JPH08337513A - Water-repellent oil-in-water type emulsion composition - Google Patents

Abstract

PURPOSE: To obtain a water-repellent oil-in-water type emulsion composition which has good thickening and gelling capability, usability and stability and gives water-repellent layer after application by combining 2 or 3 kinds of specific thickening and gelling agent in an aqueous phase with a hydrophilic surface active substance. CONSTITUTION: A polyglycerol fatty acid diester of good safety, a higher fatty alcohol and/or a higher fatty acid and a hydrophilic surfactant are included in the aqueous phase. The molar ratio of the polyglycerol higher fatty acid diester to the higher fatty alcohol and/or the higher fatty acid is 1/1-1/5 and the hydrophilic surfactant is added to the aqueous phase in 0.4-40 mole % based on the total amount of these mixture. The hydrophilic surfactant is preferably an ionic surface active substance. In this composition, the polyglycerol fatty acid diester and the higher fatty alcohol and/or the higher fatty acid are desirably associated at a molar ratio of 1:2 in the aqueous phase in the presence of the ionic surface active substance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an oil-in-water emulsion composition, and more particularly to a water-repellent oil-in-water emulsion composition in which a coating film after use has water repellency.

[0002]

2. Description of the Related Art It is well known that emulsion compositions are used in the fields of pharmaceuticals, cosmetics, etc., and especially when used as an external preparation for the skin, a refreshing feeling of use can be obtained. Oil-in-water emulsion compositions in which oil is dispersed are widely used. However, the oil phase is only dispersed in the water phase, and there is a risk that the oil phase may separate during long-term storage due to the specific gravity of the both. Therefore, it is necessary to maintain the dosage form by increasing the viscosity of the aqueous phase and, depending on the case, gelling, and various thickening gelling agents for the aqueous phase are used for that purpose. For example, as organic compounds, polysaccharides, natural polymers of casein sugar, polyoxyethylene, synthetic polymers such as acrylic acid polymers, and as inorganic compounds, various clay minerals such as montmorillonite and silica, It is appropriately selected and used according to the purpose and effect of the thickening gelling agent.

[0003]

However, in an oil-in-water emulsion composition using such a thickening gelling agent, for example, when it is applied to the skin, first, the thickening gel in the aqueous phase of the outer phase is first prepared. The agent will form a film on the skin and the oil phase will be placed on it. Moreover, since the thickening gelling agent itself is hydrophilic, the oil phase is washed away together with the thickening gelling agent during washing, and sufficient water resistance cannot be obtained despite the fact that oil is blended. However, there was a problem with the holding property on the coated surface.

That is, when an oil-in-water emulsion composition such as a cosmetic is applied to the skin, it is desired that its effect be maintained for a long time, but the above-mentioned aqueous thickening gelling agent is added. Since the oil-in-water emulsion composition has low water resistance, it is easily peeled off by sweating, bathing, etc. in summer, and it is extremely difficult to maintain its effect for a long time. Also, in the winter, cracks, red fins, and rough skin are likely to occur due to dry outdoor conditions and water work, and although creams containing various agents are used for prevention and treatment of these, the aqueous solution as described above is also used. The oil-in-water emulsion composition containing a thickening gelling agent has a problem that the effect is limited because of low retention on the skin.

The present invention has been made in view of the above-mentioned problems of the prior art, and the object thereof is to provide an oil-in-water type emulsion composition having good thickening and gelling ability, usability and stability, and It is an object of the present invention to provide a water-repellent oil-in-water emulsion composition in which the coating film after use exhibits water repellency and the coating film has excellent water resistance.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above object, polyglycerin fatty acid diester which is widely used in food additives, cosmetics and the like and has good safety, When a higher aliphatic alcohol and / or a higher fatty acid is used as an aqueous phase thickening gelling agent in an oil-in-water emulsion composition, the oil-in-water emulsion composition exhibits excellent thickening and gelling ability. It was found that the coating film after use has water repellency and the water resistance of the coating film is improved.

That is, when a polyglycerin fatty acid diester which does not have a high polymer structure and a higher aliphatic alcohol and / or a higher fatty acid are present in the aqueous phase, an aggregate having a specific structure is formed, and this aggregate forms It has been found that the system thickens and gels by functioning as if it were a water-soluble polymer. And, since polyglycerin fatty acid diesters and higher aliphatic alcohols and the like originally have relatively high lipophilicity, the oil-in-water emulsion composition thickened and gelled by the association, for example, when applied to the skin, Of course, the above-mentioned aggregates are easily destroyed and returned to polyglycerin fatty acid diesters having a low hydrophilicity, higher aliphatic alcohols, etc., so that their presence does not impair the water repellency of the oil-in-water emulsion composition and is excellent together with the oil phase component. It can exhibit water repellency.

The present inventors also conducted a detailed study using a pure polyglycerin fatty acid diester obtained by column chromatographic purification. As a result, it was difficult to disperse the pure polyglycerin fatty acid diester in water, resulting in thickening. Although it takes a long time to gel, it has been clarified that the polyglycerol fatty acid diester containing a small amount of the hydrophilic surface-active substance is easily and uniformly dispersed. That is, the water-repellent oil-in-water emulsion composition according to claim 1 of the present application contains a polyglycerin fatty acid diester, a higher aliphatic alcohol and / or a higher fatty acid, and a hydrophilic surface-active substance in the water phase. It is characterized by

The water-repellent oil-in-water emulsion composition according to claim 2 of the present application is the same as the water-repellent oil-in-water emulsion composition according to claim 1, in which the polyglycerol fatty acid diester in the aqueous phase The molar ratio of the aliphatic alcohol and / or the higher fatty acid is 1: 1 to 1: 5, and the hydrophilic surfactant is contained in an amount of 0.4 to 40 mol% with respect to the total amount of the mixture. The water-repellent oil-in-water emulsion composition according to claim 3 is characterized in that, in the water-repellent oil-in-water emulsion composition according to claims 1 and 2, the hydrophilic surface-active substance is an ionic surface-active substance. .

The water-repellent oil-in-water emulsified composition according to claim 4 has a molar ratio of polyglycerin fatty acid diester to higher aliphatic alcohol and / or higher fatty acid in the aqueous phase in the presence of an ionic surfactant. : 2 is formed. The water-repellent oil-in-water emulsion composition according to claim 5 is the water-repellent oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid are in an aqueous phase. And are associated with each other to form a lamella structure. The water-repellent oil-in-water emulsified composition according to claim 6 is contained in any one of claims 1 to 5.
The water-repellent oil-in-water emulsified composition according to the item 1, wherein the contact angle with water is 60 ° or more. The water-repellent oil-in-water emulsified composition according to claim 7 is the water-repellent oil-in-water emulsified composition according to any one of claims 1 to 6, in which 0.01 to 5% by weight of triethanolamine is added. Characterize. The water-repellent oil-in-water emulsion composition according to the present invention,
By using a polyglycerin fatty acid diester, which is generally used as a nonionic surfactant, a higher aliphatic alcohol and / or a higher fatty acid, and a hydrophilic surfactant as a thickening gelling agent, the oil-in-water type The coating film after use of the emulsion composition exhibits water repellency. Therefore, the essential components of the water-repellent oil-in-water emulsion composition of the present invention,
Polyglycerin fatty acid diesters, higher aliphatic alcohols and / or higher fatty acids, and hydrophilic surfactants are three or four kinds.

The polyglycerin fatty acid diester used in the present invention is a fatty acid having a saturated or unsaturated straight chain or branched chain having 12 to 22 carbon atoms, and the two fatty acids may be different. Other polyglycerin fatty acid ester in the polyglycerin fatty acid diester, for example the water-repellent oil-in-water emulsion composition according to the present invention can be obtained even if the polyglycerin fatty acid monoester and polyglycerin fatty acid triester are contained as impurities, The maximum content of impurities is 50%, preferably 40% or less, and more preferably 30% or less. However, when monoester and triester coexist as impurities, the ratio of monoester and triester is 1: 3.
Within the range of 1:20, the diester content is 5
It may be less than 0%, in which case the diester content is 35% or more, preferably 40% or more. Also,
The degree of polymerization of polyglycerin may be a mixture in the range of 2 to 10, but a degree of polymerization of 3 to 6 is preferable.

Generally, commercially available polyglycerin fatty acid ester is a mixture of monoester, diester, triester, and other impurities. To obtain a highly pure sucrose fatty acid diester as used in the present invention, a solvent is used. It needs to be purified by fractionation or column chromatography. If purified by column chromatography, a high-purity product having a diester purity of 99% or more can be obtained. Polyglycerin fatty acid diester alone is very difficult to disperse in water. Therefore, it is preferable to use a hydrophilic surface-active substance together in order to favorably disperse in water.

The hydrophilic surface-active substance is a surface-active substance having an HLB of 7 or higher, preferably a HLB of 10 or higher. Hydrophilic surface-active substances are classified into hydrophilic nonionic surface-active substances and hydrophilic ionic surface-active substances when classified according to their structure. Examples of hydrophilic non-ionic surface-active substances include POE sorbitan. Monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.
POE sorbitan fatty acid esters, POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, POE-sorbit monostearate and other POE sorbit fatty acid esters, POE-glycerin monostearate, POE- POE such as glycerin monoisostearate, POE-glycerin triisostearate
Glycerin fatty acid esters, POE monooleate, PO
E Distearate, POE monodioleate, POE fatty acid esters such as ethylene glycol distearate, PO
E lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE 2-octyldodecyl ether, POE cholestanol ether, etc.
POE alkyl phenyl ethers such as POE alkyl ethers, POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl phenyl ether, etc. P
OE ・ POP Monobutyl ether, POE ・ POP Hydrogenated lanolin, POE ・ POP Glycerin ether, etc. POE ・ POP alkyl ethers, Tetronic, etc. Tetra POE ・ Tetra
POP ethylenediamine condensates, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate,
POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE hydrogenated castor oil maleic acid and other POE castor oil hydrogenated castor oil derivatives, POE sorbit beeswax and other POE beeswax lanolin derivatives, coconut oil Alkanolamides such as fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, POE propylene glycol fatty acid ester, POE alkylamine,
Examples thereof include POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate, alkylethoxydimethylamine oxide, and trioleylphosphoric acid.

It is preferable to use an ionic surface-active substance as the hydrophilic surface-active substance because of its excellent stability. As the ionic surface-active substance, fatty acid soap, ether carboxylic acid and salts thereof, alkane sulfonate, sulfonate of higher fatty acid ester, dialkyl sulfosuccinate, sulfonate of higher fatty acid amide, alkyl allyl sulfonate, Higher alcohol sulfate ester salt, secondary higher alcohol sulfate ester salt, alkyl and alkyl allyl ether sulfate ester salt, sulfate ester salt of glycerin fatty acid ester, sulfate ester salt of higher fatty acid alkylolamide, sulfated oil, phosphate ester salt, Anionic surfactants such as amino acids, collagen hydrolysates and higher fatty acid condensates, collagen hydrolysates derivatives, and alkylamine salts, polyamine or alkanolamine fatty acid derivatives, alkyltrimethylammonium salts, dialky Dimethyl ammonium salt, the carbon number of alkyl dimethyl benzyl ammonium oil group such as ionic surfactants of 12-22. Particularly preferred are anionic or cationic surfactants having 12 to 22 carbon atoms in the lipophilic group. The salt when an ionic surface-active substance is used includes potassium salt, magnesium salt, sodium salt and the like, but triethanolamine salt and / or aminomethylpropanol salt is preferable from the viewpoint of excellent stability. In this case, 0.01 to 5% by weight is preferable in the total amount of the water-repellent oil-in-water emulsion composition of the present invention.

However, since the water repellency cannot be obtained when the amount of the hydrophilic surface-active substance increases, the content of the hydrophilic surface-active substance is such that the total amount of the mixture of the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid is increased. hand,
Preferably 0.4 to 40 mol%, more preferably 1 to 2
It is 0 mol%.

The higher aliphatic alcohol and / or higher fatty acid used in the present invention has a fatty chain of 1 carbon atom.
It has two or more saturated or unsaturated linear or branched chains, and one or more of these may be used. Examples thereof include cetanol, stearyl alcohol, behenyl alcohol, batyl alcohol, stearic acid and behenic acid.

In the water-repellent oil-in-water emulsion composition of the present invention, the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid form an aggregate having a molar ratio of 1: 2 in the aqueous phase to form a thickened gel. The blending ratio of the above essential components is not particularly limited as long as the ability and water repellency are exhibited, but polyglycerin fatty acid diester is preferably 10
Mol% or more and 50 mol% or less, higher aliphatic alcohol and / or higher fatty acid 50 mol% or more and 90 mol% or less, and more preferably polyglycerin fatty acid dierter 2
It is 5 mol% or more and 45 mol% or less, and the higher aliphatic alcohol and / or higher fatty acid is 55 mol% or more and 75 mol% or less. The mixing molar ratio of the polyglycerin fatty acid diester to the higher aliphatic alcohol and / or higher fatty acid is preferably 1: 1 to 1: 5, more preferably 1: 1.5 to 1: 3.

When the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or higher fatty acid are mixed in the water phase within this range, the molar ratio of polyglycerin fatty acid diester: higher aliphatic alcohol and / or higher fatty acid is 1: 2. Aggregates are formed. Further, the total amount of the polyglycerin fatty acid diester, the higher aliphatic alcohol and / or the higher fatty acid, and the hydrophilic surface-active substance is preferably 1 to 25% by weight with respect to the total amount of the water-repellent oil-in-water emulsion composition, More preferably, it is 2 to 15%.

An oil-in-water emulsion composition prepared by preparing a thickening gelling agent by changing the compounding ratio of polyglycerin fatty acid diester and higher aliphatic alcohol and preliminarily emulsifying the thickening gelling agent by 5% Was mixed at a ratio of 95%, and the relationship between the compounding ratio and gel hardness was investigated. When tetraglycerin stearic acid diester is used as the polyglycerin fatty acid diester and stearyl alcohol is used as the higher aliphatic alcohol, as shown in FIG. The fraction is about 0.5 to 0.83, that is, the molar ratio of polyglycerin fatty acid diester: higher aliphatic alcohol is 1: 1 to
It is in the range of 1: 5, preferably the molar fraction is about 0.
6 to 0.75, that is, the molar ratio is 1: 1.5 to
It is 1: 3. The thickening gelation ability is maximized when the molar ratio is about 0.67, that is, the molar ratio is 1: 2.
Is understood to be the time. Similar results can be obtained by using a higher fatty acid or a mixture thereof instead of the higher aliphatic alcohol.

Therefore, it is understood that in the water-repellent oil-in-water emulsion composition of the present invention, the structure of the aggregate formed in the aqueous phase has the following structure. That is, in the aqueous phase, polyglycerin fatty acid diester molecules and higher aliphatic alcohol and / or higher fatty acid molecules are arranged at a molar ratio of 1: 2, and hydrophilic groups and hydrophobic groups of each molecule are adjacent to each other with the same direction due to their affinity. This arrangement forms a layer in which such arrangements are continuous to form a lamellar structure in which the hydrophilic groups face the water phase side and the hydrophobic groups face each other.

The above-mentioned polyglycerol fatty acid diester: higher aliphatic alcohol and / or higher fatty acid molar ratio of 1: 2 forms at least a polyglycerin fatty acid diester: higher aliphatic alcohol molar ratio of 1: 1 or more. The fluidity of the water phase is limited by the fact that it is dispersed in the water phase, and the system thickens and gels. However, when the polyglycerin fatty acid diester is more than the above molar ratio, excess polyglycerin fatty acid diester is present, and when the higher aliphatic alcohol and / or higher fatty acid is more than the above molar ratio of 1: 2, the excess higher fatty acid is excessive. Due to the presence of the group alcohol and / or the higher fatty acid, the thickening and gelling ability tends to decrease.

In the oil-in-water emulsion composition in which the above-mentioned aggregate having a molar ratio of 1: 2 is formed in an aqueous phase and thickened and gelled, a conventional thickened gelling agent such as a hydrophilic polymer is used. The water repellency of the coating film which cannot be obtained with the oil-in-water emulsion composition is obtained.
That is, the water-repellent oil-in-water emulsified composition of the present invention has a refreshing feeling which is a characteristic of the oil-in-water emulsified composition, and is sticky and is a drawback when a hydrophilic polymer is blended. The coating film shows good water repellency after use without any slimy feeling and further does not impair the water repellency of the blended oil, and it has excellent water resistance and therefore excellent retention on the skin. It has the characteristic of being

The water repellency can be evaluated by measuring the contact angle to water. The larger the contact angle, the higher the water repellency. However, when the water repellent oil-in-water emulsion composition of the present invention is used, it is generally found. Shows extremely high water repellency with a contact angle of 60 ° or more. In order to obtain the water-repellent oil-in-water emulsion composition according to the present invention, the following methods can be mentioned. That is, polyglycerin fatty acid diester, higher aliphatic alcohol and / or higher fatty acid, and hydrophilic surface-active substance are mixed and dissolved in a solvent such as chloroform, and then the solvent is distilled off to obtain a uniform thickening gelling agent. The water-repellent oil-in-water emulsified composition of the present invention can be obtained by adding and mixing this with a previously prepared emulsion. Alternatively, the thickening gelling agent may be dissolved in water or an aqueous phase such as an aqueous solvent to give a thickening gel-like composition, which may be added to and mixed with an emulsion prepared in advance. The thickening gelling agent need not be made uniform in advance as described above, but it is preferable to make it uniform in advance in order to shorten the preparation time when preparing the thickening gel composition. Examples of the aqueous solvent include ethyl alcohol, isopropyl alcohol, methyl alcohol, propylene glycol, 1,3
-Butylene glycol, glycerin, ethylene glycol, polyethylene glycol, or an aqueous solution thereof may be used.

The water-repellent oil-in-water emulsified composition of the present invention also forms an aggregate of the above essential components in the molar ratio of 1: 2 in the process of producing the oil-in-water emulsified composition such as cosmetics and pharmaceuticals. It can be obtained by appropriately blending at a blending ratio. For example, a method of adding a higher aliphatic alcohol and / or a higher fatty acid to the oil phase, emulsifying with the aqueous phase, and then mixing the polyglycerin fatty acid diester and the hydrophilic surface-active substance can be mentioned. The polyglycerin fatty acid diester and the hydrophilic surface-active substance may be added to the aqueous phase in advance, but in that case, problems such as thickening during emulsification are likely to occur.
In addition, polyglycerin fatty acid diester is consumed as a surfactant in the emulsification process, and the amount of polyglycerin fatty acid diester required to form an aggregate in the aqueous phase is insufficient. In order to obtain, polyglycerin fatty acid diester for forming an aggregate after emulsification must be added.

Even if the method for producing the water-repellent oil-in-water emulsion composition of the present invention is a method for producing a uniform thickening gelling agent as described above, or a method for separately incorporating the essential components. Even if it is, an aggregate with the molar ratio of 1: 2 is formed. And the water-repellent oil-in-water emulsion composition of the present invention,
The hardness does not change or separates, it is very stable over time, and the coating film after use has water repellency and excellent retention on the coated surface. It is an oil-based emulsion composition.

The water-repellent oil-in-water type emulsion composition of the present invention may be provided with other substances depending on the use and purpose.
For example, for application to cosmetics, fragrances, preservatives, vitamins, powders, pigments, drugs and the like can be added. As the powder, for example, talc, talc, kaolin, silicic anhydride,
Silicate, zinc oxide, calcium carbonate, magnesium carbonate, red iron oxide, yellow iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine blue, mica, sericite, titanium dioxide, ultramarine blue, bismuth oxychloride, sintered pigment, gun Jou Pink, Chromium Hydroxide, Mica Titanium, Aluminum Cobalt Oxide, Navy Blue, Magnesium Silicate, Bentonite,
Examples thereof include mica, zirconium oxide, magnesium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, light magnesium carbonate, nylon powder, polyethylene powder, cellulose powder, acrylic resin, silicone resin powder and melamine. The powder is
They may be blended as they are, or may be blended by hydrophobizing them by silicone treatment, fluorine treatment, metal soap treatment, activator treatment and the like.

As the oil component, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, Flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin,
Liquid oils and fats such as glycerin trioctanoate and glycerin triisopalmitate, cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil,
Solid fats and oils such as pork fat, beef bone fat, mokuro kernel oil, hydrogenated oil, beef leg oil, mokuro, hydrogenated castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivotaro, whale wax, montan wax, nukarou, lanolin, Kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether,
POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol,
Waxes such as POE hydrogenated lanolin alcohol ether,
Liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, hydrocarbon oils such as microcrystalline wax, dimethylpolysiloxane, methylphenylpolysiloxane,
Chain polysiloxane such as methylhydrogenpolysiloxane, cyclic polysiloxane such as decamethylpolysiloxane, dodecamethylpolysiloxane, tetramethyltetrahydrogenpolysiloxane, silicone resin forming a three-dimensional network structure, silicone rubber, etc. The silicones mentioned above can be mentioned, but when silicone oil or hydrocarbon oil is used, the usability and water repellency tend to be further improved.

In these oil phases, oil-soluble agents, antioxidants,
An ultraviolet absorber such as octyl methoxycinnamate or a lipophilic surfactant may be added. Further, the water-repellent oil-in-water emulsion composition of the present invention can be used as cosmetics or pharmaceuticals of various dosage forms as long as its effect is not impaired, and can be blended, and creams, emulsions, lotions, beauty essences, It can be applied to O / W emulsion compositions such as makeup cosmetics, skin creams for external use, and cleansing.

[0029]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the embodiments. Further, the compounding amount is shown by weight% unless otherwise specified.

Example 1 1) Purified water 79.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethylpolysiloxane 5.0 5) Stearyl alcohol 2.0 6) Tetraglycerin stearic acid Diester 3.0 where tetraglycerin stearic acid diester is
20% of monoester and 80% or more of diester.
1) to 5) were heated and stirred to emulsify, and 6) was added to obtain a gel oil-in-water emulsion composition. This emulsified composition has a temperature of 37 ° C.
Stable at 25 ° C and 0 ° C for 1 month or more, and
It had a refreshing feeling of use and excellent usability, and its water repellency was ⊚.

In this specification, the water repellency of the coating film of the emulsion composition was evaluated by measuring the contact angle with water. The contact angle was measured at about 25 ° C. by applying the test emulsion composition to a glass plate so as to have a thickness of 0.35 mm, drying and then using an automatic contact angle meter CA-Z type (manufactured by Kyowa Interface Science Co., Ltd.). The water repellency was evaluated according to the following criteria. ◎ ... contact angle 80 ° or more ○ ・ ・ ・ contact angle 60 to less than 80 ° △ ... contact angle 40 to less than 60 ° × ... contact angle less than 40 °

Comparative Example 1 1) Purified water 81.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethylpolysiloxane 5.0 5) Montmorillonite (aqueous thickener) 3.0 1 ) To 4) are heated and stirred to emulsify, and 5) is added to obtain an oil-in-water emulsion composition. This emulsified composition is at 37 ° C. and 25
It was stable at 0 ° C and 0 ° C for 1 month or more, respectively, but the water repellency was x.

Comparative Example 2 1) Purified water 83.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethylpolysiloxane 5.0 5) Acrylic acid polymer (water-soluble polymer thickener) ) 1.5 6) Caustic potash 0.5 1) to 4) were heated and stirred to emulsify, and 5) and 6) were added to homogenize to obtain an oil-in-water emulsion composition. The emulsion composition was stable at 37 ° C., 25 ° C. and 0 ° C. for 1 month or more, respectively, but the water repellency was ×.

Comparative Examples 3 to 6 1) Purified water 83.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethyl polysiloxane 5.0 5) Stearyl alcohol 1.5 1) to 5 ) Was heated and stirred, and then a commercially available polyglycerin fatty acid ester (3.0%) was added thereto at 70 ° C. to emulsify the resulting oil-in-water emulsion composition for comparison.

Comparative Example 3 Polyglycerin stearic acid ester (monoester 1
0%, 90% or more of diester), a uniform gel oil-in-water emulsion composition could not be obtained. Comparative Example 4 Polyglycerin stearic acid ester (monoester 3
When 0% and 70% or more of diester) were used, the water repellency of the obtained gel oil-in-water emulsion composition was Δ. Comparative Example 5 Polyglycerin stearic acid ester (monoester 5
When 0% and 50% or more of diester) were used, the water repellency of the obtained gel oil-in-water emulsion composition was x. Comparative Example 6 Polyglycerin stearic acid ester (monoester 7
When 0% and 30% or more of diester) were used, the water-repellent property of the obtained gel oil-in-water emulsion composition was x.

Example 2 Nutrition cream 1) Liquid paraffin 30.0 wt% 2) Pluronic 0.8 3) Vitamin E acetate 0.2 4) Paraben 0.2 5) Flavor 0.1 6) Stearic acid 1.5 7 ) Purified water Residual amount 8) Glycerin 30.0 9) Tetraglycerin oleic acid diester 2.5 1) to 6) and 7) to 8) are separately heated to 70 ° C., and 7).
~ 8) after emulsifying by adding 1) ~ 6) to 9).
Was added, mixed and stirred, and cooled to obtain a nutrition cream. The water repellency of this nutrition cream was good.

Example 3 Hand Cream 1) Squalane 20.0 wt% 2) Polyoxyethylene sorbitan fatty acid ester 1.0 3) Vaseline 15.0 4) Vitamin E acetate 0.2 5) Paraben 0.2 6) Fragrance 0.1 7) Stearyl alcohol 0.75 8) Behenyl alcohol 0.75 9) Purified water Residual amount 10) Propylene glycol 10.0 11) Tetraglycerin stearic acid diester 3.0 1) -8) and 9) -10) Separately heated to 70 ° C,
After adding 1) to 8) to 9) to 10) with stirring and emulsifying, 11) was added and mixed and stirred, and cooled to obtain a hand cream. The water repellency of this hand cream was ◯.

Example 4 Gel whitening cosmetic composition <Gel formulation> 1) Steanoic acid 0.5 wt% 2) Triethanolamine 0.3 3) Behenyl alcohol 2.0 4) Purified water balance 5) Tetraglycerin stearic acid diester 3.0 1) to 4) were heated and dissolved at 60 ° C., then 5) was added, mixed and stirred, and cooled to obtain a gel. <Emulsified formulation> 1) squalane 40.0 wt% 2) stearic acid 0.5 3) paraben 0.1 4) fragrance 0.1 5) triethanolamine 0.3 6) propylene glycol 20.0 7) arbutin 3 0.08) Purified water Residual amount An emulsion was prepared by a conventional method with the above composition, and the above gel 7
0 g and 30 g of emulsion were mixed and cooled to 25 ° C. to obtain a gel whitening cosmetic. The water repellency of this gel whitening cosmetic was ◯.

Example 5 Sunscreen Cream 1) Beeswax 2.0 wt% 2) Shortening 2.0 3) Cetostearyl alcohol 2.0 4) Olive oil 14.8 5) p-Dimethylaminobenzoic acid 2-ethylhexyl ester 4 0.0 6) 2-Hydroxy-4-methoxybenzophenone 1.0 7) Perfume 0.1 8) Paraben 0.1 9) Ethanol 5.0 10) Purified water Residual amount 11) Polyoxyethylene hydrogenated castor oil 0. 4 12) Propylene glycol 5.0 13) Tetraglycerin oleic acid diester 2.0 1) -8) and 9) -12) are separately heated and stirred at 70 ° C., and 1) -8) are 9) -12). Was added with stirring to emulsify, then 13) was added, mixed and stirred, and cooled to obtain an O / W sunscreen cream. The water repellency of this cream was ◯.

Example 6 Sunscreen lotion 1) Vaseline 10.0 wt% 2) Olive oil 15.0 3) Oleic acid 1.5 4) Octyl methoxycinnamate 3.0 5) Paraben 0.1 6) Fragrance 0 .1 7) Purified water Residual amount 8) Propylene glycol stearate 0.3 9) Silicon treated titanium oxide 6.0 10) Propylene glycol 5.0 11) Hexaglycerin stearic acid diester 3.0 1) to 6) and 7 ) To 10) are separately heated and stirred at 70 ° C., 7) to 10) are added to 1) to 6) with stirring to emulsify, and then 11) is added and mixed and stirred, and cooled to O / W. Got a sunscreen lotion. The water repellency of this lotion was ◯.

Example 7 Premedication 1) Liquid paraffin 10.0 wt% 2) Trimethylsiloxysilicic acid 3.0 3) Behenyl alcohol 0.5 4) Stearyl alcohol 0.5 5) Perfume 0.1 6) Paraben 0 .1 7) Residual amount of purified water 8) Polyoxyethylene glyceryl 1.4 9) Polyethylene glycol 3.0 10) Spherical cellulose powder 1.0 11) Propylene glycol 8.0 12) Hexaglycerin oleic acid diester 1.5 1 ) To 6) and 7) to 11) are separately heated and stirred at 70 ° C., 1) to 6) are added to 7) to 11) with stirring to emulsify, and then 12) is added and mixed and stirred, Cooled to produce a pre-made lotion. This lotion is 37 ℃,
It was stable at 25 ° C and 0 ° C for 1 month or more, respectively. In addition, the water repellency was ◯ while having a refreshing feeling of use. Then, it showed higher water repellency than the conventional O / W type pre-make lotion, and when the powdery foundation was applied repeatedly, the makeup lasting property was improved as compared with the case without this lotion.

Example 8 Foundation 1) Cyclic polysiloxane 10.0 wt% 2) Trimethylsiloxysilicic acid 3.0 3) Stearyl alcohol 1.0 4) Triethanolamine 0.3 5) Paraben 0.1 6) Purified water Residual amount 7) Stearic acid 0.6 8) Titanium dioxide 5.8 9) Talc 4.2 10) Iron oxide 2.1 11) Propylene glycol 8.0 12) Tetraglycerin oleic acid diester 1.5 1) -5 ) And 6) to 11) are separately heated and stirred at 70 ° C., 1) to 5) are added to 6) to 11) with stirring to emulsify, and then 12) is added, mixed and stirred, and cooled. A foundation was manufactured. This foundation is 37
It was stable at ℃, 25 ℃ and 0 ℃ each for 1 month or more.
In addition, it has a refreshing feeling, but the contact angle is 9
The water repellency was 8 ° C, which is much higher than that of the conventional O / W type foundation, and the makeup retention was improved.

Example 9 Foundation 2 1) Dimethylpolysiloxane 7.0 wt% 2) Methylphenylsiloxane 5.0 3) Squalane 5.0 4) Behenyl alcohol 1.0 5) Perfume 0.1 6) Paraben 0.1 7) Residual amount of purified water 8) Polyoxyethyleneglycerin monostearate 0.6 9) Silicon-treated titanium dioxide 5.8 10) Silicon-treated Seycite 4.2 11) Silicon-treated iron oxide 2.1 12) Butylene glycol 5 0.013) Tetraglycerin stearic acid diester 2.5 1) to 6) and 7) to 12) are separately heated and stirred to homogenize, and 1) to 6) are added to 7) to 12) while stirring. After emulsification, 13) was added, mixed and stirred, and cooled to produce a foundation. This foundation is 37
It was stable at ℃, 25 ℃ and 0 ℃ each for 1 month or more.
Also, the contact angle is 1 even though it has a refreshing feel.
Compared to the conventional O / W type foundation at 01 ° C., it showed extremely high water repellency, and the makeup lasting property was improved.

Comparative Example 7 Premeation 1) Dimethyl polysiloxane 7.0 wt% 2) Cetyl alcohol 5.0 3) Perfume 0.1 4) Paraben 0.1 5) Purified water balance 6) Propylene glycol stearate 0.3 7) polyethylene glycol 5.8 8) propylene glycol 4.2 9) acrylic acid polymer 2.1 10) caustic potash 5.0 1) -4) and 5) -8) are heated separately at 70 ° C. 5)
To 8) after emulsifying 1) to 4) with stirring, and then 9),
10) was added, mixed and stirred, and cooled to produce a pre-make lotion. This pre-makeup is 37 ℃,
It was stable at 25 ° C and 0 ° C for 1 month or more, respectively, but the water repellency was x.

Comparative Example 8 Foundation 1) Cyclic polysiloxane 10.0 wt% 2) Liquid paraffin 8.0 3) Cetyl alcohol 1.0 4) Triethanolamine 0.3 5) Paraben 0.1 6) Purified water Residual amount 7) Stearic acid 0.6 8) Titanium dioxide 5.8 9) Talc 4.2 10) Iron oxide 2.1 11) Propylene glycol 8.0 12) Bentonite 1.2 1) -5) and 6) -11. ) Were separately heated and stirred at 70 ° C., 6) to 11) were added to 1) to 5) with stirring to emulsify, and then 12) was added, mixed and stirred, and cooled to prepare a foundation. This pre-makeup is 3
It was stable at 7 ° C., 25 ° C. and 0 ° C. for 1 month or more, respectively, but the water repellency was poor.

[0046]

As described above, the oil-in-water emulsion composition according to the present invention contains the polyglycerin fatty acid diester, the higher aliphatic alcohol and / or the higher fatty acid in the aqueous phase in the presence of the hydrophilic surface-active substance. By forming an aggregate in the composition, it has good thickening and gelling ability stability and usability, and the coating film after use shows water repellency and is excellent in retainability on the coated surface. Have.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the gel hardness and the blending mole fraction of a polyglycerin fatty acid diester and a higher aliphatic alcohol in a water-repellent oil-in-water emulsion composition according to an example of the present invention.

Claims (7)

[Claims] 1. A water-repellent oil-in-water emulsion composition comprising a polyglycerin fatty acid diester, a higher aliphatic alcohol and / or a higher fatty acid, and a hydrophilic surface-active substance in an aqueous phase. 2. The water-repellent oil-in-water emulsion composition according to claim 1, wherein the molar ratio of the polyglycerol fatty acid diester to the higher aliphatic alcohol and / or higher fatty acid in the aqueous phase is 1: 1 to 1: 1. 5. The water-repellent oil-in-water emulsion composition, wherein the hydrophilic surface-active substance is contained in an amount of 0.4 to 40 mol% with respect to the total amount of the mixture. 3. The water-repellent oil-in-water emulsion composition according to claim 1, wherein the hydrophilic surface-active substance is an ionic surface-active substance. 4. The water-repellent oil-in-water emulsion composition according to claim 2, wherein the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or
Alternatively, a water-repellent oil-in-water type emulsion composition, wherein the higher fatty acid forms an aggregate having a molar ratio of 1: 2 in an aqueous phase. 5. The water-repellent oil-in-water emulsified composition according to any one of claims 1 to 4, wherein the polyglycerin fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid associate in the aqueous phase to form a lamellar structure. A water-repellent oil-in-water emulsion composition. 6. The water-repellent oil-in-water emulsified composition according to any one of claims 1 to 5, which has a contact angle with water of 60 ° or more. 7. The water-repellent oil-in-water emulsified composition according to any one of claims 1 to 6, wherein 0.01 to 5% by weight of triethanolamine and / or aminomethylpropanol is added. Oil-based emulsion composition.