KR20040014190A - Emulsion composition and method of manufacturing the same - Google Patents

Abstract

PURPOSE: To obtain an o/w type emulsification composition without using a surfactant, which is excellent in stability, safety and usability, and also an o/w/o type emulsification composition excellent in stability, time stability and usability. CONSTITUTION: The emulsification composition comprises one or more oily ingredients selected from the group consisting of fatty acids and higher alcohols and one or more ionic polymers insoluble in the oily ingredient, selected from the group consisting of anionic polymers and cationic polymers, while the composition containing no surfactant.

Description

Emulsion composition and its manufacturing method {EMULSION COMPOSITION AND METHOD OF MANUFACTURING THE SAME}

The present invention relates to an emulsified composition and a method for producing the same. More specifically, the present invention relates to an oil-in-water emulsion composition, an O / W / O type emulsion composition, and a method for producing the same.

Conventional oil-in-water emulsion compositions have been prepared using water-soluble polymers such as surfactants, hydroxyethyl cellulose, sodium carboxymethyl cellulose, pullulan, and pectin. In addition, a method of using an acrylic acid / alkyl methacrylate copolymer in the fragrance journal, 26, 8, 79 (1998), and an anionic polymer in the fragrance journal, 26, 8, 42 (1998). A method of using a polymer electrolyte complex composed of a cationic polymer has been proposed. In addition, Japanese Patent Laid-Open No. 7-100356 discloses a method for producing an emulsion composition by using a complex formed from both an ionic polymer and a higher fatty acid acting as an emulsifier. However, the oil-in-water emulsion composition prepared by these methods had the following problems.

In the case of using the surfactant, it is not preferable to feel the adhesive feeling due to the surfactant, and there is a problem that many people have anxiety about the stability of the surfactant among ordinary consumers.

In the case of using a water-soluble polymer as an emulsifier, there is a problem that the water-soluble polymer has a low interfacial tension-lowering ability and a relatively low emulsification force, and thus, emulsion stability is poor compared to the surfactant.

In the case of using the acrylic acid / alkyl methacrylate copolymer, it is difficult to maintain stability over time because the dispersed particles of the resulting emulsion composition are large, and the oil-in-water emulsion composition prepared by this method is unique because it is stabilized with a polymer gel. There was problem that application range was narrow.

In addition, even when the composite formed from both the ionic polymer and the higher fatty acid is used as an emulsifier, the oil-in-water emulsified composition is actually produced by using a surfactant in combination, and the problems caused by using the surfactant are not solved.

Conventionally, O / W / O type emulsion composition was manufactured by disperse | distributing the oil-in-water type emulsion composition manufactured using the high hydrophilic surfactant in the oil phase containing a high lipophilic surfactant. However, this production method requires a large amount of surfactant because it produces an oil-in-water emulsion composition in which oil particles are finely dispersed, and there is a problem in that it is not preferable in terms of usability and safety.

An object of the present invention is to provide an oil-in-water emulsion composition having good stability over time without containing a surfactant. Moreover, an object of this invention is to provide the O / W / O type | mold emulsion composition with favorable time-lapse stability which does not mix | blend surfactant or reduces the compounding quantity of surfactant.

1 is an optical micrograph of the emulsion composition obtained in Example 1 of the present invention.

2 is an optical micrograph of the emulsion composition obtained in Example 6 of the present invention.

The present invention relates to an ionic polymer insoluble in at least one oil component selected from the group consisting of (1) fatty acids and higher alcohols, and (2) at least one oil component selected from the group consisting of anionic polymers and cationic polymers. Oil-in-water emulsified composition comprising a, and does not contain a surfactant,

The oil-in-water emulsion composition wherein the ionic polymer insoluble in the oil component is carboxymethyl cellulose sodium or vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer salt,

The manufacturing method of the said oil-in-water emulsion composition by the phase-phase emulsification method,

The phase-in-phase emulsification method adds a part of the aqueous phase forming component containing the ionic polymer 2 to the oil phase forming component containing the oil component (1) to form a water-in-oil type emulsion composition. And then adding the aqueous phase forming component to re-phase the water-in-oil emulsion composition into an oil-in-water emulsion composition,

It consists of an oil phase, an aqueous phase, and an external oil phase, and contains the said oil component (1) and the said ionic polymer (2) in an oil phase or an aqueous phase, and also an oil phase and an aqueous phase O / W / O type emulsion composition, characterized in that it does not contain a surfactant,

The above-mentioned O / W / O type emulsion composition wherein the ionic polymer insoluble in the oil component is carboxymethyl cellulose sodium or vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer salt,

A method for producing an O / W / O type emulsion composition in which the oil-in-water emulsified composition is prepared by the phase-in-phase emulsification method, and the resulting oil-in-water emulsified composition is dispersed in an oil phase, and

The phase-in-phase emulsification method adds a part of the aqueous phase forming component containing the ionic polymer (2) to the oil phase forming component containing the oil component (1) to generate a water-in-oil type emulsion composition, and then further forms the aqueous phase forming component. It is related with the said manufacturing method which is a method of adding the oil-in-water type emulsion composition to the oil-in-water type emulsion composition by addition.

The oil-in-water emulsion composition of this invention does not contain surfactant, and has the characteristic that stability with time is favorable.

Moreover, the O / W / O type emulsion composition of this invention does not mix | blend surfactant, or it has the characteristic that the compounding quantity of surfactant is small compared with the past, and its stability with time is favorable.

details

The oil-in-water emulsion composition of the present invention is an ionic polymer insoluble in at least one oil component selected from the group consisting of fatty acids and higher alcohols, and at least one oil component selected from the group consisting of anionic polymers and cationic polymers. It contains. In the present invention, fatty acids and / or higher alcohols and ionic polymers form a complex, and the complex expresses emulsification. This complex is considered to have the same action as the surfactant. Moreover, since it is a high molecular compound, it also has an effect | action as a protective colloid, and is considered to express the same effect as the case where a low molecular weight surfactant and a high molecular compound are used together.

The oil-in-water emulsion composition of the present invention is an oil component forming an oil phase, and contains at least one oil component selected from the group consisting of fatty acids and higher alcohols, and may contain other oil components as necessary. As other oil components, any form of solid, paste or liquid may be blended at room temperature, and hydrocarbon-based polar oils, non-polar oils and silicone oils may be used.

The fatty acid is not particularly limited as long as it has 6 or more carbon atoms (usually 30 or less) and is solid or liquid at normal temperature (25 ° C), but is preferably liquid at normal temperature. In fatty acids having less than 6 carbon atoms, lipophilic properties are insufficient, so that the complex with the ionic polymer is hardly oriented in the oil phase. As a fatty acid solid at normal temperature, palmitic acid, stearic acid, 12-hydroxystearic acid, etc. are mentioned. Liquid fatty acids at room temperature include straight chain fatty acids such as capron and caprylic acid; Branched fatty acids such as isopalmic acid and isostearic acid; And unsaturated fatty acids such as oleic acid, myristic acid, and palmitic acid.

The higher alcohol is not particularly limited as long as it has 6 or more carbon atoms (usually 30 or less) and is solid or liquid at room temperature (25 ° C), but is preferably liquid at room temperature. In alcohols with less than 6 carbon atoms, lipophilic properties are insufficient, and the complex with the ionic polymer is hardly oriented in the oil phase. Cetyl alcohol, stearyl alcohol, behenyl alcohol, etc. are mentioned as solid alcohol at normal temperature. Examples of the higher alcohol which is liquid at room temperature include straight chain higher alcohols such as octanol and decanol; Branched higher alcohols such as isostearyl alcohol and octyldodecanol; And unsaturated higher alcohols such as oleyl alcohol.

When using a solid fatty acid and higher alcohol at normal temperature, in order to improve compatibility with the other components which form an oil phase, it is preferable to use together a liquid fatty acid, a triglycerol ester, etc.

The blending amount of fatty acid and higher alcohol in total is preferably at least 0.1% by weight, more preferably at least 2% by weight in the emulsion composition. If it is less than 0.1 wt%, a good emulsion composition cannot be obtained. There is no upper limit in the compounding quantity of fatty acid and a higher alcohol, It can mix | blend in consideration of usability.

Anionic polymer and cationic polymer are mentioned as said ionic polymer.

As an anionic polymer, Natural polysaccharides, such as sodium alginate; Polysaccharide derivatives such as carboxymethyl cellulose sodium; The homopolymer and copolymer of acrylic acid type or methacrylic acid type, such as polyacryloyl dimethyl taurine ammonium, sodium polyacrylate, sodium polymethacrylate, an acrylamide / ammonium acrylate copolymer, are mentioned.

Examples of cationic polymers include vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer salts (e.g. ethyl sulfate), dimethyldiallylammonium chloride / acrylamide copolymers, cationic cellulose, cationic guar And cationized polysaccharides such as gums. These ionic polymers can use a commercial item as it is.

The molecular weight of the ionic polymer is preferably 1,000 to 1,500,000, more preferably 5,000 to 500,000. The ionic polymer having a weight average molecular weight of less than 1,000 may be absorbed transdermally, and when an ionic polymer of more than 1,500,000 is used, the viscosity of the emulsified composition rises, resulting in poor usability in terms of adhesiveness and mucus.

The compounding quantity of an ionic polymer becomes like this. Preferably it is 0.05-10 weight%, More preferably, it is 0.1-2 weight% in an emulsion composition. If it is less than 0.05% by weight, the emulsifying power is insufficient, and if it exceeds 10% by weight, the usability is poor in terms of adhesiveness, mucoadhesiveness, difficulty in spreading during coating, and the like.

The oil-in-water emulsion composition of this invention does not contain surfactant.

The oil-in-water emulsion composition of the present invention includes a moisturizer, a fungicide, a preservative, an antioxidant, a pH adjuster, an ultraviolet absorber, a powder such as titanium oxide or zinc oxide, iron oxide, in addition to the oil component, other oil components, and the ionic polymer. A coloring material etc. can also be mix | blended.

Although the ratio of the oil phase and the water phase in the oil-in-water emulsion composition of this invention is not specifically limited, Preferably it is oil phase: water phase (weight ratio) = 70-0.1: 30-99.9, More preferably, it is 20-5: 80-95. . If the oil phase is less than 0.1% by weight, no emulsion can be obtained. If the oil phase is more than 70% by weight, the oil-in-water emulsion composition obtained tends to be difficult to stabilize.

In the oil-in-water emulsion composition of the present invention, for example, an oil phase forming component comprising at least one oil component selected from the group consisting of fatty acids and higher alcohols is added to the aqueous phase containing the ionic polymer, It can manufacture by processing with.

In addition, a part of the water phase forming component containing the ionic polymer is added to an oil phase including at least one oil component selected from the group consisting of fatty acids and higher alcohols to form a water-in-oil emulsion composition, and then further water phase formation. By adding components to rephase the oil-in-water emulsion composition with the oil-in-water emulsion composition (phase emulsification method), a finer and more stable oil-in-water emulsion composition can be produced. Here, the ionic polymer may be added in its entirety when preparing the water-in-oil emulsion composition, or may be added a part when preparing the water-in-oil emulsion composition, and the rest may be added when the oil-in-water emulsion composition.

The oil-in-water emulsifying composition can be prepared using the phase-in-phase emulsification method, and a polyhydric alcohol can be blended in the water phase. By blending a polyhydric alcohol, a gelled substance is formed at the interface between the aqueous phase and the oil phase or the oil phase, and the stability of the water-in-oil emulsion composition produced at the beginning of the phase-phase emulsification is improved. As the polyhydric alcohol, trihydric or higher alcohols such as glycerin, sorbitol, diglycerin, and polyglycerol can be used.

The compounding quantity of a polyhydric alcohol becomes like this. Preferably it is 1-20 weight%, More preferably, it is 3-15 weight%. If it is less than 1% by weight, no gelled material is formed, and if it is more than 20% by weight, a tacky feeling of use is formed.

In the phase-in-phase emulsification method, in consideration of the ratio of the oil phase and the water phase when preparing the water-in-oil type emulsion composition, the generation and the phase of the water-in-oil type emulsion composition can be adjusted at the rate of addition of the aqueous phase.

In addition, by controlling the ratio of fatty acids and / or higher alcohols and ionic polymers, the amount of complexes formed from fatty acids and / or higher alcohols and ionic polymers, and the like, stable phase can be generated. For example, when the ratio of the oil phase to the water phase is high, a stable oil-in-water emulsion composition can be obtained by lowering the ratio of fatty acids and / or higher alcohols to the ionic polymer to reduce the amount of the complex produced.

The oil-in-water emulsion composition of this invention can be applied to formation of the oil-in-water phase and the water phase of O / W / O type emulsion composition.

The O / W / O type emulsion composition of the present invention is at least one oil component selected from the group consisting of fatty acids and higher alcohols in the oil or water phase, and at least one selected from the group consisting of anionic polymers and cationic polymers. It contains an insoluble ionic polymer in the oil component. The O / W / O type emulsion composition may contain a surfactant in the external oil phase, or contain one or more compounds selected from the group consisting of inorganic acid salts, organic acid salts, amino acids and salts thereof in the aqueous phase, Fatty acids and / or higher alcohols.

Examples of the surfactant include sorbitan fatty acid esters such as sorbitan isotate and sorbitan oleate; Glycerin fatty acid esters such as glycerin stearate; Polyglycerol fatty acid esters such as diglycerin diisostearate and polyglycerol pentaoleate; Those with high lipophilic properties such as sucrose fatty acid esters such as sucrose ercaic acid ester and sucrose polylauric acid ester are used.

The compounding quantity of surfactant is preferably 0.01 to 10% by weight, more preferably 0.5 to 2% by weight in the O / W / O type emulsion composition. If it is less than 0.01% by weight, the oil-in-water emulsion composition forming the oil and water phases of the O / W / O type emulsion composition cannot be dispersed in the external oil phase.

In one or more compounds selected from the group consisting of an inorganic acid salt, an organic acid salt, an amino acid, and a salt thereof in the aqueous phase, in an O / W / O type emulsion composition containing a fatty acid and / or a higher alcohol in an external oil phase, an inorganic acid salt, an organic acid salt, Due to the action of amino acids and / or amino acid salts, the hydrophobicity of the complex formed by the fatty acids and / or higher alcohols contained in the external oil phase and the ionic polymers contained in the oil or water phase is increased, so that the external oil phase is not used without a surfactant. The oil-in-water emulsion composition can be disperse | distributed in an O / W / O type emulsion composition.

The inorganic acid salts, organic acid salts, amino acids and salts thereof are not particularly limited as long as they are water-soluble and exhibit salting effect.

Examples of the inorganic acid salts include sodium sulfate, magnesium sulfate, sodium hydrogen phosphate, sodium dihydrogen phosphate, and the like.

Examples of the organic acid salt include citrate salts such as monosodium citrate, disodium citrate, trisodium citrate and monopotassium citrate; Succinate salts such as sodium succinate and sodium succinate; And tartarate salts such as disodium tartarate. The organic acid salt may be added as a hydrate of organic acid salt, but may be generated by adding it as an organic acid and neutralizing with alkali.

Examples of the amino acid and salts thereof include glycine, proline, alanine, sodium aspartate, sodium glutamate, and the like.

Among the inorganic acid salts, organic acid salts, amino acids and salts thereof, sulfates, carbonates, phosphates, citrates and the like are preferably used, and sulfates such as sodium sulfate are particularly preferable. Moreover, although it does not specifically limit, It is preferable to use sodium salt, potassium salt, magnesium salt, etc.

The total amount of the inorganic acid salt, organic acid salt, amino acid and salt thereof is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight in the O / W / O type emulsion composition. If it is less than 0.1 wt%, the salting effect is insufficient, and if it exceeds 10 wt%, precipitation of salts or the like tends to be unstable.

The O / W / O type emulsion composition of the present invention can contain an oil component other than the oil component as a component for forming an oil phase. As oil components other than the said oil component, it can mix | blend any form of solid, paste form, or liquid at normal temperature, and can use hydrocarbon type polar oil, nonpolar oil, silicone oil, etc.

In the O / W / O type emulsion composition of the present invention, the ratio of the oil-in-water emulsion composition and the external oil phase forming the oil-in-water phase and the water phase is not particularly limited, but preferably the oil-in-water emulsion composition: external oil phase (weight ratio) = 90 to 0.1: 10 to 99.9, more preferably 80 to 10:20 to 90. If the oil-in-water emulsion composition is less than 0.1% by weight, a practical O / W / O type emulsion composition cannot be obtained. If it is more than 90% by weight, a stable O / W / O type emulsion composition tends not to be obtained.

O / W / O type emulsion composition containing surfactant in the external oil phase of this invention is manufactured by adding the oil-in-water emulsion composition of this invention, for example, stirring the oil phase containing surfactant by hand.

The O / W / O type emulsion composition containing at least one compound selected from the group consisting of inorganic acid salts, organic acid salts, amino acids and salts thereof in the aqueous phase of the present invention is, for example, from the group consisting of fatty acids and higher alcohols. An oil-in-water emulsified composition according to the present invention is prepared by incorporating one or more compounds selected from the group consisting of inorganic acid salts, organic acid salts, amino acids, and salts thereof in an aqueous phase while stirring the oil phase containing one or more selected oil components. It is prepared by adding.

The oil-in-water emulsion composition of the present invention is effectively used as an oil-in-water emulsion composition having good stability over time without containing a surfactant. Moreover, the O / W / O type emulsion composition which contains surfactant in the external oil phase of this invention is used effectively as an O / W / O type emulsion composition with favorable time-lapse stability with few compounding quantities of surfactant. In addition, the O / W / O type emulsion composition of the present invention, which contains at least one compound selected from the group consisting of an inorganic acid salt, an organic acid salt, an amino acid, and a salt thereof in an aqueous phase, has good stability over time without containing a surfactant. It is effectively used as a / W / O type emulsion composition.

The oil-in-water emulsion composition and the O / W / O type emulsion composition of the present invention include, for example, basic cosmetics such as milky lotion and moisturizing cream; Makeup cosmetics such as foundation and rouge; Hair cosmetics; Body cosmetics; Aroma cosmetics; Medicines such as sustained release preparations; food; pesticide; It can be applied to the production of microcapsules.

Examples 1-4 and Comparative Examples 1-2 (oil-in-water emulsion composition)

In Table 1, isostearic acid in phase A corresponds to fatty acids, glyceryl trioctanoate, liquid paraffin, and dimethylpolysiloxane to other components forming an oil phase. Sodium carboxymethyl cellulose, vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer diethyl sulfate in sodium B and sodium polyacrylate are equivalent to ionic polymers and glycerin to polyhydric alcohols. In the C phase, the carboxyvinyl polymer is a water-soluble polymer and the triethanolamine is a neutralizing agent (pH regulator).

The water-in-oil emulsion composition was obtained by gradually adding the B phase uniformized while stirring the A phase of the mixing | blending composition (weight ratio) shown in Table 1 at room temperature. Further, phase C was added while stirring with a homomixer at room temperature to prepare an oil-in-water emulsion composition. The photograph which took the emulsion composition obtained in Example 1 with the optical microscope (VC-1000 by Omron Corporation) was shown in FIG. 1 (magnification: 500x). In Fig. 1, 1 represents an aqueous phase (gray portion), and 2 represents an oil phase (black portion). From FIG. 1, production of an oil-in-water emulsion composition was confirmed.

The stability of the obtained emulsion composition was evaluated according to the following evaluation methods and evaluation criteria.

<Stability evaluation method>

The obtained emulsion composition is filled into a sample bottle, and it is left to stand at 50 degreeC for 1 month, and a state is visually observed.

<Stability evaluation standard>

○: no separation at all

△: Some separation is seen

×: Clear separation is seen

TABLE 1

1) Sodium Carboxymethylcellulose: weight average molecular weight 100,000, etherification degree 0.75

2) Vinylpyrrolidone / N, N-dimethylaminoethylmethacrylate Copolymer Diethyl Sulfate: Average Molecular Weight 100,000

3) Sodium polyacrylate: average molecular weight 500,000

Examples 5 and 6 (O / W / O Type Emulsion Composition)

In Table 2, isostearic acid in phase A corresponds to fatty acids, glyceryl trioctanoate, liquid paraffin, and dimethylpolysiloxane to other components forming an oil phase. Sodium carboxymethylcellulose in phase B is an ionic polymer insoluble in the oil component, and glycerin corresponds to a polyhydric alcohol. In phase C, carboxymethylcellulose sodium is an ionic polymer insoluble in the oil component, xanthan gum is an insoluble polymer, and sodium glutamate corresponds to a salt of an amino acid. In phase D, isostearic acid is a fatty acid, sucrose fatty acid ester is a surfactant, glyceryl trioctanoate, liquid paraffin, and decamethylcyclopentasiloxane are equivalent to other components forming an oil phase.

The water-in-oil emulsion composition was obtained by gradually adding the B phase uniformized, stirring the phase A of the mixing | blending composition (weight ratio) shown in Table 2 with a homomixer at room temperature. Further, phase C was added while stirring with a homomixer at room temperature to obtain an oil-in-water emulsion composition. An O / W / O type emulsion composition was prepared by gradually adding the obtained oil-in-water emulsion composition while stirring by hand on the uniformed D phase. The photograph taken by the electron microscope of the emulsion composition obtained in Example 6 is shown in FIG. 2 (magnification: 1000 times). In Fig. 2, 3 represents an external oil phase, 4 represents an aqueous phase, and 5 represents an oil phase. From FIG. 2, the production | generation of O / W / O type emulsion composition was confirmed.

The stability of the obtained emulsion composition was evaluated according to the said evaluation method and evaluation criteria.

TABLE 2

1) Sodium Carboxymethylcellulose: weight average molecular weight 100,000, etherification degree 0.75

According to the present invention, an oil-in-water emulsion composition excellent in safety and stability over time without using a surfactant by blending at least one oil component selected from the group consisting of fatty acids and higher alcohols and an insoluble ionic polymer in the oil component Can be provided. Moreover, according to this invention, the O / W / O type emulsion composition excellent in safety and aging stability can be provided.

Claims (8)

(1) at least one oil component selected from the group consisting of fatty acids and higher alcohols, and (2) at least one oil component selected from the group consisting of anionic polymers and cationic polymers An oil-in-water emulsified composition comprising an insoluble ionic polymer, and containing no surfactant. The method of claim 1, An oil-in-water emulsion composition in which the ionic polymer insoluble in the oil component is carboxymethyl cellulose sodium or vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer salt. At least one oil component selected from the group consisting of (1) fatty acids and higher alcohols, and (2) at least one selected from the group consisting of anionic polymers and cationic polymers by the phase-phase emulsification method The manufacturing method of the oil-in-water emulsion composition containing the insoluble ionic polymer in the said oil component, and containing no surfactant. The method of claim 3, The said phase-in-phase emulsification method adds a part of the water phase formation component containing the said ionic polymer 2 to the oil phase formation component containing the said oil component (1), and is water-in-oil type | mold A method for producing an oil-in-water emulsified composition, which is a method of producing an oil-in-water emulsified composition by further adding an aqueous phase forming component after producing an oil-in-water emulsified composition. At least one oil component consisting of an oil phase, an aqueous phase and an external oil phase, selected from the group consisting of (1) fatty acids and higher alcohols in the oil phase or aqueous phase, and (2) anions O / W / O type, characterized in that it contains an ionic polymer insoluble in at least one oil component selected from the group consisting of a polymer and a cationic polymer, and does not contain a surfactant in the oil and water phases. Emulsifying composition. The method of claim 5, O / W / O type emulsion composition wherein the ionic polymer insoluble in the oil component is carboxymethyl cellulose sodium or vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer salt. (1) at least one oil component selected from the group consisting of fatty acids and higher alcohols, and (2) at least one oil component selected from the group consisting of anionic polymers and cationic polymers. A method for producing an O / W / O type emulsion composition in which an oil-in-water emulsion composition containing no surfactant is prepared by the phase-in-phase emulsification method, and the resulting oil-in-water emulsion composition is dispersed in an oil phase. The method of claim 7, wherein The above-mentioned phase emulsification method adds a part of the aqueous phase forming component containing the ionic polymer (2) to the oil phase forming component containing the oil component (1) to form a water-in-oil emulsion composition, and then further forms an aqueous phase. A method for producing an O / W / O type emulsion composition, wherein the oil-in-water type emulsion composition is added to components to re-emerge the oil-in-water type emulsion composition.