KR100211781B1 - Stabilization emulsion of perfluoropolyethers and fatty substances and preparation method thereof - Google Patents

Abstract

The present invention relates to perfluoropolyethers having perfluoroalkyl end groups and stabilizing emulsions of fatty substances:

One or more perfluoroethers having perfluoroalkyl end groups: 1 50 weight

At least one polyhydroxylated compound selected from glycerol comprising at least three hydroxy groups and polyalcohols other than glycerol and sugars, the compound is soluble in water or a hydrophilic solvent when the compound is a solid: 95 weight (Including water and hydrophilic solvents), if any

-100 At least one fatty substance having a melting temperature of: 80 weight ,

At least one emulsifier: 0.1 10 weight .

In particular, the emulsion is used in cosmetics and dermatology.

Description

Stabilization emulsion of perfluoropolyethers and fatty substances and preparation method thereof

The present invention relates to a stable emulsion of perfluoropolyethers having perfluoroalkyl end groups and fatty substances.

The perfluoropolyethers have very high hydrophilicity and hydrophobicity, and therefore, it is possible to prepare their stable aqueous emulsion solutions only with specific combinations of the same emulsion components.

US Pat. No. 4,803,067 describes stable emulsions of perfluoropolyethers with perfluoroalkyl end groups in oil / water emulsions or water / oil emulsions obtained using emulsifiers. The emulsions are specifically used as lotions and creams in cosmetics and dermatology, and the excellent properties of the perfluoropolyethers are specific to waterproof, oxygen permeable and carbon dioxide permeation protective films that allow normal skin respiration on the skin. Because of the formation.

EP 390,206 describes the preparation of stable emulsions of perfluoropolyethers with perfluoroalkyl end groups in glycerol or polyhydroxylated compounds using emulsifiers.

In cosmetic or dermatological products, the emulsion is added to a base formulation comprising other ingredients.

Until now, it was impossible to obtain stable emulsions of fatty substances and perfluoropolyethers, but the need for anhydrous or virtually anhydrous emulsions, etc. has been strongly felt in the fields of cosmetics and dermatology or industrial applications. Or substantially anhydrous emulsions should be made to maintain the hydrophilicity of the anhydrous product at the place where the emulsion is introduced.

If one or more fatty substances in liquid state are added to the emulsion of perfluoropolyethers in glycerol or other polyhydroxylated compounds under agitation in the presence of a surfactant soluble in glycerol or other polyhydroxylated compounds It has been found that it is possible to obtain stable emulsions of perfluoropolyethers with perfluoroalkyl end groups (hereafter simply called perfluoropolyethers) and fatty substances.

The presence of such stable emulsions of perfluoropolyethers and fatty substances in glycerol or other polyhydroxylated compounds has made it impossible to emulsify the fats in glycerol or other polyhydroxylated compounds and perfluoropolys in fatty substances. It was very surprising that it was impossible to emulsify the ether. The presence of perfluoropolyethers in the emulsion in glycerol or other polyhydroxylated compounds can emulsify fatty substances in perfluoropolyether-glycerol-based or perfluoropolyether-other polyhydroxylated compounds. To make it possible.

It is therefore an object of the present invention to provide emulsions of stable, anhydrous or substantially anhydrous perfluoropolyethers and fatty substances.

Another object is to provide a method for preparing the emulsion.

The former object is achieved by obtaining a stable emulsion of a perfluoropolyether having a fatty substance and a perfluoroalkyl end group according to the present invention, consisting of the following.

One or more perfluoropolyesters having perfluoroalkyl end groups: 1 to 50% by weight At least one polyhydroxylated compound selected from glycerol and non-glycerol polyalcohols and saccharides comprising three or more hydroxy groups, soluble in water or a hydrophilic solvent when the compound is solid: 10-95 weight (If any, including water and hydrophilic solvents),

-100 melting point At least one fatty substance of less than 10 to 80

One or more emulsifiers: from 0.1 to 10 weight

Fatty material means:

1) a liquid product (oil) that is insoluble in water and polyhydroxylated compounds as defined above, and

2) insoluble in water and polyhydroxylated compounds and having a melting point of 100 The product (fat) which is a solid at room temperature which is below.

Perfluoropolyethers having perfluoroalkyl end groups, ie free from functional groups, are known compounds and are described in British Patent 1,104,482, US Patent 3,242,218; 3,665,041; 3,715,378; 4,523,039; European Patent Application 148,482; 151,877 and 191,490 and the international patent applications WO 87/00538 and WO 87/02992 are described together with the preparation method. Several perfluoropolyethers are available under the trade names Fomblin _(R) , Galden _(R) , Krytox _(R) and Demum _(R) .

Suitable perfluoropolyethers are characterized as having one or more of the following perfluorooxyalkylene repeat units.

a) (CF ₂ -CF ₂ O)

b) (CF ₂ O)

c) ( For a simple formula, (C ₃ F ₆ O)

d) (CF ₂ O-CF ₂ -CF ₂ O)

e) (CF ₂ -CF ₂ -CF ₂ O)

f) ( )

e)

[Wherein, R _f 'groups are the same or different and each is a fluorine atom or perfluoroalkyl group, preferably 1 carbon atom. Contains 3.]

Suitable perfluoropolyethers in the present invention are preferably each a combination of the following perfluorooxyalkylene units or the following perfluorooxyalkylene units:

I) (CF ₂ -CF ₂ O) and (CF ₂ O), wherein the units were statistically distributed along the perfluoropolyether chain; or

II) ( ) And (CFXO), wherein X is F or CF ₃ and the units are distributed statistically along the chain .; or

III) (CF ₂ -CF ₂ O), ( ) And (CFXO), wherein X is F or CF ₃ and the units are distributed statistically along the chain.

IV) ( ); or

V) (CF ₂ -CF ₂ -CF ₂ O); or

VI) (CF ₂ -CF ₂ O); or

VII)

[F _f 'group in the formula is the same or different, fluorine atom or preferably 1 carbon 3 is a perfluoroalkyl group.]; or

VIII) (CF ₂ O-CF ₂ -CF ₂ O)

Also suitable are perfluoropolyethers containing the following perfluorooxyethane rings.

or

[Wherein T, A, B and R are the same or different and are a perfluorooxyalkyl, a perfluoropolyoxyalkyl or a perfluoroalkyl group, preferably 1 carbon Contains 6.]

Examples of suitable perfluoropolyethers having perfluorooxyalkylene repeating units fall into the following categories:

A)

Wherein R _f and R _f ′ are the same or different and are selected from the group consisting of CF ₃ , C ₂ F ₅ and C ₃ F ₇ ; Unit C ₃ F ₆ O (oxytrifluoromethyltrifluoroethylene), And CF ₂ O is statistically distributed along the chain; a is an integer; b and c are integers or 0; If the sum (b + c) is not zero, Rain is 5 40];

B) CF ₃ O- (C ₂ F ₄ O) _d (CF ₂ O) _E -CF ₃

[Wherein, units C ₂ F ₄ O and CF ₂ O were statistically distributed along the chain; d and e are integers; d / e ratio is 0.3 Changes to 5];

C) CF ₃ O- (C ₃ F ₆ O) _f (C ₂ F ₄ O) _G- (CFXO) _h -CF ₃

[Formula C ₃ F ₆ O, C ₂ F ₄ O and CFXO were statistically distributed along the chain;

X is F or CF ₃ ;

f, g and h are integers;

Rain is 1 50, Rain is 1 10];

D) R ³ _q O- (CF ₂ CF ₂ CF ₂ O) _j R ⁴ _q g

D) R ³ _q and R ⁴ _q are the same or different and are -CF ₃ or -C ₂ F ₅ and j is an integer.]

Perfluoropolyethers suitable for use in the present invention generally have a number average molecular weight of 500 20,000, more typically 1,000 Has 10,000.

Polyhydroxylated compounds suitable for the present invention are described in more detail in the cited European patent application 390,206 in the name of the same applicant and described in the present specification by reference.

When the polyhydroxylated compound is a solid, the compound is dissolved in water or a hydrophilic solvent. It is preferable to use the minimum amount of water or hydrophilic solvent required to dissolve the compound. Suitable hydrophilic solvents are, for example, glycerol, glycols, lower alcohols, ethereal solvents and diglyme, and also mixed with water.

However, water is usually used as a solvent. Suitable are usually useful as concentrated aqueous solutions (syrups) of polyalcohols and sugars.

Usually the concentration of the solution is 50 80 weight to be.

Most preferred polyhydroxylated compounds are glycerin, diglycerol, triglycerine and tetraglycerine.

The oils and fats according to the invention may be vegetable, animal, hydrocarbon or synthetic. These are in particular fatty alcohols, acids, esters and amides, silicone oils and hydrocarbon fats and oils.

Emulsifiers may be soluble in the polyhydroxylated compounds. Among the suitable emulsifiers, the following may be mentioned.

Sodium lauryl sulfate,

Sulfosuccinate (sulfosuccinic acid hemiester),

Coco amphoteric carboxyglycinates,

Potassium cetyl phosphate,

Sodium alkyl-polyoxyethylene-ether carboxylate,

Benzalkonium chloride,

Alkylamidopropylbitane,

Coco Amidopropylbitine,

The emulsion according to the invention preferably has the following composition.

-Perfluoropolyether or perfluoroethers: 5 25 weight ;

At least one polyhydroxyated compound: 10 59 weight ;

Fatty substances or substances: 35 80 weight ;

Emulsifiers or emulsifiers: 0.3 3 weight .

The most preferred emulsion is 10 of the polyhydroxylated compound 40 weight It includes.

Typically, the emulsion contains only one perfluoropolyether and only one polyhydroxylated compound.

Depending on the proportions and the nature of the components, the emulsions of the present invention exhibit a very wide range of viscosities, which have a wide range of applications. For example, the minimum viscosity emulsion is 25 While at 2,000 cps (centipoise), for example, the largest viscous emulsion has a viscosity of at least 1,000,000 cps.

The viscosity increases with the concentration of fatty substances and perfluoropolyethers, and the viscosity increases further when using polyhydroxylated compounds.

Also, at the same concentration, the nature of the fatty substance affects the viscosity.

The viscosity of the emulsion can be reduced by adding water or alcohols, if necessary. For example, suitable alcohols are 1 carbon 4 alkyl alcohols and 2 carbon atoms Ethylene glycol containing 4.

Since the addition of water or alcohol tends to reduce the stability of the emulsion, it is calculated as the weight of the total emulsion, about 20 It is not preferable to add the above.

Minimum dropwise amount of water or alcohol, for example 1 to be. If water or alcohol is added, of course the percentage amount of the other components is reduced, but their interactivity remains unchanged.

In the application of the present invention, it is useful for water or alcohol containing emulsions to have a small or relatively small viscosity without high hydrophobicity.

Stable emulsion according to the invention is centrifuged at 4,000 rpm for 30 minutes, 50 It is observed that after one week of treatment in the oven, no phase separation occurs.

The emulsions according to the invention can be prepared as follows. While stirring in an emulsion of one or more perfluoropolyethers in one or more polyhydroxylated compounds comprising one or more emulsifiers soluble in the polyhydroxylated compounds (the emulsion is simply called pre-emulsion). Add one or more fatty substances that are in the liquid state. The pre-emulsion is not critical but is in most cases at room temperature.

If the fatty substance is a solid at room temperature, pre-emulsion is applied in the molten state or specifically heated and dissolved if necessary to facilitate dissolution in the liquid fatty substance according to the invention, preferably hydrocarbon oil.

When the fatty substance is added at a temperature above room temperature, it is desirable to preheat the pre-emulsion to the temperature of the fatty substance or to the next temperature.

The preparation of the pre-emulsions is described in detail in European Patent Application 390,206, which is incorporated herein.

The emulsion can be prepared by adding perfluoropolyether or perfluoropolyether to one or more emulsifier solutions in one or more polyhydroxylated compounds under agitation.

Stirring at low speed after addition to obtain the best homogenization (eg 30 For 120 minutes) is preferred.

The outer layer of the emulsion according to the present invention consists of polyhydroxylated compounds or compounds, whereas the internal dispersibility consists of perfluoropolyether or perfluoropolyethers and fatty substances or substances. In fact, the emulsion can be diluted with glycerol and water (no mechanical agitation) but not with perfluoropolyethers and fatty substances (otherwise mechanical agitation is used). In addition, the fact that the viscosity increases with increasing perfluoropolyethers or fatty substances indicates that both forms of the component form an internal phase.

The emulsions of the present invention can be used in a wide range of fields in cosmetics, dermatology and industry.

The introduction of fat-soluble substances (eg vitamins or soul filters) or glycerol-soluble substances in the oil phase imparts functionality to cosmetic and dermatological products.

Examples cited in the use of cosmetics are lip balms and anhydrous cosmetics such as protective creams, sun-preparations, lipsticks and sticks.

Examples cited in regard to dermatological use are skin protective preparations and drug-slow-reaease preparations.

Among industrial applications to be cited are lubricants and waterproofing of fibers and leather.

Anhydrous, or in some cases, emulsions, the presence of a small amount of water in the emulsion makes it possible to more biochemically produce cosmetic and dermatological products made from the emulsion. In addition, the anhydrous nature of the emulsion results in a higher persistence of the product on the skin. In addition, the advantages that occur in the same field of application is that the emulsions according to the invention are cited above. It is a fact that smaller amounts of surfactant are required than are included in the emulsions of perfluoropolyethers in water / oil or oil / water emulsions described in patent 4,803,067. The following examples are for illustrative purposes only and should not be considered limiting of the invention.

Example 1 33 shows various emulsions according to the invention and aspects for preparing them. All compositions are by weight Represented by

The stability test was described previously.

The structure and the characteristic of the used perfluoropolyether are indicated below.

Fomblin HC / 25

nm-20 40

M.W. (number average molecular weight) -3,200.

Galden DO3

General formula same as the above product

n / m = 20 40

M.W. = 870

Pomblelin HC / R

General formula same as the above product

n / m = 20 40

M.W. = 6,600

Denumum S-65

F (CF ₂ -CF ₂ -CF ₂ O) _n CF ₂ CF ₃

M.W. = 4,500

Pomblin Z25

CF _3- (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q -OCF ₃

p / q = 0.6 0.7

M.W. = 9,400

Example 1

Pre-emulsion of Pombulin HC / 25, Glycerol and Texafon N / 40 with 5,000 Silverson L / 2R turboemulsifiers Vaseline oil is added at room temperature with stirring at 6,000 rpm.

Unless otherwise indicated, the emulsions used in the examples below were prepared according to the same method.

The emulsion was stable. The viscosity as well as the emulsion of the following examples were measured with a Brookfield digital eight-speed viscosimeter (model RTV-II) according to the manufacturer's rules.

Viscosity: 25 At 36,600 CPS (centipoise) (5 r.pm, impeller 29).

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

Example 10

Example 11

Example 12

Example 13

Example 14

Example 15

Example 16

45 Pre-emulsion preheated to about 55 Add Ropi Vaseline in a molten state at a temperature of

Stable Emulsion.

Example 17

Premix Ropi Vaseline and Paraffin before adding to the pre-emulsion.

Stable Emulsion.

Example 18

Example 19

Example 20

Example 21

Example 22

Example 23

Example 24

Example 25

Example 26

Example 27

Example 28

Example 29

Example 30

Example 31

Example 32

Example 33

Viscosity increases at high oil concentrations, and it is difficult to obtain such concentrations under cooling, so about 50 The preparation is carried out in a hot state by preheating the pre-emulsion at.

Viscosity: 20 At 500,000CPS

Stable Emulsion.

Example 34

For comparison, Example 34 37, it is not a composition according to the present invention.

Easily separating at rest will make the emulsion completely unstable.

Example 35

Emulsification is completely unstable if the formbline HC / 25 is quickly separated at rest.

Example 36

Stability: Same as Example 35.

Example 37

Stability: Same as Example 35.

Example 38

This embodiment describes a protective cream and its manufacturing method.

Approximately 55 Phase B is gradually added to the pre-emulsion A preheated to it under stirring. It is then carried out with less stirring until it reaches room temperature. Cream viscosity is 20 At 290,000 cps (1 rpm, impeller 6).

Example 39

This example represents a vitamin-based hydrating cream, prepared according to the form of Example 38:

Cream viscosity is 20 At 180,000 cps (1 rpm, impeller 6).

Example 40

One Except for the addition of chamomile glycol extract of, other vitamin-based hydrating cream is prepared by the method described above.

The presence of the small amount of glycol results in a viscosity of 180,000 cps It is enough to bring up to 50,000 cps.

Example 41

Sun-cream was prepared in the same manner as in Example 38 except that Phase B was preheated.

Cream viscosity is 20 At 480,000 cps (1 rpm, impeller 6).

Claims (11)

Stabilizing emulsions of perfluoropolyethers and fatty substances having a perfluoroalkyl end group, characterized in that: One or more perfluoropolyethers having perfluoroalkyl end groups; One 50 weight At least one polyhydroxylated compound selected from glycerol and polyalcohols other than glycerol, and saccharides, which are soluble in water or a hydrophilic solvent when solid and have three or more hydroxyl groups; If present, including hydrophilic solvent or water, 10 95 , -100 At least one fatty substance having a melting point of less than or equal to; 10 80 At least one emulsifier soluble in the polyhydroxylated compound or compounds: 10 . The method of claim 1, wherein the perfluoropolyether or perfluoropolyether is 500 Stabilized emulsion, characterized in that it has a number average molecular weight of 20,000. The stabilizing emulsion of claim 1 or 2 wherein said polyhydroxylated compound is selected from glycerol, diglycerol, triglycerine and tetraglycerine. The stabilizing emulsion according to claim 1 or 2, wherein the fatty substance is selected from the group consisting of fatty alcohols, acids, esters and amides, silicone oils and hydrocarbon oils and fats. The stabilizing emulsion according to claim 1 or 2, wherein the emulsifier is ionic. 3. One or more perfluoropolyethers according to claim 1 or 2 having a perfluoroalkyl end group: 25 weight At least one polyhydroxyated compound: 10 59 ,-One or more fatty substances: 35 80 At least one emulsifier: 0.3 3 Stabilized emulsion containing. The method of claim 6, wherein the one or more polyhydroxylated compounds is 10 40 weight Stabilizing emulsion containing. The weight of water or alcohol according to claim 1 or 2, based on the total emulsion. Stabilizing emulsion, characterized in that further comprises, other components do not change their mutual properties. At least one fatty substance in the liquid state under stirring is added to a pre-emulsion of at least one perfluoropolyether in at least one polyhydroxylated compound containing at least one emulsifier that is soluble in the polyhydroxylated compound. The method for producing a stabilized emulsion as claimed in claim 1. 10. The method of claim 9, wherein when the fatty substance is solid at room temperature, it is added to a pre-emulsion in the molten state or dissolved in a liquid fatty substance. The stabilizing emulsion of claim 1 used in the manufacture of cosmetics and dermatological products.