, and 0°C. . Safety was also good.

Example 3 W10 solid foundation ■ Macadamia nut oil 25 (parts) ■ Vaseline
5■ Ceresin
5 ■ Magnesium hydroxide obtained in Production Example 3 4 ■ Kaolin 15 ■ Mica 20 ■ Titanium oxide
8 ■ Red iron oxide 1
■ Yellow iron oxide 3 [phase] Methyl paraoxybenzoate 0.10 Fragrance
0.10 Paddy ice making
10.80 Propylene glycol 3
Production method ① to ③ are uniformly melted at 80°C, ③ to 0 are added and dispersed, and [phase] and 0 are further added and emulsified. After adding 0 while stirring, the mixture was poured into a container and cooled to obtain a W10 solid foundation.

[Effects of the Invention] The W10 emulsion composition according to the present invention has extremely good storage stability (emulsion stability and dispersion stability) over a wide temperature range compared to conventional compositions. It is also an emulsified composition with extremely high safety in terms of skin irritation. Therefore, it can be applied as a W10 emulsion composition in various fields, and is a particularly useful emulsion composition in the cosmetics field.

Claims (15)

[Claims] (1) A metal oxide with an average particle size of 0.01 μm to 1 μm, uniformly coated with the silicon compound of formula (A), and/or
Or a water-in-oil emulsion composition characterized by containing a metal hydroxide. [R_1SiO_3_/_2]_a [R_1R_2Si
O]_b(A) [In the formula, R_1 is a lower alkyl group or aryl group, R_2
represents a hydrogen atom, an alkyl group, or an aryl group. a represents a positive integer, and b represents 0 or a positive integer. ] (2) The water-in-oil emulsion composition according to claim (1), wherein in formula (A), a and b satisfy the following relational expression 20≦100a/(a+b)≦100. (3) The water-in-oil emulsion composition according to any one of claims (1) to (2), wherein the silicon compound of formula (A) has a molecular weight of 200,000 or more. (4) The coating amount of the silicon compound of formula (A) is 0.1 to 2
The water-in-oil emulsion composition according to any one of claims (1) to (3), which has a content of 0% by weight. (5) The water-in-oil emulsion composition according to any one of claims (1) to (4), wherein R_2 in formula (A) is a hydrogen atom. (6) The metal oxide is magnesium oxide, calcium oxide, aluminum oxide, silica, red iron oxide, black iron oxide, yellow iron oxide, titanium dioxide, lower titanium oxide, zirconium oxide, chromium oxide, manganese oxide, cobalt oxide, or The water-in-oil emulsion composition according to any one of claims (1) to (5), which is nickel oxide. (7) The water-in-oil emulsion composition according to claim (6), wherein the titanium dioxide is fine particle titanium dioxide with a particle size of 0.001 to 0.1 μm. (8) The oil according to any one of claims (1) to (6), wherein the metal oxide is a metal composite oxide of silica alumina, iron titanate, cobalt titanate, lithium cobalt titanate, or cobalt aluminate. Water-in-water emulsion composition. (9) Water-in-oil type according to any one of claims (1) to (5), wherein the metal hydroxide is magnesium hydroxide, calcium hydroxide, aluminum hydroxide, yellow iron oxide, or chromium hydroxide. Emulsifying composition. (10) The water-in-oil emulsion composition according to claim (6), wherein the yellow iron oxide is rod-shaped yellow iron oxide. (11) The water-in-oil emulsion composition according to any one of claims (1) to (10), wherein R_2 is a hydrocarbon chain having 2 to 30 carbon atoms. (12) The silicon compound of formula (A) has the following formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) [In the formula, R_1 represents a lower alkyl group or aryl group, and R_2 represents an alkyl group or aryl group. represents. k is a positive integer, l is 0 or a positive integer, and the following relational expression k+l=3-100 20≦100K/(k+l)≦100 shall be satisfied. ] Claims (1) to (1) are silicon compounds obtained by contacting a cyclic silicon represented by a metal oxide and/or a metal hydroxide and causing a surface polymerization reaction.
The water-in-oil emulsion composition according to any one of 2). (13) The water-in-oil emulsion composition according to claim (12), wherein l in formula (B) is 0 and k is 3 to 7. (14) A product obtained by further adding an alkene or alkyne to unreacted Si-H groups remaining on the surface of the metal oxide and/or metal hydroxide coated with the silicon compound of formula (A). A water-in-oil emulsion composition containing a metal oxide and/or a metal hydroxide. (15) The water-in-oil emulsion composition according to claim (14), wherein the double bond of the alkene is in the 1 position.